EPA/600/4-90/010
April 1990
Compendium of Methods for the
Determination of Air Pollutants
in Indoor Air
by
William T. Winberry, Jr., Linda Forehand, Norma T. Murphy,
Angela Ceroli, Barbara Phinney, and Ann Evans
Engineering-Science
One Harrison Park, Suite 305
401 Harrison Oaks Boulevard
Gary, NC 27513
Contract No. 68-04-4467 (V.A. *13)
and
Contract No. 68-02-4396 (V.A. *9 and «2)
EPA Project Managers
Frank F. McElroy and Larry J. Purdue
Quality Assurance Division
and
Charles Rodes
Exposure Assessment Research Division
Atmospheric Research and Exposure Assessment Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
REPRODUCED BY
U.S. DEPARTMENT OF COMMERCE
NATIONAL TECHNICAL INFORMATION SERVICE
SPRINGFIELD, VA. 22161
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EPA/600/4-90/010
April 1990
PART 1 OF 2
Compendium of Methods for the
Determination of Air Pollutants
in Indoor Air
by
William T. Winberry, Jr., Linda Forehand, Norma T. Murphy,
Angela Ceroli, Barbara Phinney, and Ann Evans
Engineering-Science
One Harrison Park, Suite 305
401 Harrison Oaks Boulevard
Gary, NC 27513
Contract No. 68-04^4467 (W.A. *13)
and
Contract No. 68-02-4398 (W.A. M and 132)
EPA Project Managers
Frank F. McElroy and Larry J. Purdue
Quality Assurance Division
and
Charles Rodes
Exposure Assessment Research Division
Atmospheric Research and Exposure Assessment Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
REPRODUCED BY
U.S. DEPARTMENT OF COMMERCE
NATIONAL TECHNICAL INFORMATION SERVICE
SPRINGRELO, VA. 22161
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PART 2 OF 2
Method IP-SB
f DETERMINATION OF NITROGEN DIOXIDE (NO2) IN INDOOR AIR
i! USING PALMES DIFFUSION TUBES
fr
• 1. Scope
2. Applicable Documents
3. Summary of Method
4. Significance
5. Definitions
6. Interferences
7. Apparatus
8. Reagents and Materials
9. Sampling System
9.1 System Description
9.2 Sampling Procedures
10. Analysis
10.1 Reagent Preparation
10.2 Construction Calibration Curve
10.3 Sample Analysis
11. Calculations
12. Performance Criteria and Quality Assurance
12.1 Standard Operating Procedures
12.2 Method Sensitivity, Linearity, and Reproducibility
12.3 Method Bias
12.4 Method Safety
13. Reference
Revised 9/30/89 Page
REPRODUCED BY ,r-r,/sr-
U S DEPARTMENT OF COMMERCE
NATIONAL TECHNICAL
INFORMATION SERVICE
SPRINGFIELD, VA 22161
-------
Method IP-SB
DETERMINATION OF NITROGEN DIOXIDE (NO2) IN INDOOR AIR
USING PALMES DIFFUSION TUBES
1. Scope
1.1 In order to perform sampling and analysis of indoor air pollutants it is necessary to
develop highly sensitive, lightweight and affordable instrumentation. The technology and
methods for sampling and analysis of nitrogen dioxide (NO2) use both passive and active
samplers and an array of analytical systems.
\2 Among the methods for determining NO2 is the Palmes tube (1). This is a passive
sampler which employs sorption for NO2 collection and spectrophotometry for detection.
13 The Palmes tube is based on sorption of NO2 gas onto a surface coated with
triethanolamine. The coated surface is then extracted with a mixture of sulfanilamide
reagent and N-1-napthylethylene-diamine-dihydrochloride (NEDA) reagent.
1.4 The method gives a time-weighted average and can be used for 8 hour as well as week
long sampling periods for personal exposure or area concentrations. This method stands
out as the most sensitive method used at low levels of NO2 around the 0.1 ppm level, but
has some variance at higher levels above approximately 5 ppm.
2. Applicable Documents
2.1 ASTM Standards
D1356 Definitions of Terms Related to Atmospheric Sampling
E275 Recommended Practice for Describing and Measuring Spectrophotometers
22 Other Documents
U.S. Environmental Protection Agency Technical Assistance Document (2) Laboratory
Studies (3-7)
3. Summary of Method
3.1 The Palmes diffusion tube consists of a hollow acrylic tube with one end permanently
sealed and the other equipped with a top which can be removed and replaced. At the
sealed end of the tube are three stainless steel mesh screens previously coated with a
solution of triethanolamine. The diffusion tube has a cross sectional area to length ratio
of 0.1 cm. A typical Palmes Tube is shown in Figure 1.
32 The principle of sample collection is based on Picks First Law of Diffusion. For
analysis, a color reagent is added to the tube, mixed, and allowed time to develop. Within
the period between 20 and 30 min. after the reagent is added, the absorbance of the diazo
coupling of the NO2 and N-1-napthylethylene-diamine dihydrochloride (NEDA) in the color
reagent is measured spectrophotometrically at 540 nm. The concentration of NO2 in the
Revised 9/30/89 Page 3
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Method IP-SB Nitrogen Dioxide
sampled atmosphere is calculated from the nanomoles of nitrite measured, the exposure
time, the diffusion coefficient of NO2 through air, and the sampler's diffusion characteristics.
3.3 To commence sampling, the end of the tube is opened. Air is free to flow through the
tube to the absorbent on the interior screens. When the collection period is through, the
tube is recapped and stored until analysis is performed.
3.4 For analysis, a color reagent is added to the tube, mixed, and allowed time to develop.
Within the period between 20 and 30 minutes after the reagent is added, the absorbance
of the diazo coupling of the NO2 and N-1-napthylethylene-diamine-dihydrochloride (NEDA)
in the color reagent is measure spectrophotometrically at 540 nm. The concentration of
NO2 in the sampled atmosphere is calculated form the nanomoles of nitrite measure, the
exposure time, the diffusion coefficient of NO2 through air, and the sampler's diffusion
characteristics.
3.5 This standard may involve hazardous materials, operations, and equipment. This does
not purport to address all of the safety problems associated with its use. It is the
responsibility of whoever uses this standard to consult and establish appropriate safety and
health practices and determine the applicability of regulatory limitation prior to use.
4. Significance
4.1 Personal exposure to indoor air pollutants is becoming more of an industrial concern
with the formation of OSHA and other groups, but indoor air pollutants have become a
general public concern as well. Of particular concern are domestic and non-industrial areas
such as homes, public offices, theaters, etc. where many air pollutants have been found in
excess of ambient levels. So, it has become imperative to have personal and indoor
sampling devices to accurately measure indoor public, industrial and domestic areas for air
pollutants.
42 Nitrogen dioxide is a reactive gas product of combustion. Household combustion
sources include gas stoves, gas heating, wood burning stoves, furnaces and fireplaces.
Indoors, NO2 may result form infiltration of outdoor air containing NO2, use of combustion
appliances, and from processes involving nitric acid, nitrates, use of explosives, and welding
in industrial workplace environments.
4 J Concentrations as low as five parts per million (ppm) can cause respiratory distress;
approximately 50 ppm can cause chronic lung disease and above 150 ppm is lethal.
4.4 Historically, NO2 has been determined by colorimetric methods and chemiluminescence
methods using catalytic oxidation which converts the NO2 to NO. In turn, NO reacts with
ozone and causes measurable cherniluminescence. Consequently, NO interferes with the
NO2 analysis.
Revised 9/30/89 Page 4
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Method IP-SB Nitrogen Dioxide
5. Definitions
Definitions used in this document and any user prepared SOPs should be consistent with
ASTM D1356. All abbreviations and symbols are defined with this document at the point
of use.
5.1 Absorbent - material on which absorption occurs.
52 Spectrophotometry - a method for identifying substances by determining their
concentration by measuring light transmittance in different parts of the spectrum.
5.3 Molecular diffusion - a process of spontaneous intermixing of different substances,
attributable to molecular motion and tending to produce uniformity of concentration.
5.4 Colorimetry - the science of color measurement (Spectrophotometry).
5.5 Transmittance - that fraction of the incident light of a given wavelength which is not
reflected or absorbed, but passes through a substance.
6. Interferences
6.1 Sampling times under 15 minutes when NO2 level is 0.5 ppm or lower.
62 At levels of NO2 above 5 ppm precision of the method decreases.
63 Temperatures that vary from 70°F will effect the theoretical calculated value of the
diffusion coefficient, thereby effecting the calculated quantity of NO2 gas transferred from
the air to the TEA substrate, as illustrated by the following equation:
D « T3'2/?
where:
D = diffusion coefficient, cm2/s
T = absolute temperature, °K
P = atmospheric pressure, mm Hg
The diffusion coefficient (D) changes proportionately to T372, and P changes inversely
proportionately to T. Overall, P then is proportional to the square root of T.
Note: Studies show that a 1% per 10°F over or below 70°F correction factor can be used
for temperature changes during sampling. For most applications no adjustment is needed.
6.4 Collection efficiency of NO2 by the diffusion tube is affected by temperature.
Triethanolamine has a liquid-solid phase transition at 21°C. In laboratory tests, collection
efficiency was found to decrease by 15% when the temperature decreased from 27°C to
15°C (4). If the temperature history is known for the exposure period, correction factors
may be applied (4).
6.5 Collection efficiency of NO2 by the diffusion tube is affected by humidity. Collection
efficiency decreased by approximately 20% in controlled tests when humidity was decreased
Revised 9/30/89 Page 5
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Method IP-SB Nitrogen Dioxide
from 85% to 5% (5). If the humidity history is known for the exposure period, correction
factors may be applied (5).
6.6 Collection efficiency of NO2 by the diffusion tube is affected by the air velocity at the
open end of the tube. Collection efficiency increases with increasing wind velocity (1). In
controlled tests, collection efficiency increased by an average of 12% when windspeed
increased from 52 to 262 cm/s (1). The diffusion tube will not yield accurate results in an
essentially stagnant atmosphere. Sampler starvation may occur at very low air velocities.
Correction for the theoretical sampling efficiency caused by low face velocity can be applied
using available equations (4,6) if the air velocity history is known for the exposure period.
6.7 Peroxyacetyl nitrate (PAN) and some nitroso compounds may be positive interferences
in this method, but no applicable experimental data exist.
6.8 In very dusty environments, particles may deposit in the samplers and be resuspended
in the analytical reagent, resulting in a positive bias in the spectrophotometric reading.
7. Apparatus
7.1 Palmes sampling tubes - a diffusion device used for collecting NO2 samples. Palmes
tubes and their modification are available from numerous commercial vendors.
12 Spectrophotometer - capable of measuring adsorbance at 540 nm.
73 Volumetric flasks - 100 mL for making combined reagent and standard solutions.
7.4 Pipettes - 50 mL, 5 mL for preparing NEDA reagent and standard solutions.
7.5 Graduated cylinders - 50 mL, 5 mL for preparing NEDA reagent and combined
reagent.
7.6 Tared measuring dishes, best source.
8. Reagents
Note: Reagent-grade chemicals should be used in all tests. Unless otherwise indicated, all
reagents should conform to the specifications of the Committee on Analytical reagents of
the American Chemical Society, where such specifications are available. Other grades may
be used, provided it is first ascertained that the reagent is of sufficiently high purity to
permit its use without lessening the accuracy of the determination.
8.1 Sulfanilamide - reagent grade used to extract NO2 from TEA coated filters, best source.
82 N-1-napthylethylene-diamine-dihydrochloride (NEDA) -reagent grade - used to extract
NO2 from the TEA coated filters, best source.
8.3 Phosphoric acid - concentrated - used in sulfanilamide reagent, best source.
8.4 Water - reagent grade - preparing standard solutions and extract, best source.
Revised 9/30/89 Page 6
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Method IP-SB Nitrogen Dioxide
8.5 NaNO2 - reagent grade used as a source of NO2 in preparing standard solutions, best
source.
9. Sampling System
9.1 System Description
9.1.1 Commercially available tubes
9.1.1.1 The diffusion tube (see Figure 1) consists of commercial acrylic tubing with
outside dimensions of approximately 1.27 cm (0.5 in.) and inside dimensions of 0.95 cm
(0.37 in.) cut to a length of approximately 7.1 cm (2.8 in.) to yield a cross-sectional area (A)
to length (L) ratio of 0.2 cm (0.04 in.). It is permanently sealed on one end and has a
removable cap on the other end. The unsealed end is exposed to the air when the cap is
removed. A Palmes tube is shown in Figure 1.
9.1.12 Inside the tube are three stainless steel wire mesh screens coated with a
substrate of triethanolamine (TEA). These are permanently affixed in the interior of the
tube at the sealed end of the tube. The metal screens are approximately 1.11 cm (0.438 in.)
in diameter 0.025 cm (0.010 in.) wire size, 40 x 40 mesh, 316 stainless steel (approximately
120 mg per three screens).
9.1.1.3 Commercial tubes may be wrapped in a label which serves two functions.
The label is used for identification purposes, and with a clip attached serves as the holder
for the sampling device.
9.1.1.4 The tube should be clipped to an individual clothing when sampling or
individual exposure or appropriately placed in an area to sample indoor environments.
9.1.1.5 The sampler should be situated vertically with the open end down to avoid
moisture or dust from entering the tube.
9.12 User prepared tubes
9.12.1 Acquire commercial acrylic tubing (O.D. 1.27 cm, I.D. 0.95 cm) to an area
to length ratio of 0.2 cm specification from a local vendor.
9.122 Measure the inside diameter and the length of the tubes to determine if the
area-to-length (A/L) are within a tolerance of + 5% of the 0.2 cm specification. If the
tubes are outside these predetermined quality control limits, then the tubing should be recut
or rejected.
9.1.2.3 Clean the acrylic tubes and end closures with TEA-free detergent. Rinse
with tap water three or more times to remove all detergent solution. Rinse a minimum of
three times with reagent water. Dry overnight at temperature below 40°C. Store in sealed
plastic bags or plastic tubs.
9.12.4 Clean screens with detergent solution in ultrasonic bath for 10 minutes.
Rinse with tap water to remove all detergent solution. Rinse once with reagent water.
Immerse screens in 3 N HC1 and allow to stand for 2 hours. Rinse the screens at least
three times with reagent water. Then clean the screens in reagent water in an ultrasonic
bath for 5 minutes. Rinse the screens with reagent water. Dry overnight at 110°C.
Revised 9/30/89 Page 7
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Method IP-SB Nitrogen Dioxide
9.1.2.5 The triethanolamine (TEA) solution used to coat the screens is prepared
by mixing TEA with acetone in a ratio of TEAracetone of 1:7 (v/v). Keep reagent covered
when not in use to minimize contact with air. A fresh solution must be prepared each day
screens are coated.
9.12.6 Prepare an area for drying coated screens by placing several layers of paper
towels on a flat surface.
9.12.1 Pour a portion of the TEA solution into a container that can be capped
when not being used.
9.12.8 Using clean stainless steel or TeflpnR-coated forceps, immerse screens into
the solution in batches of 50 or fewer at one time. As an alternative, screens may be
dipped into the solution individually. (Immersion time is not critical; screens may be
dipped and removed immediately or left immersed indefinitely.)
9.12.9 Remove screens one at a time and place on paper towels to dry. Allow to
dry no fewer than 2 nor more than 5 minutes, to minimize contamination of the screens.
9.12.10 Place three screens into a bottom cap; insert acrylic tube into the bottom
cap; then place top (flanged) cap on the other end for final assembly.
9.12.11 Select approximately 5% of the tubes for analysis as production blanks.
(If absorbance of any of the production blanks exceeds 0.025, additional blanks should be
analyzed. If absorbance of any additional blanks exceed 0.030, the production batch should
be rejected.)
9.12.12 Store assembled diffusion tubes in heat-sealed foil bags or in sealed plastic
bags. Tubes can be stored in well-sealed containers for periods up to 6 months after
preparation and before use and for 6 months after exposure and before analysis.
92 Sampling Procedures
92.1 Take the tube out of its well-sealed container and label properly the start date,
time and sampling location identification.
922 Place the tube in the appropriate area to be sampled.
Note: Representative sampling must be considered, therefore, placement of a sampling
tube should be determined with considerable planning.
923 Appropriate time and placement of the tube should follow the following
guidelines.
92 J.I Avoid sampling when seasonal alterations in insulation or building lightness
are occurring or will occur during the sampling period.
9232 Avoid sampling if remodeling or redecorating is occurring. During the
sampling period there should be no changes in furnishings or appliances such as: carpeting,
stoves, HVAC systems, etc.
9233 Open and close doors in a usual manner and keep windows closed if
possible.
923.4 Ventilation should not be altered in any way during sampling.
923.5 Air conditioning and heating should not be altered from normal use.
923.6 Humidifiers and dehumidifiers should not be used where sampling is being
performed.
Revised 9/30/89 '. Page 8
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Method IP-SB Nitrogen Dioxide
Normal occupancy and activity should continue.
9.2.3.8 The placement of the sampler should not obstruct normal occupancy or
activity.
9.23.9 Avoid locations near sinks, tubs, showers, washers.
9.23.10 Avoid locations near heating elements such as: direct sunlight, furnaces,
electric lights or electrically operated devices.
9J3.11 Avoid locations where a known draft or pressure differential occurs or
areas near furnace vents, HVAC intake/exhaust, compacter cooling fans and appliance fans.
92.4 Placement of the sampler should ideally be at least 8 inches below the ceiling 20
inches above the floor and 6 inches from a wall.
Note: Outside walls should not be used, and suspension from the ceiling may be suitable.
92.5 Remove the cap from the unsealed end of the tube. Sampling commences
immediately.
Note: The sampling tube should be oriented with the open end facing downward to
minimize contamination by particulate matter.
92.6 Re-cap the tube when the sampling time is complete.
92.7 Record the time and date that finishes on the label, and store the tube at room
temperature until analysis is performed.
10. Analysis
10.1 Reagent Preparation
Note: Unless otherwise indicated, references to water shall be understood to mean reagent
water as defined by Type II of ASTM Specification D 1193.
10.1.1 Preparation of sulfanilamide reagents (1%) - combine 10 g sulfanilamide and
25 mL concentrated (85%) H3PO4 in a 1000 mL volumetric flask. Dilute to 1000 mL with
water.
10.L2 Preparation of N-1-napthylethylene-diamine-dihydrochloride (NED A) Reagent
(0.14%) - weigh 70 mg NEDA in a beaker. Dissolve in 50 mL of deionized distilled water.
10.13 Combined reagent preparation - mix 50 mL of the NEDA solution and 1000
mL of the sulfanilamide solution. Check solution for pinkish color or immediately measure
the reagent on the spectrophotometer at 540 nm to verify that the reagent is free of
contamination. If the adsorbance is greater than 0.015 adsorption units, discard the reagent
and prepare a new reagent.
Note: The reagent will be stable for 1 to 2 months if kept well-stoppered in an amber
glass bottle in the refrigerator.
10.1.4 Preparation of sodium nitrite standard stock solution (1.725 g/L) - dissolve
0.1725 g of previously dried and assayed sodium nitrite (NaNO2) in water and make up to
100 mL in a volumetric flask. This solution (25 mM NO2) is used to prepare working
standards.
Revised 9/30/89 Page 9
#5-2.
•' -y
U ?
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Method IP-SBNitrogen Dioxide
10.1.5 Preparation of Working Standards
10.1.5.1 Pipette different volumes of NaNO2 Standard Stock solution into seven 50
mL volumetric flasks.
Note: A good range of standards range from 0 to 40 nanomoles and the following additions
are advised: 0.0 mL, 0.5 mL, 1.0 mL, 1.5 mL, 2.0 niU 3.0 mL, and 4.0 mL.
10.1.52 Bring to the 50-mL mark with deionized distilled water.
102 Construction Calibration Curve
102.1 Add 2.0 mL of the color reagent to each of seven test tubes. Prepare calibration
standards of approximately 0, 5,10, 15, 20,30, and 40 nanomoles of NO2 by adding 20 uL
of the appropriate working standard to the respective labeled tube for the calibration
standard. Vortex briefly.
Note: Prepare calibration standards daily.
1022 Allow color to develop for a period of approximately 10-15 minutes. A water
bath may be used if room temperature cannot be controlled adequately during the analysis
session.
1023 Transfer the solution to a cuvette and read absorbance, not lapsing 20 minutes
from the beginning of color development, at 540 nm after zeroing spectrophotometer with
a reference cell containing reagent water.
102.4 Plot absorbance versus nanomoles of NO2 per tube. The absorbance follows
Beer's Law and the slope should be approximately 40+ nmol per absorbance unit.
Note: Reagent volumes may be adjusted for different curvette sizes; maintain the ratios
of reagent volumes specified above. Automated methods may be used to conduct the
analysis. Ratios of reagent volumes specified above should be maintained.
103 Sample Analysis
103.1 Remove the top (flanged) cap and pipet 2.0 mL of the color reagent directly
into each tube to be analyzed. Re-cap and mix contents of tube well.
1032 Allow 20 to 30 minutes for color development. Volume of the color reagent
should be the same as that used for calibration (see Section 10.1).
1033 Transfer the solution to a curvette and read absorbance at 540 nm in a
spectrophotometer previously zeroed with a reference cell containing reagent water.
103.4 If the absorbance is greater than the 40 nmol calibration standard, dilute the
sample by adding 1.0 mL of the sample to 2.0 mL of color reagent. Mix and allow 20 to
30 minutes for color development. Record the dilution factor.
103.5 If automated methods are used, reagent volumes for analysis should be the same
as those used for calibration.
103.6 For each analytical session, a number of laboratory or field blanks should be
analyzed as prescribed in internal procedures for quality control.
11. Calculations
11.1 In this method the volume of the calibration standards is 2.02 mL (2 mL color reagent
plus 20 pL of working standard, as documented in Section 10) but the volume of the
Revised 9/30/89 "~~~~Pagelo
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Method IP-SB Nitrogen Dioxide
samples is only 2.0 mL (only color reagent). Therefore, to simplify calculations, the
calibration standard concentration is corrected to correspond to the 2.0 mL sample volume
by multiplying by 2.0/2.02 (0.99) to yield nanomoles of NO2 per 2.0 mL. If the standard
stock solution is 25 nmol NO2, the standard concentrations are 0, 4.95, 9.90, 14.85, 19.80,
29.70, and 39.60 nmol NO2. Plot absorbances of the standards against standard
concentrations (nmol NO2).
112 Perform a least-squares linear regression analysis on the date [absorbance (y-axis) vs.
nitrogen dioxide concentration (x-axis)] to derive a standard curve slope, calculated
intercept, and correlation coefficient. Though absolute values are somewhat dependent
upon the specific spectrophotometer used, values and standard deviations similar to
intercept = 0.0158 + 0.0301 slope « 0.0230 + 0.0023, and R squared greater than 0.999
should be obtained.
11 J Calculate the number of nanomoles of nitrogen dioxide collected for each passive
monitor using the standard curve parameters and measured absorbances at 540 nm by the
following equation:
F = (A540 - a)/b
where:
F = nanomoles of nitrogen dioxide eluted into 1.0 mL
A = absorbance of the sample at 540 nm
a = standard curve calculated intercept, AU
b = standard curve slope, AUmL/nanomole
11.4 Calculate the concentration of nitrogen dioxide in the sampled atmosphere as follows:
ppm NO2 = (F - B)/(2.3 x t)
where:
F = NO2 collected, nanomoles
B = NO2 blank, nanomoles
t = exposure time, hours
Note: The concentration of NO2 in the monitored air is computed based on diffusion
coefficient of 0.154 cm2/s (1). When sampled with a tube having a cross-sectional area (A)
to length (L) ratio of exactly 0.1 cm, the following formula is used:
ppb NO2 - (nmol NO2 x 1000)/(23 x thr)
= (435 x nmol NO2)/[(A/L) x thr]
For tubes having an A/L ratio different than 0.1 cm, the following formula should be used:
ppb NO2 = (nmol NO2 x 1000)/[23 x (A/L) x 10 x thr]
= (43.5 x nmol NO2)/[(A/L) x thr]
11.5 To calculate the concentration of NO2 in micrograms per cubic meter at 25°C,
multiply the ppb NO2 by the conversion factor of 1.88 pg/m3/ppb.
Revised 9/30/89 Page 11
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Method IP-SB Nitrogen Dioxide
12. Performance Criteria and Quality Assurance
12.1 Standard Operating Procedures (SOPs)
12.1.1 Users should generate SOPs describing and documenting the following activities
in their laboratory: 1) assembly, calibration, leak check, and operation of the specific
sampling system and equipment used, 2) preparation, storage, shipment, and handling of
samples, 3) assembly, calibration, and operation of the analytical system, addressing the
specific equipment used, 4) sampler storage, and transport 5) all aspects of data recording
and processing, including lists of computer hardware and software used.
12.1.2 SOPs should provide specific stepwise instructions and should be readily
available to, and understood by, the laboratory personnel conducting the work.
122 Method Sensitivity, Linearity, and Reproducibility
12.2.1 Sensitivity - the sensitivity of the method has a limit of detection of 0.1 ppm
(188 0g/m3) for an 8 hour sampling period and 0.005 ppm (9.4 Mg/m3) for a one week
sampling period.
1222 Linearity - the method is linear from 0.005 ppm to 10 ppm and is dependent
upon the dilution used in the analytical scheme.
12.2.3 Reproducibility (Single Analyst) - precision estimates of 1.68 /ig/m3 have been
reported for pairs of diffusion tubes located in outdoor, bedroom, and kitchen locations.
Precision estimates of 1.0 /Jg/m3 for 93 replicate pairs and 132 0g/m3 for 81 replicate pairs
have also been reported for week-long samples in residential dwellings and outdoors (9).
In a laboratory study with exposure periods of 15 minutes to 8 hours (10 to 79,000 ppb.hr),
the coefficient of variation for triplicate tubes ranged form 0.8% to 10% (10). In reported
interlaboratory comparisons, the difference between means for two laboratories was 1.16
jig/m3 or 3.3% for one set of samples and 3.29 /ig/m3 or 6.51% for a second set of samples
(9).
12 3 Method Bias
12.3.1 Bias was evaluated in a laboratory study by exposing diffusion tubes to
concentrations of NO2 of 0.5 ppm, 5 ppm, or 10 ppm for periods of 15 minutes to 8 hours.
1232 The determined recovery with the diffusion tubes differed from that measured
with an NO2 chemiluminescent analyzer by between -13.6% to +16.7% (10). An accuracy
within 10% for preparation and analysis procedures nearly identical to those of this method
has been reported (11-12).
13. References
1. Palmes, E. D., Gunnison, A. F., DiMatto, J., and Tomcyzk, C, "Personal Sampler for
Nitrogen Dioxide," American Industrial Hygiene Association Journal, 46:462-475, 1981
2. Ralph M. Riggin, Technical Assistance Document for Sampling and Analysis of Toxic
Organic Compounds in Ambient Air, EPA - 600/4-83-027, U.S. Environmental Protection
Agency, Research Triangle Park, NC, 1983.
Revised 9/30/89 Page 12
iul^
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Method IP-5C
DETERMINATION OF NITROGEN DIOXIDE (NO2) IN INDOOR
AIR USING PASSIVE SAMPLING DEVICE
1. Scope
2. Applicable Documents
3. Summary of Methods
4. Significance
5. Limitations
6. Apparatus Description
6.1 Sample Collection
6.2 Analytical System
7. Equipment
7.1 Sampling
7.2 Analysis
8. Reagents and Materials
9. Preparation and Application of the Passive Sampling
Device (PSD)
9.1 Filter Preparation
9.2 Filter Treatment
9.3 PSD Assembly
10. Placement of the PSD and Sampling
11. Analysis of PSD
11.1 Sample Preparation
11.2 Preparation of Analytical Reagents
11.2.1 Nitrate Standard Solution
11.2.2 Ion Chromatograph Operating Solutions
11.3 Ion Chromatograph Operation
11.3.1 Start-Up
11.3.2 Analysis
11.3.3 Shut-Down
11.4 Calculations
12. Standard Operating Procedures
13. References
Revised 9/30/89 Page 1
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Method IP-5C
DETERMINATION OF NITROGEN DIOXIDE (NO2) IN INDOOR AIR
USING PASSIVE SAMPLING DEVICE
1. Scope
1.1 In the past, active sampling devices have been the method of choice for collection of
NO2 from indoor air. More specifically, Compendium Method IP-5A uses a real-time,
direct measurement monitor for characterizing NO2 involving the detection of fluorescent
energy emitted from the reaction of NO2 with a Luminol solution (5-amino-2,3-dihydro-
1,4 phthalazine dione). Active sampling systems utilizing a pump have been successfully
used for occupational exposure assessment both inside and outside of the workplace (1,2).
12 As illustrated, real-time, direct measurement monitors are active sampling devices that
require a mechanical pump to move the sample to the collection medium. Consequently,
the sampling devices require some form of power to drive the pump and are usually heavy
and bulky in appearance.
13 In recent years, interest has been increasing in the use of diffusion-based passive
sampling devices (PSDs) for the collection of NO2 in indoor air.
1.4 PSDs are more attractive for indoor air because of their characteristics of small size,
quiet operation (no pump), and low unit cost.
1.5 Real-time monitors have been used more at fixed monitoring stations, thus not always
reflecting the actual concentration of pollutant that people come in contact with in their
daily lives.
1.6 Since the PSD is lighter and smaller than the real-tune monitors, they can be worn
by the person or in close proximity to where people spend most of their time, thus enabling
epidemiologists to better attribute health effects of NO2 to indoor air concentrations.
1.7 Application of the diffusion technique has been successful in monitoring NO2 in indoor
air utilizing the Palmes tube (3). Compendium Method IP-SB has standardized this
sampling approach and variations of the device are commercially available. However, the
Palmes tube lacks the sensitivity needed to obtain 8 to 24 hour tune weighted average
(TWA). With a sampling rate of -1.0 cm3/min, the sensitivity of the Palmes tube is 300
ppbv-hr when spectrophotometrically analyzed. Therefore, to determine a lower level of
NO2, a 5- to 7-day exposure is required.
1.8 To address the need for a 8 to 24 hour TWA PSD, the EPA funded several projects
(4-8) in developing a PSD for monitoring a variety of indoor pollutants.
1.9 Initial studies centered around the application of the PSD to monitoring volatile
organic compounds (VOCs) in indoor air (9-12). Both activated charcoal and Tenax* solid
adsorbents were investigated as possible constituents of the PSD.
1.10 Such problems as sorbent contamination (4), atmospheric humidity (5), air velocity
(6, 5, 10) and reverse sorption (6) were studied extensively in development of the VOC
Revised 9/30/89 Page 3
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Method IP-5C Nitrogen Dioxide
PSD. A commercial version of the VOC PSD has subsequently become available (Scientific
Instrumentation Specialists, Moscow, ID).
1.11 In the commercial version, a granular sorbent (activated carbon, Tenax®) was used
to collect the compounds of interest from air. To address the application of monitoring
NO2 in indoor air, a modification of the VOC PSD was evaluated (13) by replacing the
granular sorbent with filter paper treated with specific reagent to trap NO2.
2. Applicable Documents
2.1 ASTM Standards
D 1356 Standard Definitions of Terms Relating to Atmospheric Sampling and Analysis
D 3609 Standard Practice for Calibration Techniques Using Permeation Tubes
D 1357 Practice for Planning the Sampling of the Ambient Atmosphere
D 1605 Recommended Practices for Sampling Atmospheres for Analysis of Gases and
Vapors
22 Other Documents
Existing Procedures (14-16)
US EPA Technical Assistance Document (17)
3. Summary
3.1 The passive sampling method involves placing triethanolamine-coated glass fiber filters
behind sets of diffusion barriers on each side of a containment cavity of a PSD and locating
the PSD hi the sampling area.
3 2 NO2 hi the indoor air specifically reacts with the triethanolamine-coated glass fiber
filters according to Pick's First Law of Diffusion.
M = EKA/LXQ. - c0)
where:
M = mass flow, cm3/min
D = diffusion coefficient, cm2/min
A = cross sectional area of diffusion channel, cm2
L = length of diffusion channel, cm
Q, = concentration of NO2 in surrounding PSD
C0 = concentration of NO2 at surface of treated filter (generally zero)
3.3 After sampling is complete, the PSD sampler is capped, returned to the laboratory,
dissembled, extracted with 10 mL of distilled-deionized water and analyzed by ion
chromatography.
3.4 Evaluation of the NO2 PSD sampler utilizing an exposure chamber found it to be
linear from 10.6 ppb (-20 /Jg/m3) to 244.8 ppb (-460 pg/m3) while sensing standard gas
test atmospheres (14). Correlation coefficient was 0.9955 over this range. Under these
Revised 9/30/89 Page 4
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Method IP-5C _ Nitrogen Dioxide
test conditions, it was found that 91 0g/m3 of nitric oxide and a relative humidity of 57%
had no deleterious effect on the efficiency of the PSD.
3.5 The use of triethanolamine-coated glass fiber filters as part of a PSD sampler coupled
with ion chromatography analysis has a minimum detectable quantity (MDQ) of 30 ppb-
hr for an 8 to 24 hour time weighted average.
4. Significance
4.1 The monitoring of NO2 at sub-ppm and low-ppb levels is of primary concern in indoor,
nonindustrial locations such as the home. The trends toward much more airtight homes
which began during the energy crisis of the early 1970s has caused concern among health
experts about increase levels of NO2 indoors.
42 Nitrogen dioxide is a combustion product found in houses mostly due to gas or wood
burning stoves, heaters and/or fireplaces. Hazardous concentrations can occur in closed
environments such as kitchens and family rooms where ventilation is minimal.
4.3 Most health effects associated with nitrogen oxides (NOX) have been attributed to
nitrogen dioxide (NO2). Levels of NO2 above 282 mg/m3 (150 ppm) can be lethal while
concentrations in the range of 94-282 mg/m3 (50-150 ppm) can produce chronic lung
disease (18). The earliest response to NO2 occurs in the sense organs. Odor can be
perceived at 0.23 mg/m3 (0.12 ppm) and reversible changes in dark adaptation at exposures
of 0.14 - 0.50 mg/nr (0.075 - 0.26 ppm) (19). Animal studies have suggested that reduced
resistance to respiratory infection is the most sensitive indicator of respiratory damage.
Recent studies show a small but apparently higher incidence of respiratory symptoms and
disease for children living with gas stoves (an NOX source) versus those in homes with
electric stoves. When indoor concentrations were measured, the levels were much lower
than were previously thought to contribute to lung function changes or disease effect.
These effects were not observed in adults living in the same or similar environments.
5. Limitations
5.1 The effects of indoor temperature and pressure fluctuations on the diffusion coefficient
or sampling rate of a PSD may be estimated from the equation:
D
where:
D = diffusion coefficient, cm2/min
T = absolute temperature, °K, and
P = atmospheric pressure, mm Hg
The theoretical temperature coefficient was found to be -0.6% per °C and the pressure
coefficient -0.1% per mm Hg.
Revised 9/30/89 Page 5
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Method IP-5C Nitrogen Dioxide
52 Humidity effects are less predictable, but may be pronounced for hydrophilic collectors *
or sorbents. During evaluation (13) of the EPA PSD, no interferences were observed at T
57% and 80% relative humidity.
5.3 Sampling rates are affected by the velocity of air movement over the face of the device,
particularly if there are protrusions around the channel openings or if one side of a two-
sided badge is obstructed. Protrusions can contribute to the formation of secondary layers
of stagnant air, which reduces the uptake rates. For chemicals that are weakly sorbed,
significant equilibrium vapor pressures may exist at the face of the sorbent, which effectively
reduce sampling rates according to Pick's law (i.e., C0 > O). Theoretical predictions
suggest that the magnitude of this decrease will depend on air concentrations. Since most
passive samplers have relatively large time constants and since the rates of migration into
the sorbent bed are slow compared to the time constant, diffusional samplers may not
respond accurately to rapidly fluctuating air concentrations. However, such fluctuations are
not usually characteristic of pollutant levels in indoor air.
6. Apparatus Description
6.1 Passive Sampling Device (PSD)
6.1.1 Passive air monitors may be either permeation or diffusion controlled. In
operation, a collector or sorbent material is separated from the external environment by
a physical barrier that determines the sampling characteristics of the device.
6.1.2 Permeation-limited devices employ a membrane in which the test compounds
are soluble. Because of this solubility requirement, it is possible to achieve some selectivity
with permeation devices by choice of the membrane material.
6.13 With diffusion-limited devices (see Figure 1), the collector is isolated from the
environment by a porous barrier containing a well defined series of channels or pores.
The purpose of these channels is to provide a geometrically well-defined zone of essentially
quiescent space through which mass transport is achieved solely by diffusion.
6.1.4 As a general criterion for this condition, the length/diameter ratio (L/d) of the
pores should be at least three. Under such conditions, the mass flow rate to the collector
is given by Pick's first law.
M = D(A/L)(C. - C0)
where:
M = mass flow, cm3/min
D = diffusion coefficient, cm2/min
A = cross sectional area of diffusion channel, cm2 v
L = length of diffusion channel, cm
Ca = concentration of NO2 in surrounding PSD
C0 = concentration of NO2 at surface of treated filter (generally zero)
The component D(A/L) is in units of volume/time or sampling rate.
Revised 9/30/89 Page 6
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Method IP-5C Nitrogen Dioxide
6.1.5 For most commercial diffusion-controlled devices, the effective sampling rate
varies from 1 to 150 cm3/min depending on the molecular species. Pump-based personal
monitors may sample at rates up to 8,000 cm3/min. Consequently, longer exposure times
are often required for passive monitors in order to achieve equivalent sensitivities to pump-
based personal monitors.
6.1.6 Figure 2 illustrates an exploded view of the current design of the EPA PSD.
6.1.7 Using the current design of the EPA PSD, the effective sampling rate of the EPA
PSD was calculated from Pick's First Law of Diffusion to be 154 cm3/min.
62 Analytical System
62.1 Ion chromatography (1C) is a technique which employs ion exchange, eluent
suppression, and conductometric detection to quantify levels of strong acid anions such as
sulfate, nitrate and chloride.
622 The basic components of a commercially available ion chromatographic instrument
are illustrated in Figure 3. The instrument uses three (3) columns to protect, separate and
detect the anions. In operation, the sample first enters the guard column which is used
primarily to protect the main analytical column. The guard column filters paniculate
matter from the eluent and prevents poisoning by strongly present ions of the analytical
column.
623 The sample stream now enters the analytical column which provides high
efficiency separation of anions through competition of the anions and the eluent (0.0018
M Na2CO3 and 0.0017 M NaHCO3) for active sites on the column. The degree of species
separation and retention time depends on the relative affinities of different ions for the
active sites, eluent strength and eluent flow rate.
62A After separation the eluent plus sample stream passes through a suppressor
column which converts the eluent from a high conductivity form to a low conductivity form
(H2C03).
62.5 The anions of strong acids remain dissociated and are detected by means of their
electrical conductivity.
6.2.6 The basic components of the 1C with supporting reagents are:
• Guard Column HPIC AG4A
• Analytical Column HPIC AS4A
• Suppressor Column AMMSI Anion micro membrane
. Eluent 0.0018 M NaCO3
0.0017 M NH3CO3
• Regenerant 0.025 M H2SO4
7. Equipment
7.1 Sampling
7.1.1 Passive sampling device (PSD) - Scientific Instrumentation Specialists, P.O. Box
8941, Moscow, ID, 83843.
Revised 9/30/89 Page 7
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Method IP-5C Nitrogen Dioxide
7.12 Glass fiber filters - 37 mm, Whatman GF/B Glass Microfibre, Whatman Inc., 9
Bridgewell Place, Clifton, NJ, 07014, 800-922-0361.
12 Analysis
72.1 The Dionex Model 14 or Model 4000 may be used for this procedure. The
procedure addresses the use of the Model 14. The master components of this system are
listed below.
72.1.1 Guard column - 3 x 150 mm anion column which serves to guard the
separator column from reactive ions and paniculate matter. Guard columns are used
primarily to protect analytical columns. The guard column is normally a shorter version
of the analytical column. It filters paniculate matter from the eluent and the sample
aliquot. In addition, strongly retained ions which could lead to "poisoning" of the analytical
column are trapped within the guard column.
Note: Guard columns have a finite lifetime and when expended, the contaminants will
reach the more critical analytical column. There are no general rules for estimating the
effective life of a guard column since the life is very dependent upon the matrix being
injected. However, they need to be cleaned or replaced on a periodic basis.
7 2.1 2 Analytical column - 3 x 250 mm anion column (HPIC AS4A) containing the
resin on which the ion separation occurs. The analytical column is the heart of ion
chromatography (1C). In all cases, the 1C separation is due to difference in the equilibrium
distribution of sample component between the mobile phase and the analytical column
(stationary phase). High performance Ion Chromatography (HPIC) involves the use of low
capacity pellicular ion exchange materials in a separation mode dominated by ion exchange.
The ion exchange material is a resin base consisted of polystyrene.
72.13 Micromembrane suppressor column - column (AMMSI) containing a resin
which converts anions to their hydrogen forms. This column has limited capacity and must
be frequently refreshed with a regeneration process. The most popular mode of detection
in 1C is conductivity. However, the conductivity of the eluent used in 1C is usually high.
Therefore, a micromembrane suppressor column is used to chemically suppress (lower) the
eluent prior to detection by conductivity. The suppressor column is a micromembrane fiber
device that is placed downstream of the analytical column (see Figure 3). The suppressor
column (anion exchange technique) changes the concentration of highly conductive eluent
ions (carbonate) to species which are significantly less conductive (carbonic acid). In
addition, solute ions are converted to their corresponding acids or hydroxides as they pass
through the suppressor column, which are more conductive.
Note: As with the guard column, the micromembrane suppressor column can be
periodically regenerated with 0.025 N H2SO4.
72.1.4 Conductivity cell - a 6 microliter volume cell in which the electrical
conductivity of the eluent stream is measured.
72.1.5 Pumps - Milton Roy positive displacement pumps are used to pump the
required liquids at pressures up to about 1000 psi. Flow rates are continuously adjustable
from 0 to 400 mL/hour.
Revised 9/30/89 Page 8
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Method IP-5C ^ Nitrogen Dioxide
- 122 Valve system - a complex array of air-actuated valves controls the liquid flow
| through the system. Valves and columns are interconnected with Teflon* tubing (1/32
inch i.d. by 1/16 inch o.d.).
72.3 Integrator - a Hewlett-Packard Model 3385A Integrator or similar instrument is
used to produce a strip chart recording of the chromatogram and may also be used to
measure the areas under specified peaks of the chromatogram. This system also generates
valve switching signals for automatic control of the ion chromatograph.
7.2.4 Pressurized air system - a continuous supply of 80 psi compressed air is required
for valve actuation. Either a house air supply or compressed air cylinders with regulators
may be used.
8. Reagents and Materials
8.1 Triethanolamine (TEA) - absorbing solution (1.68 M) used to coat filters used in the
EPA PSD, best source.
$2 Glove box - used to provide preparation area to assemble and disassemble PSDs, best
source.
83 Nitrogen - used to condition glove box during filter preparation and PSD
assembly/disassembly, NO2 free, best source.
8.4 Syringes - used to apply TEA to filters, best source.
8.5 Plastic Petri dishes or watch glasses - used to contain filters during TEA application,
best source.
8.6 Metal cans - used to transport PSDs, 0.5 pt and 1.0 gallon, best source
8.7 Activated charcoal - used to place in bottom of 1.0 gallon metal can to protect PSDs
during transport, best source.
8.8 Gelman Acrodisc® - used to filter extracted PSD solution prior to injection into the
ion chromatograph, Gelman Sciences, 600 S. Wagner Rd., Ann Arbor, MI 48106 (800-
521-1520).
8.9 Sodium carbonate (0.0018 M) - used as part of the 1C eluent, best source.
8.10 Ammonium bicarbonate (0.0017 M) - used as part of the 1C eluent, best source.
8.11 Sulfuric acid (0.025 M) - used to regenerate 1C columns, best source.
8.12 Guard column - used to protect analytical column from poisoning and paniculate
matter, Dionex Corporation, 1228 Titan Way, Sunnyvale, CA 94086, (408-737-0700), Model
HPIC AG4A.
8.13 Analytical column - used to separate ions from the eluent, Dionex Corporation, 1228
Titan Way, Sunnyvale, CA 94086, (408-737-0700), Model HPIC AS4A.
Revised 9/30/89 Page 9
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Method IP-5C Nitrogen Dioxide
8.14 Micromembrane suppressor column - used to chemically suppress the eluent prior
to detection by conductivity.
8.15 Calcium sulfate - used in the desiccator during drying of filters, best source.
8.16 Desiccator - used to store filters prior to application of TEA, best source.
8.17 Vacuum oven - used to dry filters during preparation, best source.
8.18 35 mL screen-capped polpropylene bottle - used to extract exposed filters with
deionized water.
8.19 Sonification bath - used to assist in the filter extraction process, best source.
8.20 Potassium nitrate - used to prepare calibration standards, best source.
821 Volumetric flasks (100, 200 and 1000 mL) - used to prepare calibration standards.
822 Pipettes (1, 2, 3, 4, 5, 10, 20 mL) - used to prepare calibration standards.
9. Preparation and Application of the Personal Sampling Device
9.1 Filter Preparation
9.1.1 Unpack the 37 mm filters from their shipping container. Insure that the filters
are separated without tearing.
9.12 Observe filter construction to note any tears or holes in the material or soiling
and abrasions.
9.13 Place the filters on a piece of cardboard. Using a wooden mallet and a 33 mm
circular diameter stainless steel die, cut the number of filters needed for completion of
the project objectives.
9.1.4 To prepare the filters for treatment, place five at a time in a Buchner funnel and
rinse with five 100 mL volumes of charcoal-filtered deionized water.
9.1.5 Remove the filters from the funnel and place in a vacuum oven at 60°C for 1
hour.
9.1.6 After drying, remove the filters from the oven and store in a desiccator containing
anhydrous calcium sulfate until cooled to room temperature.
92 Filter Treatment
92.1 Remove five clean filters from the desiccator and place on a watch glass in a
glove box under a nitrogen atmosphere.
922 Using a syringe, add 0.5 mL of 1.68 M solution of TEA in acetone to the center
of each filter and allow it to disperse.
92 J Allow to equilibrate in the nitrogen atmosphere for -80 minutes. This will allow
the solution to diffuse completely throughout the filter.
Note: One may need to apply solution to the edges of the filter to insure complete
application.
Revised 9/30/89 Page 10
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1
Method IP-5C Nitrogen Dioxide
9.3 PSD Assembly
93.1 The PSD is a dual-faced sampler made up from a series of diffusion barriers
placed on either side of a cavity, as illustrated in Figure 2. The PSD is 3.8 cm in diameter,
1.2 cm in depth and weighs 36 grams.
9.32 With the aid of a glove box under a nitrogen blanket, remove the treated TEA
filter papers from the watch glass and place behind each set of the diffusion barriers of
the PSD.
933 Reassemble the PSD, attach the protective caps and place in small (0.5 pt) can
while still in the glove box. For further protection from exposure, place the small cans
into a large (1 gal) can containing activated charcoal when removing from glove box for
field application.
10. Placement of the PSD
10.1 Take the PSD out of its protective shipping can and complete Field Test Data Sheet
(see Figure 4) with the start date, time and sampling location identification.
10.2 Place the PSD in the appropriate area to be sampled.
Note: Representative sampling must be considered, therefore, placement of a PSD should
be determined with considerable planning.
103 Guidelines for the appropriate time and placement of passive monitors are found
below and in Appendix C-3 of this Compendium.
103.1 Avoid sampling when seasonal alterations in insulation or building tightness are
occurring or will occur during the sampling period.
1032 Avoid sampling if remodeling or redecorating is occurring. During the sampling
period there should be no changes in furnishings or appliances such as: carpeting, stoves,
HVAC systems, etc.
1033 Open and close doors in a usual manner and keep windows closed if possible.
103.4 Ventilation should not be altered in any way during sampling.
103.5 Air conditioning and heating should not be altered from normal use.
10.3.6 Humidifiers and dehumidifiers should not be used where sampling is being
performed.
103.7 Normal occupancy and activity should continue.
103.8 The placement of the sampler should not obstruct normal occupancy or activity.
103.9 Avoid locations near sinks, tubs, showers,and washers.
103.10 Avoid locations near heating elements such as: direct sunlight, furnaces, electric
lights or electrically operated devices.
103.11 Avoid locations where a known draft or pressure differential occurs or areas
near furnace vents, HVAC intake/exhaust, computer cooling fans and appliance fans.
10.4 Placement of the PSD should ideally be at least 8 inches below the ceiling, 20 inches
above the floor and 6 inches from a wall.
Note: Outside walls should not be used, and suspension from the ceiling may be suitable.
Revised 9/30/89 Page 11
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Method IP-5C Nitrogen Dioxide
10.5 Remove the protective caps from the PSD. Sampling commences immediately. Place
samples at predetermined location.
10.6 Complete information on the Field Test Data Sheet (see Figure 4).
10.7 Recap the PSD when the sampling time is complete.
10.8 Record the tune and date that sampling finishes on the Field Test Data Sheet and
store the PSD in the 0.5 pt can which will be stored in the larger can containing activated
charcoal until analysis.
11. Analysis of PSD
11.1 Sample Preparation
11.1.1 After exposure, the PSDs are returned to the lab hi the large cans containing
activated charcoal. Remove the small returned (0.5 pt) can from the larger paint can.
Log sample I.D. into laboratory notebook.
11.12 Under a nitrogen blanket in a glove box, remove the PSD from the smaller can
and disassemble the filter cassette.
11.13 Place the exposed filters in a 35 mL screw-capped polypropylene bottle.
11.1.4 Add 10 mL of deionized water to the bottle, tightly cap and place in a
Bonification bath at room temperature for 30 minutes.
11.1.5 At the end of 30 minutes, remove the polypropylene bottle from the sonification
bath. Filter the anion extract through a Gelman Acrodisc* disposable filter assembly by
attaching the Acrodisc* to the 1C syringe and drawing the solution through the Acrodisc*
into the cavity of the syringe.
Note: The use of the Acrodisc* removes extraneous fibers from the anion solution as a
result of the filter.
Preparation of Analytical Reagents
Nitrate Standard Solutions
112.1.1 Nitrate Stock Standard, 1000 mg/L - dry a few grams of ACS reagent grade
crystals in an air oven at 100°C for 1 hour. Store the dried crystals in a desiccator over
silica gel until use. Dissolve 1.629 gm of dry sodium nitrate in about 600 mL of distilled
water. Dilute to 1 liter and mix thoroughly.
112.12 Nitrate Intermediate Standards, 100 mg/L - make a 100 mg/L standard
solution by pipetting 10.0 mL of the nitrate stock standard into a 100 mL volumetric flask.
Dilute to volume with distilled water and mix thoroughly. Keep refrigerated. Stable for
1 month.
112.13 Working Standards - prepare the working standard by pipetting aliquots of
the nitrate intermediate standards into each 100 mL volumetric flask, according to the
following table:
Revised 9/30/89 Page 12
-------
Method IP-5C
Nitrogen Dioxide
SM
A
B
C
D
E
F
G
H
Std fug/mL)
100
100
100
100
100
100
100
100
Aliquot
25.0
20.0
15.0
10.0
5.0
3.0
1.5
0.5
Cone (ug/mL)
25.0
20.0
15.0
10.0*
5.0*
3.0*
1.5*
0.5*
Flask
Cone (ug/mL)
0.25
0.20
0.15
0.10
0.05
0.03
0.015
0.005
•Normal Working Range
Mix thoroughly. Prepare daily and keep refrigerated.
1122 Ion Chromatograph Operating Solutions
The following produces the 1C eluent. Preparation of these solutions need only be accurate
to several percent:
• Sodium carbonate solution - Prepare 0.0018 M sodium carbonate solution by dissolving
0.7631 g into 4 liters of deionized water. Mix thoroughly.
• Ammonium bicarbonate solution - Prepare 0.0017 M ammonium bicarbonate by
dissolving 0.5712 g into 4 liters of deionized water. Mix thoroughly.
• Regenerant solution - Prepare the regenerant solution by adding 3 mL of concentrated
H2SO4 to 4 liters of deionized water. Mix thoroughly.
113 Ion Chromatograph Operation
The following procedures address the Dionex Model 14 ion chromatographic system.
113.1 Start-up
11.3.1.1 Ascertain that there are sufficient levels of eluent, regenerate and deionized
water in the 1C reservoirs. Refill if necessary.
11 3.12 If not already on, turn on main power to 1C If the red "Ready" lamp does
not glow, depress the red "Reset" button.
113.13 Flip toggle switch on front panel for pump 1 to "On". The pressure gauge
should indicate 50 psi or higher. If not, the pump has probably lost prime and the following
procedure should apply: Slide pump tray out; with 3/8 inch wrench, loosen the stainless
steel fitting for the exit side of the eluent pump (upper fitting). Allow the pump to run
until only fluid is being pumped (no escaping air bubbles). Retighten the fitting.
113.1.4 Flip toggle switch to Eluent 1 position.
113.1.5 Switch "Analyt" and "Suppress" toggle up respectively.
113.1.6 Allow approximately 30 minutes for system equilibration.
113.1.7 Check all column and valve fittings for leaks.
113.1.8 Turn Mode switch for the detector to "Lin" position and select the proper
operating range for the detector - 3 is the usual position.
Revised 9/30/89
Page 13
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Method IP-5C Nitrogen Dioxide
113.1.9 Using the offset adjustments, adjust the specific conductance to
approximately 0.1 on the linear scale. This allows for some baseline drift downward during
the course of analysis.
11.3.2 Analysis
Note: Samples may be injected either automatically with the autosampler or manually.
1132.1 Analysis preparation - prepare working standards in a range to bracket the
sample concentration expected. Include extraction blanks, quality control samples and
replicate standards.
11322 For the Model 14 Autosampler, use clean disposable 13 x 100 mm test
tubes to contain the unknowns. Prepare a list which sequentially lists the unknown samples
and quality control solutions which will be analyzed. A suggested "Run Sequence" is
outlined below. Load the autosampler tray with the samples in sequence. Enter an
identification number on the HP 3385 strip chart recording and press "Start Run". As
analysis proceeds, label the chromatogram according to the sequence.
Test Tube
Number Sample Type
1 D.I. Water
2-7 Six Calibrants from High to Low
8 Extraction Blank
9 External Standard (High)
10 External Standard (Low)
11-30 20 Filter Samples
31 Internal Standard (Medium)
32-52 20 Filter Samples
53-58 Repeat Six Calibrants High to Low
59 Repeat of Extraction Blank
60 Internal Standard (Medium)
61 Internal Standard (Low)
11323 For a manual injection draw 5 mL of the desired solution through the
Acrodisc* into a 5 mL disposable pipet. Remove air bubbles from the syringe by lightly
tapping with the tip pointed upward. Push the plunger in until liquid starts to run out.
Attach syringe to injection port. Set Inject/Load toggle to the Load position and inject the
aliquot. Enter the ID number in the Hewlett-Packard and press "Start Run". After 45
seconds, move the Inject/Load toggle back to the Load position.
1133.4 Figure 5 illustrates a typical Dionex Model 14 chromatogram.
1133 Shutdown
1133.1 Turn "Pumps" switch to OFF.
11332 Turn "Analyt" toggle switch. Turn Suppressor/Bypass/Rgn to Bypass/Rgn
(Suppress down on Model 14) down.
Revised 9/30/89 Page 14
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Method IP-5C Nitrogen Dioxide
a
111.3.3.3 Ascertain that there is a 3:1 rinse ratio programmed into the regeneration
program, e.g., 30 minutes regenerate and 90 minutes rinse.
11.3.3.4 Turn detector to "Zero" position.
fc 11.3.3.5 Push button for regeneration.
11.4 Calculation
11.4.1 Peak Height Measurement
11.4.1.1 An engineer's fully divided scale (using the 50 scale) is used for
measurement of peak heights and drawing of baselines. Measured peak heights should
be indicated on the strip chart recording.
11.4.1.2 Sample concentrations may be calculated on the basis of the following
formula:
Sample concentration = sample peak ht. x calibration concentration/calibration peak ht.
Example: A 10.0 neq/mL sulfate standard gave a peak height of 42 units. An unknown
had a peak height of 37 units. The concentration of the unknown was:
37 x (10 neq/mL)/42 = 8.8 neq/mL
11.4.2 Sample Analysis by Area Measurement
11.4.2.1 The Hewlett-Packard Integrator calculates the area under specified peaks.
11.4.2.2 Unknown concentrations are determined by comparing the peak area to
that of a standard.
Sample concentration = sample area x calibration concentration/calibration area
12. Standard Operating Procedures (SOPs)
12.1 Users should generate SOPs describing and documenting the following activities in
their laboratory: 1) assembly, calibration, leak check, and operation of the specific sampling
system and equipment used, 2) preparation, storage, shipment, and handling of samples, 3)
assembly, calibration, and operation of the analytical system, addressing the specific
equipment used, 4) sampler storage and transport, and 5) all aspects of data recording and
processing, including lists of computer hardware and software used.
12.2 SOPs should provide specific stepwise instructions and should be readily available to,
and understood by, the laboratory personnel conducting the work.
13. References
1. Wallace, L. A., and Ott, W. R., Personal Monitors: A State-of-the-Art Survey, J. Air
Pollution Control Assoc., 32:601, 1982.
2. Callis, C. F., and Firth, J. G., Detection and Measurement of Hazardous Gases, Eds.
Heinemann, London (1981).
Revised 9/30/89 Page 15
U
-------
Method IP-5C Nitrogen Dioxide
3. Palmes, E. O., Gunnison, A. F., DiMattio, J., and Tomczyn, G, "Personal Sampler for
Nitrogen Dioxide," Amer. Ind. Hyg. Assoc., 37:510, 1976.
4. Coutant, R. W., and Scott, D. R., "Applicability of Passive Dosimeters for Ambient Air
Monitoring of Toxic Organic Compounds," Environ. ScL Tech., 16:410, 1982.
5. Lewis, R. G., Coutant, R. W., Woolen, G. W., McMillin, C. R., and Mulik, J. D.,
"Applicability of Passive Monitoring Device to Measurement of Volatile Organic Chemicals
in Ambient Air," 1983 Spring National Meeting, American Institute of Chemical Engineers).
6. Lewis, R. G., Mulik, J. D., Coutant, R. W., Wooten, G. W., and McMillin, C. R.,
"Thermally Desorbable Passive Sampling Device for Volatile Organic Chemicals in Air,"
Anal Chem., 57:214, 1985.
7. Coutant, R. W., Lewis, R. G., and Mulik, J. D., "Passive Sampling Devices with
Reversible Adsorption," Anal Chem., 57:219-223, 1985.
8. Miller, M. P., Analysis of Nitrite in NOZ Diffusion Tubes Using Ion Chromatography, U.S.
Environmental Protection Agency, EPA 600/2-87-000, Research Triangle Park, NC, 1987.
9. Coutant, R. W., and Scott, D. R., "Applicability of Passive Dosimeters for Ambient Air
Monitoring of Toxic Organic Compounds," Environ. ScL Tech., 16:410, 1982.
10. Walling, J. F., "The Utility of Distributed Air Volume Sets When Sampling Ambient
Air Using Solid Adsorbents," Atmos. Environ., 18:855-859, 1984.
11. McClenny, W. A., Lumpkin, T. A., Pleil, J. D., Oliver, K. D., Bubacz, D. R., Faircloth,
J. W., and Daniels, W. H., "Canister Based VOC Samplers," Proceedings of the 1986
EPA/APCA Symposium on Measurement of Toxic Air Pollutants, pp. 402-407, Air Pollution
Control Association Publication VIP-7, U.S. Environmental Protection Agency, EPA 600/9-
86-013, Research Triangle Park, NC, 1986.
12. "Intercomparison of Sampling Techniques for Volatile Organic Compounds in Indoor
Air," Proceedings of the 1986 EPA/APCA Symposium on Measurement of Toxic Air Pollutants,
pp. 45-60, Air Pollution Control Association Publication VIP-7, U.S. Environmental
Protection Agency, EPA 600/9-86-013, Research Triangle Park, NC, 1986.
13. Mulik, J. D., Lewis, R. G., and McClenny, W. A., "Modification of a High-Efficiency
Passive Sampler to Determine Nitrogen Dioxide or Formaldehyde in Mr," Anal Chem.,
61,2:187-189, 1989.
14. Petreas, M., Liu, K-S, Chang, B-H, Hayward, S. B., and Saxton, K., "A Survey of
Nitrogen Dioxide Levels Measured Inside Mobile Homes," JAPCA, 38:647-651, 1988.
15. Woebkenberg, M. L., "A Comparison of Three Passive Personal Sampling Methods
for NO2," Am. Ind. Hyg. Assoc., 43(8):553-561, 1982.
Revised 9/30/89 Page 16
-------
Method IP-5C Nitrogen Dioxide
16. Yanagisawa, Y., and Nishimura, H., "A Badge-Type Personal Sampler For
Measurement of Personal Exposure to NO2 and NO in Ambient Air," Envir. Inter., Vol.
8:235-242, 1982.
17. Riggin, R. M., Technical Assistance Document for Sampling and Analysis of Toxic
Organic Compounds in Ambient Air, EPA-600/4-83-027, U.S. Environmental Protection
Agency, Research Triangle Park, NC, 1983.
18. Ferris, B. G., "Health Effect of Exposure to Low Levels of Regulated Pollutants - A
Critical Review,"/. AirPollut. Control Assoc., 28:482-497, 1978.
19. NAS: Nitrogen Oxides, National Academy of Sciences, Washington, D.C., 1977
Revised 9/30/89 Page 17
-------
Method IP-5C
Nitrogen Dioxide
Figure 1. Commercially Available NO2 Passive Sampling Device
Revised 9/30/89
Page 18
-------
Method IP-5C
Nitrogen Dioxide
Protective Cap
Internal 'C* Clip
Perforated Plate
200 Mesh Diffusion Screen
Internal 'C' Clip
Perforated Plate
200 Mesh Diffusion Screen
Treated Filter
Body
Treated Filter
200 Mesh Diffusion Screen
Perforated Plate
Internal 'C' Clip
Perforated Plate
200 Mesh Diffusion Screen
Internal 'C' Clip
Protective Cap
Figure 2. Exploded View of a Commercially Available Passive Sampling Device
Revised 9/30/89
Page 19
-------
Method IP-5C
Nitrogen Dioxide
Eluent
Reservoir
Pump
Sample
Injector
HPIC AG4A
Guard Column
HPIC AS4A
Analtical
Column
Micromembrane
Suppressor
Column
Conductivity
Cell
Data Mode
Recorder
j
Electronic
Integrator
1
Computer
I
Figure 3. Major Components of a Commercially Available Ion Chromatograph
Revised 9/30/89
Page 20
-------
Method IP-5C
Nitrogen Dioxide
r
PROJECT:
SITE:
LOCATION:
FIELD TEST DATA SHEET
(One Sample per Data Sheet)
DATE(S)
SAMPLER INFORMATION:
Type:
Adsorbent:
SAMPLING DATA:
Start Time:
Start Temperature:
Start KH(%):
Calculated Sampling Rate:
SAMPLING LOCATION:
TIME PERIOD SAMPLED:
OPERATOR:
Serial Number:
Sample Number:
Stop Time:
Stop Temperature:
Stop RH(%):
Figure 4. Field Test Data Sheet for PSD
Revised 9/30/89
Page 21
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Method IP-5C
Nitrogen Dioxide
I I I I I I r
83 ppbv NO2
I I
I!
0
10 15 20
Minutes
25 30
Figure 5. Typical Dionex Model 14 Chromatogram
Revised 9/30/89
Page 22
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Chapter IP-6
DETERMINATION OF FORMALDEHYDE AND OTHER
ALDEHYDES IN INDOOR AIR
• Method IP-6A - Solid Adsorbent Cartridge
• Method IP-6B - Continuous Colorimetric Analyzer
• Method IP-6C - Passive Sampling Device
1. Scope
This document describes three methods for determination of formaldehyde in indoor air.
The first method (IP-6A) utilizes solid adsorbent sampling followed by high performance
liquid chromatographic analysis (HPLC). The second method (IP-6B) for formaldehyde
determination employs a commercially available continuous colorimetric gas analyzer. The
analyzer operates on the principle of monitoring the amount of color change produced
when the air sample is scrubbed with liquid reagents. Finally, the third method (IP-6C)
utilizes a passive technique wherein 2,4-dinitrophenylhydrazine (DNPH) is loaded on glass
fiber filters and placed behind diffusion screens of a personal sampling device (PSD).
Formaldehyde and other aldehydes diffuse to the PSD sampler and react specifically with
the DNPH treated filters. For analysis, the filters are extracted with acetonitrile and
analyzed by HPLC.
2. Significance
2.1 Indoor air quality has become a significant environmental health issue because
generally people spend most of their time indoors, as well as concerns with improved
insulation and new materials issues. As with outdoor and occupational air quality,
monitoring indoor air pollutant concentrations is an essential part of evaluating potential
health threats and identifying abatement approaches.
22 Short term exposure to formaldehyde and other specific aldehydes (i.e., acetaldehyde,
acrolein, crotonaldehyde) is known to cause irritation of the eyes, skin, and mucous
membranes of the upper respiratory tract. Animal studies indicate that high concentrations
can injure the lungs and other organs of the body. Formaldehyde may contribute to eye
irritation and unpleasant odors that are common annoyances in polluted atmospheres.
2.3 Indoor sources of formaldehyde include particleboard, plywood, hardwood paneling,
furniture, urea-formaldehyde foam insulation, tobacco smoke, and gas combustion. Some
of the highest concentrations, exceeding 0.1 ppm, have been found in tightly constructed
mobile homes where internal volumes are small compared with surface areas of
formaldehyde-containing materials. Formaldehyde emissions increase with increasing
temperature and humidity.
2.4 The procedures described herein provide the user with a choice of methodologies and
instrumentation for sampling and analysis of formaldehyde in indoor air. All sampling
systems can be set up in domestic, industrial, or office environments for monitoring indoor
air atmospheres.
Revised 9/30/89 Pa8e
-------
Method IP-6A
DETERMINATION OF FORMALDEHYDE AND OTHER
ALDEHYDES IN INDOOR AIR USING A SOLID ADSORBENT
CARTRIDGE
1. Scope
2. Applicable Documents
3. Summary of Method
4. Significance
5. Definitions
6. Interferences
7. Apparatus
8. Reagents and Materials
9. Preparation of Reagents and Cartridges
9.1 Purification of 2,4-Dinitrophenylhydrazine (DNPH)
9.2 Preparation of DNPH-Formaldehyde Derivative
93 Preparation of DNPH-Formaldehyde Standards
9.4 Preparation of DNPH-Coated Sep-PAK« Cartridges
9.4.1 DNPH Coating Solution
9.4.2 Coating of Sep-PAK® Cartridges
10. Sample Collection
11. Sample Analysis
11.1 Sample Preparation
11.2 Sample Desorption
11.3 HPLC Analysis
11.4 HPLC Calibration
12. Calculations
13. Performance Criteria and Quality Assurance
13.1 Standard Operating Procedures (SOPs)
13.2 HPLC System Performance
13.3 Process Blanks
13.4 Method Precision and Accuracy
14. Detection of Other Aldehydes and Ketones
14.1 Sampling Procedures
14.2 HPLC Analysis
15. References
Revised 9/30/89 Page 1
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Method IP-6A Formaldehyde
Method IP-6A
DETERMINATION OF FORMALDEHYDE AND OTHER ALDEHYDES IN INDOOR
AIR USING A SOLID ADSORBENT CARTRIDGE
1. Scope
1.1 This method describes a procedure for determination of formaldehyde (HCHO) and
other aldehydes in indoor air. The method is specific for formaldehyde, but with
modification, fourteen other aldehydes can be detected.
12 Method TO-5, "Method For the Determination of Aldehydes and Ketones in Ambient
Air Using High Performance Liquid Chromatography (HPLC)" of the Compendium of
Metfiods for the Determination of Toxic Organic Compounds in Ambient Air (1) involves
drawing ambient air through a midget impinger sampling train containing 10 mL of 2N
HC1/0.05% 2,4-dinitrophenylhydrazine (DNPH) reagent. Aldehydes and ketones readily
form a stable derivative with the DNPH reagent The DNPH derivative is analyzed for
aldehydes and ketones utilizing HPLC. The solid sorbent sampling procedure in Method
IP-6 modifies the sampling procedures outlined in Method TO-5 by introducing a coated
adsorbent (instead of the impinger) for sampling formaldehyde in indoor air.
1.3 This current method is based on the specific reaction of carbonyl compounds
(aldehydes and ketones) with DNPH-coated cartridges in the presence of an acid to form
stable derivatives according to the following equation (2):
N02
+ "
C-0 + H2N-NH- -N02 - - - »- .N
C-0 + H2N-NH-<' ^>~NO, » fc-N-NH-^' VV-N02 + H20
CARBONYL GROUP 2.4-DINITROPHENYLHYDRAZINE r,M=u nCr.u,.T,t« W»TCD
•ALDEHYDES AND KETONES) (DNPH) DNPH-DERIVATIVE WATER
where R and R1 are alkyi or aromatic groups (ketones) or either substituent is a hydrogen
(aldehydes). The determination of formaldehyde from the DNPH-formaldehyde derivative
is similar to Method TO5 in incorporating HPLC. The detection limits have been extended
and other aldehydes and ketones can be determined as outlined in Section 14. The method
can determine formaldehyde concentrations in the low ppb (v/v) or higher ppm (v/v) levels.
Revised 9/30/89 Page 3
46Y
-------
Method IP-6A Formaldehyde
1.4 The sampling method gives a time-weighted average (TWA) sample. It can be used
for long-term (1-24 hr) or short-term (5-60 min) sampling of indoor air for formaldehyde.
1.5 The sampling flow rate, as described in this document, is presently limited to about
1.5 L/min. This limitation is principally due to the high pressure drop ( >30 inches of water
at 1.0 L/min) across the DNPH-coated silica gel cartridges. Because the pumps are not
adequate, the procedure is not compatible with pumps used in personal sampling
equipment.
1.6 The method instructs the user to purchase Sep-PAK*chromatographic grade silica gel
cartridges (Waters Associates, 34 Maple St., Milford, MA 01757) and apply acidified DNPH
in sjlu to each cartridge as part of the user-prepared quality assurance program (2,3).
Commercially precoated cartridges are also available. Thermosorb/F cartridges
(Thennedics, Inc., 470 Wildwood St., P.O. Box 2999, Woburn, MA 01888-1799, or
equivalent) can be purchased prepacked. The cartridges are 1.5 cm I.D. x 2 cm long
polyethylene tubes with Luer* type fittings on each end. The adsorbent is composed of
60/80-mesh Florisil (magnesium silicate) coated with DNPH. The adsorbent is held in
place with 100 mesh stainless steel screens at each end. The precoated cartridges are used
as received and are discarded after use. The cartridges are stored in glass culture tubes with
polypropylene caps and placed in cold storage when not in use. [Caution: Recent studies
have indicated abnormally high formaldehyde background levels in commercially prepacked
cartridges. Three cartridges randomly selected from each production lot should be analyzed
for formaldehyde before use to determine if background formaldehyde levels are
acceptable.]
1.7 Similarly, ORBO*-24 cartridges (Supelco, Inc., Supelco Park, Bellefonte, PA, 16923-
0048) are also available. ORBO*-24 tubes (4 mm x 10 cm) were developed by the Organic
Method Evaluation Branch of the Occupational Safety and Health Administration (OSHA)
for collection and solvent desorption of formaldehyde and acrolein. ORBO-24 tubes contain
either 150 mg or 75 mg adsorbent beds of 10% 2-(hydroxymethyl)piperidine coated and
Supelpak* 20N, allowing sampling up to 24 liters of indoor air for more accurate time-
weighted average values. The advantage of the ORBO*-24 cartridges is that they allow the
use of a personal sampling pump, having only a 4 inches water pressure drop at a flow rate
of 200 mL/min, whereas the user prepared DNPH-coated silica gel cartridges requires the
use of a laboratory type Thomas pump which is able to maintain a flow of 1 L/min at a
pressure drop of greater than 30 inches of water. DNPH coated silica gel cartridges with
a sufficiently large gel matrix (20/40 mesh) to greatly reduce the pressure drop, allowing
for the use of personal sampling pumps, have been custom ordered through Supelco.
However, validation tests to determine if cartridges of this type will exhibit break through
when high volumes of air are drawn and tests to determine recovery efficiencies have not
been completed. In Addition the background level of formaldehyde in the Supelco
cartridges, which are precoated with DNPH, may be high. Because the user can certify the
low level concentration of formaldehyde in the DNPH, the method instructs the user to use
the Sep-PAK® cartridges over other available techniques.
Revised 9/30/89 Page 4
-------
Method IP-6A Formaldehyde
1.8 This method may involve hazardous materials, operations, and equipment. This
method does not purport to address all the safety problems associated with its use. It is the
user's responsibility to develop and implement appropriate safety and health practices and
determine the applicability of regulatory limitations prior to use. Specific precautions are
outlined in Section 9.
2. Applicable Documents
2.1 ASTM Standards
D1356 Definition of Terms Relating to Atmospheric Sampling and Analysis
E682 Practice for Liquid Chromatography Terms and Relationships
22 Other Documents
Existing Procedures (3-5)
Ambient Air Studies (6-8)
U.S. EPA Technical Assistance Document (9)
Indoor Air Studies (10-11)
3. Summary of Method
3.1 A known volume of indoor air is drawn through a prepacked silica gel cartridge coated
with acidified DNPH at a sampling rate of 500-1200 mL/min for an appropriate period of
time. Sampling rate and time are dependent upon carbonyl concentrations in the test
atmosphere.
22 After sampling, the sample cartridges are capped and placed in borosilicate glass
culture tubes with polypropylene caps. The capped tubes are then placed in a friction-top
can containing a pouch of charcoal and returned to the laboratory for analysis.
Alternatively, the sample vials can be placed hi a styrofoam box with appropriate padding
for shipment to the laboratory. The cartridges may either be placed in cold storage until
analysis or immediately washed by gravity feed elution of 6 mL of acetonitrile from a plastic
syringe reservoir to a graduated test tube or a 5-mL volumetric flask. The eluate is then
topped to a known volume and refrigerated until analysis.
33 The DNPH-formaldehyde derivative is determined using isocratic reverse phase HPLC
with an ultraviolet (UV) absorption detector operated at 360 nm.
3.4 A cartridge blank is likewise desorbed and analyzed as per Section 33.
3.5 Formaldehyde and other carbonyl compounds in the sample are identified and
quantified by comparison of their retention times and peak heights or peak areas with those
of standard solutions.
Revised 9/30/89 Page 5
-------
Method IP-6A Formaldehyde
4. Significance
4.1 This method uses an active sampling system, requiring a pump to move sample air
through the DNPH coated cartridge. The cartridge is coated by the user in order to avoid
the high background levels often encountered in commercially prepared cartridges. The
portable sampling system allows for flexible employment of this sampling technique hi close
proximity to people within their work and living environment. Appendix C-3 of this
Compendium, Placement of Stationary Active Samplers in Indoor Environments, discusses
factors regarding monitor placement
42 Subsequent HPLC analysis provides a very accurate measure of indoor formaldehyde
concentrations.
5. Definitions
Note: Definitions used in this document and any user-prepared SOPs should be consistent
with ASTM Methods D1356 and E682. All pertinent abbreviations and symbols are defined
within this document at point of use. Additional definitions, symbols, and abbreviations are
provided in Appendices A-l and B-2 of this Compendium.
6. Interferences
6.1 The solid sorbent sampling procedure is specific for sampling and analysis of
formaldehyde. Interferences in the method are certain isomeric aldehydes or ketones that
may be unresolved by the HPLC system when analyzing for other aldehydes and ketones.
Organic compounds that have the same retention time and significant adsorbance at 360
nm as the DNPH derivative of formaldehyde will interfere. Such interferences can often
be overcome by altering the separation conditions (e.g., using alternative HPLC columns
or mobile phase compositions). Other aldehydes and ketones can be detected with a
modification of the basic procedure. In particular, chromatographic conditions can be
optimized to separate acrolein, acetone, and propionaldehyde and the following higher
molecular weight aldehydes and ketones (within an analysis time of about one hour) by
utilizing two Zorbax ODS columns in series under a linear gradient program.
formaldehyde crotonaldehyde o-tolualdehyde
acetaldehyde butyraldehyde m-tolualdehyde
acrolein benzaldehyde p-tolualdehyde
acetone isovaleraldehyde hexanaldehyde
propionaldehyde valeraldehyde 2,5-dimethylbenzaldehyde
The linear gradient program varies the mobile phase composition periodically to achieve
maximum resolution of the C-3, C-4, and benzaldehyde region of the chromatogram. The
following gradient program was found to be adequate to achieve this goal: upon sample
injection, linear gradient from 60-75% acetonitrile/40-25% water in 30 minutes, linear
gradient from 75-100% acetonitrile/25-0% water in 20 minutes, hold at 100% acetonitrile
for 5 minutes, reverse gradient to 60% acetonitrile/40% water in 1 minute, and maintain
isocratic at 60% acetonitrile/40% water for 15 minutes.
Revised 9/30/89 Page 6
-------
Method IP-6A _ Formaldehyde
62 Formaldehyde contamination of the DNPH reagent is a frequently encountered
problem. The DNPH must be "purified by multiple recrystallizations in UV grade
acetonitrile. Recrystallization is accomplished at 40-60°C by slow evaporation of the solvent
to maximize crystal size. The purified DNPH crystals are stored under UV grade
acetonitrile until use. Impurity levels of carbonyl compounds in the DNPH are determined
by HPLC prior to use and should be less than 0.025 /Jg/mL.
Ozone has been shown to interfere negatively by reacting with both DNPH and its
hydrazone derivatives in the cartridge (15). Ozone emission factors can be in the 0-546
/jg/min range for electrostatic air cleaners installed in central air conditioning units and
the 2-158 /ig/copy range (at a typical copy rate of 5/min) for photocopying machines
(16,17). The presence of high indoor ozone concentrations may be very site specific. The
user must determine whether ozone interference will be significant to the sample location.
The extent of interference depends on the temporal variations of both the ozone and the
carbonyl compounds during samping. The presence of ozone in the sample stream is
readily inferred from the appearance of new compounds with retention times shorter than
that of the hydrazone of formaldehyde. Figure 1 shows chromatographs of cartridge
samples of a formaldehyde spiked air stream with and without ozone (15). Ozone
interference can be removed by selectively scrubbing the ozone from the sample stream
before it reaches the cartridge. A simple denuder (scrubber) device has been developed
and tested to accomplish this. The denuder is made by coiling a copper tubing (3 ft x 1/4
in O.D. x 4.6 mm I.D.) and coating the inside surface with potassium iodide (KI). The
copper-KI ozone denuder is connected to the sampling cartridge by a short piece of silicone
or Tygon tubing. For in-depth information regarding this method of removal of ozone
interference, see Section 15, reference 15.
7. Apparatus
7.1 Sampling system - capable of accurately and precisely sampling 100-1500 mL/min of
indoor air (see Figures 2, 3 and 4). The dry test meter in Figure 3(b) may not be accurate
at flows below 500 mL/min, and should then be replaced by recorded flow readings at the
start, finish, and hourly intervals during the collection. The sample pump consists of a
diaphragm or metal bellows pump capable of extracting an air sample between 500-1200
mL/min.
Note: A normal pressure drop through the sample cartridge approaches 14 cm Hg at a
sampling rate of 1.5 L/min.
12 Isocratic HPLC system - consisting of a mobile phase reservoir; a high pressure pump;
an injection valve (automatic sampler with an optional 25-/iL loop injector); a Zorbax ODS
(DuPont Instruments, Wilmington, DE), or equivalent C-18, reverse phase (RP) column,
or equivalent (25 cm x 4.6 mm ID); a variable wavelength UV detector operating at 360
nm; and a data system or strip chart recorder (see Figure 5).
7.3 Stopwatch.
Revised 9/30/89 Page 7
-------
Method IP-6A Formaldehyde
7.4 Friction-top metal can (e.g., 1-gallon paint can) or a styrofoam box with polyethlyene
air bubble padding - to hold sample vials.
7.5 Thermometer - to record indoor temperature.
7.6 Barometer (optional).
7.7 Suction filtration apparatus - for filtering HPLC mobile phase.
7.8 Volumetric flasks - various sizes, 5-2000 mL.
7.9 Pipets - various sizes, 1-50 mL.
7.10 Helium purge line (optional) - for degassing HPLC mobile phase.
7.11 Erlenmeyer flask - 1 L, for preparing HPLC mobile phase.
7.12 Graduated cylinder - 1 L, for preparing HPLC mobile phase.
7.13 Syringes - 100-250 liL, for HPLC injection.
7.14 Sample vials.
7.15 Melting point apparatus.
7.16 Rotameters.
7.17 Calibrated syringes.
7.18 Mass flowmeters and mass flow controllers - for metering/setting air flow rate of 500-
1200 mL/min through sample cartridge.
Note: The mass flow controllers are necessary because cartridges have a high pressure drop
and at maximum flow rates, the cartridge behaves like a "critical orifice." Recent studies
have shown that critical flow orifices may be used for 24-hour sampling periods at a
maximum rate of 1 L/min for atmospheres not heavily loaded with particulates without any
problems. Flow drop of less than 5% of the initial flow was generally observed for a 24-
hour sampling episode.
7.19 Positive displacement, repetitive dispensing pipets (Lab-Industries, or equivalent) -
0-10 mL range.
7.20 Cartridge drying manifold with multiple standard male Luer* connectors.
7.21 Liquid syringes (polypropylene syringes are adequate) - 10 mL, used to prepare
DNPH-coated cartridges.
7.22 Syringe rack - made of an aluminum plate (0.16 x 36 x 53 cm) with adjustable legs
on four corners. A matrix (5 x 9) of circular holes of diameter slightly larger than the
diameter of the 10-mL syringes was symmetrically drilled from the center of the plate to
enable batch processing of 45 cartridges for cleaning, coating, and/or sample elution (see
Figure 6).
Revised 9/30/89 Page 8
t *
H
-------
Method IP-6A Formaldehyde
7.23 Luer* fittings/plugs - to connect cartridges to sampling system and to cap prepared
cartridges.
724 Hot plates, beakers, flasks, measuring and disposable pipets, volumetric flasks, etc.
used in the purification of DNPH.
125 Borosilicate glass culture tubes (20 mm x 125 mm) with polypropylene screw caps -
used to transport Sep-PAK* coated cartridges (Fisher Scientific, Pittsburgh, PA, or
equivalent).
726 Heated probe - necessary when temperature of sampled air is below 60°F, to insure
effective collection of formaldehyde as a hydrazone.
727 Cartridge sampler - prepacked silica gel cartridge, Sep-PAK* (Waters Associates,
Milford, MA 01757, or equivalent) coated in situ with DNPH according to Section 9.
728 Polyethylene gloves - used to handle Sep-PAK* silica gel cartridges, best source.
8. Reagents and Materials
8.1 2,4-Dinitrophenylhydrazine (DNPH) - Aldrich Chemical or J.T. Baker, reagent grade
or equivalent. Recrystallize at least twice with UV grade acetonitrile before use.
82 Acetonitrile - UV grade, Burdick and Jackson "distilled-in-glass," or equivalent.
8.3 Deionized-distilled water - charcoal filtered.
8.4 Perchloric acid - analytical grade, best source.
8.5 Hydrochloric acid - analytical grade, best source.
8.6 Formaldehyde - analytical grade, best source.
8.7 Aldehydes and ketones - analytical grade, best source, used for preparation of DNPH
derivative standards (optional).
8.8 Ethanol or methanol - analytical grade, best source.
8.9 Sep-PAK« silia gel cartridges - Waters Associates, 34 Maple St., Milford, MA 01757,
or equivalent.
8.10 Nitrogen - high purity grade, best source.
8.11 Charcoal - granular, best source.
8.12 Helium - high purity grade, best source.
8.13 ORBO*-24 cartridges -Supelco, Inc., Supelco Park, Bellefonte, PA, 16823-0048
(optional).
Revised 9/30/89 Page 9
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Method IP-6A Formaldehyde
9. Preparation of Reagents and Cartridges
9.1 Purification of 2,4-Dinitrophenylhydrazine (DNPH)
Note: This procedure should be performed under a properly ventilated hood.
9.1.1 Prepare a supersaturated solution of DNPH by boiling excess DNPH in 200 mL
of acetonitrile for approximately one hour.
9.1.2 After one hour, remove and transfer the supernatant to a covered beaker on a
hot plate and allow gradual cooling to 40-60°C.
9.13 Maintain the solution at this temperature (40°C) until 95% of solvent has
evaporated.
9.1.4 Decant solution to waste, and rinse crystals twice with three times their apparent
volume of acetonitrile.
Note: Various health effects result from the inhalation of acetonitrile. At 500 ppm in air,
brief inhalation has produced nose and throat irritation. At 160 ppm, inhalation for 4 hours
has caused flushing of the face (2 hour delay after exposure) and bronchial tightness (5 hour
delay). Heavier exposures have produced systemic effects with symptoms ranging from
headache, nausea, and lassitude to vomiting, chest or abdominal pain, respiratory
depression, extreme weakness, stupor, convulsions and death (dependent upon concentration
and time).
9.1.5 Transfer crystals to another clean beaker, add 200 mL of acetonitrile, heat to
boiling, and again let crystals grow slowly at 40-60°C until 95% of the solvent has
evaporated.
9.1.6 Repeat rinsing process as described in Section 9.1.4.
9.1.7 Take an aliquot of the second rinse, dilute 10 times with acetonitrile, acidify with
1 mL of 3.8 M perchloric acid per 100 mL of DNPH solution, and analyze by HPLC.
9.1.8 The chromatogram illustrated in Figure 7 represents an acceptable impurity level
of < 0.025 /Jg/mL of formaldehyde in recrystallized DNPH reagent. An acceptable impurity
level for an intended sampling application may be defined as the mass of the analyte (e.g.,
DNPH-formaldehyde derivative) in a unit volume of the reagent solution equivalent to less
than one tenth (0.1) the mass of the corresponding analyte from a volume of an air sample
when the carbonyl (e.g., formaldehyde) is collected as DNPH derivative in an equal unit
volume of the reagent solution. An impurity level unacceptable for a typical 10-L sample
volume may be acceptable if sample volume is increased to 100 L. The impurity level of
DNPH should be below the sensitivity (ppb, v/v) level indicated in Table 1 for the
anticipated sample volume. If the impurity level is not acceptable for intended sampling
application, repeat recrystallization.
9.1.9 Transfer the purified crystals to an all-glass reagent bottle, add 200 mL of
acetonitrile, stopper, shake gently, and let stand overnight. Analyze supernatant by HPLC
according to Section 11. The impurity level should be comparable to that shown in Figure
7.
9.1.10 If the impurity level is not satisfactory, pipet off the solution to waste, then add
25 mL of acetonitrile to the purified crystals. Rinsing should be repeated with 20 mL
portions of acetonitrile until a satisfactorily low impurity level in the supernatant is
Revised 9/30/89 Page 10
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Method IP-6A Formaldehyde
confirmed by HPLC analysis. An impurity level of < 0.025 Mg/mL formaldehyde should be
achieved, as illustrated in Figure 7.
9.1.11 If the impurity level is satisfactory, add another 25 mL of acetonitrile, stopper
and shake the reagent bottle, then set aside. The saturated solution above the purified
crystals is the stock DNPH reagent.
9.1.12 Maintain only a minimum volume of saturated solution adequate for day to day
operation. This will minimize waste of purified reagent should it ever become necessary
to rerinse the crystals to decrease the level of impurity for applications requiring more
stringent purity specifications.
9.1.13 Use clean pipets when removing saturated DNPH stock solution for any
analytical applications. Do not pour the stock solution from the reagent bottle.
9 2 Preparation of DNPH-Formaldehyde Derivative
9.2.1 Titrate a saturated solution of DNPH in 2N HC1 with formaldehyde (other
aldehydes or ketones may be used if their detection is desired).
922 Filter the colored precipitate, wash with 2N HC1 and water, and allow precipitate
to air dry.
9.2.3 Check the purity of the DNPH-formaldehyde derivative by melting point
determination or HPLC analysis. If the impurity level is not acceptable, recrystallize the
derivative in ethanol. Repeat purity check and recrystallization as necessary until
acceptable level of purity (e.g., 99%) is achieved.
93 Preparation of DNPH-Formaldehyde Standards
93.1 Prepare a standard stock solution of the DNPH-formaldehyde derivative by
dissolving accurately weighed amounts in acetonitrile.
9.3.2 Prepare a working calibration standard mix from the standard stock solution. The
concentration of the DNPH-formaldehyde compound in the standard mix solutions should
be adjusted to reflect relative distribution in a real sample.
Note: Individual stock solutions of approximately 100 mg/L are prepared by dissolving 10
mg of the solid derivative in 100 mL of acetonitrile. The individual solution is used to
prepare calibration standards containing the derivative of interest at concentrations of 0.5-
20 Mg/L, which spans the concentration of interest for most indoor air work.
9.33 Store all standard solutions in a refrigerator. They should be stable for several
months.
9.4 Preparation of DNPH-Coated Sep-PAK* Cartridges
Note: This procedure must be performed in an atmosphere with a very low aldehyde
background. All glassware and plasticware must be scrupulously cleaned and rinsed with
deionized water and aldehyde free acetonitrile. Contact of reagents with laboratory air
must be minimized. Polyethylene gloves must be worn when handling the cartridges.
Revised 9/30/89 Page
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Method IP-6A Formaldehyde
9.4.1 DNPH Coating Solution
9.4.1.1 Pipet 30 mL of saturated DNPH stock solution to a 1000 mL volumetric
flask, then add 500 mL acetonitrile.
9.4.12 Acidify with 1.0 mL of concentrated HC1.
Note: The atmosphere above the acidified solution should preferably be filtered through
a DNPH-coated silica gel cartridge to minimize contamination from laboratory air. Shake
solution, then make up to volume with acetonitrile. Stopper the flask, invert and shake
several times until the solution is homogeneous. Transfer the acidified solution to a reagent
bottle equipped with a 0-10 mL range positive displacement dispenser.
9.4.1.3 Prime the dispenser and slowly dispense 10-20 mL to waste.
9.4.1.4 Dispense an aliquot solution to a sample vial, and check the impurity level
of the acidified solution by HPLC according to Section 9.1.
9.4.1.5 The impurity level should be < 0.025 Mg/mL formaldehyde, similar to that
in the DNPH stock solution.
9.42 Coating of Sep-PAK* Cartridges
9.42.1 Open the Sep-PAK* package, connect the short end to a 10-mL syringe, and
place it in the syringe rack. The syringe rack for coating and drying the sample cartridges
is illustrated in Figures 6(a) and 6(b).
9.4.2.2 Using a positive displacement repetitive pipet, add 10 mL of acetonitrile
to each of the syringes.
9.423 Let liquid drain to waste by gravity.
Note: Remove any air bubbles that may be trapped between the syringe and the silica
cartridge by displacing them with the acetonitrile in the syringe.
9.42.4 Set the repetitive dispenser containing the acidified DNPH coating solution
to dispense 7 mL into the cartridges.
9.42.5 Once the effluent flow at the outlet of the cartridge has stopped, dispense
7 mL of the coating reagent into each of the syringes.
9.42.6 Let the coating reagent drain by gravity through the cartridge until flow at
the other end of the cartridge stops.
9.42.7 Wipe the excess liquid at the outlet of each of the cartridges with clean
tissue paper.
9.42.8 Assemble a drying manifold with a scrubber or "guard cartridge" connected
to each of the exit ports. These "guard cartridges" are DNPH-coated and serve to remove
any trace of formaldehyde in the nitrogen gas supply. This process is illustrated in Figure
6(b).
9.42.9 Remove the cartridges from the syringes and connect the short ends to the
exit end of the scrubber cartridge.
9.42.10 Pass nitrogen through each of the cartridges at about 300-400 mL/min for
5-10 minutes.
9.42.11 Within 10 minutes of the drying process, rinse the exterior surfaces and
outlet ends of the cartridges with acetonitrile using a Pasteur pipet.
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Method IP-6A Formaldehyde
9.42.12 Stop the flow of nitrogen after 15 minutes and insert cartridge connectors
(flared at both ends, 0.25 O.D. x 1 in Teflon* FEP tubing with I.D. slightly smaller than the
O.D. of the cartridge port) to the long end of the scrubber cartridges.
9.42.13 Connect the short ends of a batch of the coated cartridges to the scrubbers
and pass nitrogen through at about 300-400 mL/min.
9.42.14 Follow procedure in Section 9.4.2.11.
9.42.15 After 15 minutes, stop the flow of nitrogen, remove the dried cartridges
and wipe the cartridge exterior free of rinse acetonitrile.
9.42.16 Plug both ends of the coated cartridge with standard polypropylene Luer*
male plugs and place the plugged cartridge in a borosilicate glass culture tube with
polypropylene screw caps.
9.42.17 Put a serial number and a lot number label on each of the individual
cartridge glass storage containers and refrigerate the prepared lot until use.
9.42.18 Store cartridges in an all-glass stoppered reagent bottle in a refrigerator
until use.
Note: Plugged cartridges could also be placed in screw-capped glass culture tubes and
placed in a refrigerator until use. Cartridges will maintain their integrity for up to 90 days
stored in refrigerated, capped culture tubes, and can remain in refrigerated storage for
much longer provided the background level is acceptable.
9.42.19 Before transport, remove the glass-stoppered reagent bottles (or screw-
capped glass culture tubes) containing the adsorbent tubes from the refrigerator and place
the tubes individually in labeled glass culture tubes. Place culture tubes in a friction-top
metal can containing 1-2 inches of charcoal for shipment to sampling location.
9.4220 As an alternative to friction-top cans for transporting sample cartridges,
the coated cartridges could be shipped in their individual glass containers. A big batch of
coated cartridges in individual glass containers may be packed in a styrofoam box for
shipment to the sampling location. The box should be padded with clean tissue paper or
polyethylene air bubble padding. Do not use polyurethane foam or newspaper as padding
material.
9.4221 The cartridges should be immediately stored in a refrigerator upon arrival
to the sampling site.
10. Sample Collection
10.1 The sampling system is assembled and should be similar to that shown in Figures 2,
3 or 4.
Note: Figure 3a illustrates a three tube/one pump configuration. The tester should ensure
that the pump is capable of constant flow rate throughout the sampling period. The coated
cartridges can be used as direct probes and traps for sampling indoor air when the
temperature is above freezing.
Note: For sampling indoor air below freezing, a short length (30-60 cm) of heated (50-
60°C) stainless steel tubing must be added to condition the air sample before collection on
adsorbent tubes. Two types of sampling systems are shown in Figure 2. For purposes of
discussion, the following procedure assumes use of a dry test meter.
Revised 9/30/89 Page 13
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Method IP-6A Formaldehyde
Note: The dry test meter may not be accurate at flows below 500 mL/min and should be
backed up by recorded flow readings at the start, finish, and hourly intervals during sample
collection.
102 Before sample collection, the system is checked for leaks. Plug the input end of the
cartridge so no flow is indicated at the output end of the pump. The mass flowmeter
should not indicate any air flow through the sampling apparatus.
10.3 The entire assembly (including a dummy cartridge not to be used for sampling) is
installed and the flow rate checked at a value near the desired rate. In general, flow rates
of 500-1200 mL/min should be employed. The total moles of carbonyl in the volume of
air sampled should not exceed that of the DNPH concentration (2 mg/cartridge). In
general, a safe estimate of the sample size should be approximately 75% of the DNPH
loading of the cartridge (-200 /tg as CH2O). Generally, calibration is accomplished using
a soap bubble flowmeter or calibrated wet test meter connected to the flow exit, assuming
the system is sealed.
Note: ASTM Method 3686 describes an appropriate calibration scheme that does not
require a sealed flow system downstream of the pump.
10.4 Ideally, a dry gas meter is included in the system to record total flow. If a dry gas
meter is not available, the operator must measure and record the sampling flow rate at the
beginning and end of the sampling period to determine sample volume. If the sampling
period exceeds two hours, the flow rate should be measured at intermediate points during
the sampling period. A rotameter is included to allow observation of the flow rate without
interruption of the sampling process.
10.5 Before sampling, remove the glass culture tube from the friction-top metal can or
styrofoam box. Let the cartridge warm to room temperature in the glass tube before
connecting it to the sample train.
10.6 Using polyethylene gloves, remove the coated cartridge from the glass tube and
connect it to the sampling system with a Luer* adapter fitting. Seal the glass tube for later
use, and connect the cartridge to the sampling train so that the short end becomes the
sample inlet. Record the following parameters on the sampling data sheet (Figure 8): date,
sampling location, time, room temperature, barometric pressure (if available), relative
humidity (if available), flow rate, rotameter setting, and cartridge batch number.
10.7 The sampler is turned on and the flow is adjusted to the desired rate. A typical flow
rate through one cartridge is 1.0 L/min and 0.8 L/min for two cartridges in tandem.
10.8 The sampler is operated for the desired period, with periodic recording of the
variables listed above.
10.9 At the end of the sampling period, the parameters listed in Section 10.6 are recorded
and the sample flow is stopped. If a dry gas meter is not used, the flow rate must be
checked at the end of the sampling interval. If the flow rates at the beginning and end of
the sampling period differ by more than 15%, the sample should be marked as suspect.
Revised 9/30/89 Page 14
if 71
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Method IP-6A Formaldehyde
10.10 Immediately after sampling, remove the cartridge (using polyethylene gloves) from
the sampling system, cap with Luer* end plugs, and place it back in the original labeled
glass culture tube. Cap the culture tube, seal it with Teflon* tape, and place it in a friction-
top can containing 1-2 inches of granular charcoal or styrofoam box with appropriate
padding. Refrigerate the culture tubes until analysis. Refrigeration period of exposed
cartridges prior to analysis should not exceed 90 days.
Note: If samples are to be shipped to a central laboratory for analysis, the duration of the
non-refrigerated period should be kept to a minimum, preferably less than two days.
10.11 If a dry gas meter or equivalent total flow indicator is not used, the average sample
flow rate must be calculated according to the following equation:
QA = (Q, + Ch + • • • + QN)/N
where:
QA = average flow rate, mL/min
Qi» QZV-QN = flow rates determined at beginning, end and intermediate points during
sampling
N = number of points averaged
10.12 The total flow is then calculated using the following equation:
Vm = [(T2 - TO x QJ/1000
where:
Vm = total volume sampled at measured temperature and pressure, L
T2 = stop time, min
TI = start time, min
T2 - Tj = total sampling time, min
QA = average flow rate, mL/min
10.13 The total volume (V.) at standard conditions, 25°C and 760 mm Hg, is calculated
from the following equation:
V, = Vm x (PA/760) x [298/(273 + tA)]
where:
V. = total sample volume at 25°C and 760 mm Hg pressure, L
Vm = total sample volume at measured temperature and pressure, L
PA = average indoor pressure, mm Hg
tA = average indoor temperature, °C
11. Sample Analysis
11.1 Sample Preparation
The samples are returned to the laboratory in a friction-top can containing 1-2 inches of
granular charcoal and stored in a refrigerator until analysis. Alternatively, the samples may
Revised 9/30/89 Page 15
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Method IP-6A Formaldehyde
also be stored alone in their individual glass containers. The time between sampling and
analysis should not exceed 30 days.
112 Sample Desorption
112.1 Remove the sample cartridge from the labeled culture tube. Connect the sample
cartridge (outlet end during sampling) to a clean syringe.
Note: The liquid flow during desorption should be in the reverse direction of air flow
during sample collection.
1122 Place the cartridge/syringe in the syringe rack.
1123 Backflush the cartridge (gravity feed) by passing 6 mL of acetonitrile from the
syringe through the cartridge to a graduated test tube or to a 5-mL volumetric flask.
Note: A dry cartridge has an acetonitrile holdup volume slightly greater than 1 mL. The
eluate flow may stop before the acetonitrile in the syringe is completely drained into the
cartridge because of air trapped between the cartridge filter and the syringe Luer* tip. If
this happens, displace the trapped air with the acetonitrile in the syringe using a long-tip
disposable Pasteur pipet.
112.4 Dilute to the 5-mL mark with acetonitrile. Label the flask with sample
identification. Pipet two aliquots into sample vials with Teflon* -lined septa. Analyze the
first aliquot for the derivative carbonyls by HPLC. Store the second aliquot in the
refrigerator until the results of the analysis of the first aliquot are complete and validated.
The second aliquot should be used for confirmatory analysis, if necessary.
11 3 HPLC Analysis
113.1 The HPLC system is assembled and calibrated as described in Section 11.4 and
as illustrated hi Figure 5. Before each analysis, the detector baseline is checked to ensure
stable conditions. The operating parameters are as follows:
Column - Zorbax ODS (4.6 mm inner diameter x 25 cm, or equivalent)
Mobile Phase - 60% acetonitrile/40% water, isocratic
Detector - ultraviolet, operating at 360 run
Flow Rate - 1.0 mL/min
Retention Time - 7 minutes for formaldehyde with one Zorbax ODS column.
13 minutes for formaldehyde with two Zorbax ODS columns.
Sample Injection Volume - 25
11.3.2 The HPLC mobile phase is prepared by mixing 600 mL of acetonitrile and 400
mL of water. This mixture is filtered through a 0.22-um polyester membrane filter in an
all-glass and Teflon* suction filtration apparatus. The filtered mobile phase is degassed by
purging with helium for 10-15 minutes (100 mL/min) or by heating to 60°C for 5-10 minutes
in an Erlenmeyer flask covered with a watch glass. A constant back pressure restrictor (350
kPa) or short length (15-30 cm) of 0.25 mm (0.01 inch) inner diameter Teflon* tubing
should be placed after the detector to eliminate further mobile phase outgassing.
1133 The mobile phase is placed in the HPLC solvent reservoir and the pump is set
at a flow rate of 1.0 mL/min and allowed to pump for 20-30 minutes before the first analy-
Revised 9/30/89 Page 16
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Method IP-6A Formaldehyde
sis. The detector is switched on at. least 30 minutes before the first analysis, and the
detector output is displayed on a strip chart recorder or similar output device.
113.4 A 100 ML aliquot of the sample is drawn into a clean HPLC injection syringe.
The sample injection loop (25 /iL) is loaded and an injection is made. The data system, if
available, is activated simultaneously with the injection, and the point of injection is marked
on the strip chart recorder.
113.5 After approximately one minute, the injection valve is returned to the "inject"
position and the syringe and valve are rinsed or flushed with acetonitrile/water mixture in
preparation for the next sample analysis.
Note: The flush/rinse solvent should not pass through the sample loop during flushing.
The loop is clean while the valve is in the "inject" mode.
11.3.6 After elution of the DNPH-formaldehyde derivative (see Figure 9), data
acquisition is terminated and the component concentrations are calculated as described in
Section 12.
113.7 After a stable baseline is achieved, the system can be used for further sample
analyses as described above.
Note: After several cartridge analyses, buildup on the column may be removed by flushing
with several column volumes of 100% acetonitrile.
113.8 If the concentration of analyte exceeds the linear range of the instrument, the
sample should be diluted with mobile phase, or a smaller volume can be injected into the
HPLC.
113.9 If the retention time is not duplicated (± 10%), as determined by the calibration
curve, the acetonitrile/water ratio may be increased or decreased to obtain the correct
elution time. If the elution time is too long, increase the ratio; if it is too short, decrease
the ratio.
Note: The chromatographic conditions described here have been optimized for the
detection of formaldehyde. Analysts are advised to experiment with their HPLC system to
optimize chromatographic conditions for their particular analytical needs.
11.4 HPLC Calibration
11.4.1 Calibration standards are prepared in acetonitrile from the DNPH-formaldehyde
derivative. Individual stock solutions of 100 mg/L are prepared by dissolving 10 mg of solid
derivative in 100 mL of mobile phase. These individual solutions are used to prepare
calibration standards at concentrations spanning the range of interest.
11.4.2 Each calibration standard (at least five levels) is analyzed three times and area
response is tabulated against mass injected (see Figure 10). All calibration runs are
performed as described for sample analyses in Section 11.3. Using the UV detector, a
linear response range of approximately 0.05-20 Mg/mL should be achieved for 25-0L
injection volumes. The results may be used to prepare a calibration curve, as illustrated in
Figure 11. Linear response is indicated where a correlation coefficient of at least 0.999 for
a linear least-squares fit of the data (concentration versus area response) is obtained. The
retention times for each analyte should agree within 2%.
Revised 9/30/89 Page 17
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Method IP-6A Formaldehyde
11.43 Once linear response has been documented, an intermediate concentration
standard near the anticipated levels of each component, but at least 10 times the detection
limit, should be chosen for daily calibration. The day to day response for the various
components should be within 10% for analyte concentrations of 1 Mg/mL or greater and
within 15-20% for analyte concentrations near 0.5 Mg/mL. If greater variability is observed,
recalibration may be required or a new calibration curve must be developed from fresh
standards.
12. Calculations
12.1 The total mass of analyte (DNPH-formaldehyde) is calculated for each sample using
the following equation:
Wd = W. - Wb
where:
Wd = total analyte mass from volume of sampled air, fig
W. = analyte mass in the sample cartridge, #g
= A, x (CM/A^) x v, x d,
Wb = analyte mass in the blank cartridge, ng
= A, x (C^/A«d) x vb x d,
A, = area counts, sample cartridge
Ab = area counts, blank cartridge
AM= area counts, standard
Qtd= concentration of analyte in the daily calibration standard, ng/miL
\, = total volume of the sample cartridge eluate, mL
vb = total volume of the blank cartridge eluate, mL
d, = dilution factor for the sample cartridge eluate
= 1 if sample was not rediluted
= vd/va if sample was rediluted to bring detector response within linear range
vd = redilution volume
v, = aliquot used for redilution
db = dilution factor for the blank cartridge eluate
= 1
12.2 The concentration of aldehyde (formaldehyde) in the original sample is calculated
from the following equation:
CA = Wd x (MW^/MW^) x 1000/Vm (or V.)
where:
CA = concentration of aldehyde (formaldehyde) in the original sample, ng/L
Wd = weight of the aldehyde (formaldehyde) derivative collected on the sample
cartridge, from Section 11.4, blank corrected, pg
Vm = total sample volume under indoor conditions, from Section 10.13, L
V, = total sample volume at 25°C and 760 mm Hg, from Section 10.13, L
Revised 9/30/89 Page 18
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Method IP-6A Formaldehyde
MWa1d = molecular weight of aldehyde (formaldehyde), g/g-mole
MWder = molecular weight of the DNPH derivative of the aldehyde (formaldehyde), g/g-
mole
The aldehyde (formaldehyde) concentrations can be converted to ppbv using the following
equation:
CA(ppbv) = CA(ng/L) x (24.4/MWald)
where:
CA(ppbv) = concentration of aldehyde (formaldehyde) by volume, ppb
CA = concentration of aldehyde (formaldehyde) in the original sample, calculated
using Vs, ng/L
MWald = molecular weight of the aldehyde (formaldehyde), g/g-mole
13. Performance Criteria and Quality Assurance
This section summarizes required quality assurance measures and provides guidance
concerning performance criteria that should be achieved within each laboratory.
13.1 Standard Operating Procedures (SOPs)
13.1.1 Users should generate SOPs describing the following activities in their laboratory:
1) assembly, calibration, and operation of the sampling system, with make and model of
equipment used, 2) preparation, purification, storage, and handling of sampling reagent and
samples, 3) assembly, calibration, and operation of the HPLC system, with make and model
of equipment used, and 4) all aspects of data recording and processing, including lists of
computer hardware and software used.
13.12 SOPs should provide specific stepwise instructions and should be readily available
to and understood by the laboratory personnel conducting the work.
132 HPLC System Performance
132.1 The general appearance of the HPLC system should be similar to that illustrated
in Figure 5.
1322 HPLC system efficiency is calculated according to the following equation:
N = 5.54(tr2/W1/2)
where:
N = column efficiency (theoretical plates)
tr = retention tune of analyte, seconds
W1/2= width of component peak at half height, seconds
A column efficiency of > 5,000 theoretical plates should be obtained.
1323 Precision of response for replicate HPLC injections should be ± 10% or less, day
to day, for analyte calibration standards at 1 /Jg/mL or greater levels. At the 0.5 /ig/mL
level and below, precision of replicate analyses could vary up to 25%. Precision of
retention tunes should be ±2% on a given day.
Revised 9/30/89 Page 19
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Method IP-6A Formaldehyde
13.3 Process Blanks
At least one field blank or 10% of the field samples, whichever is larger, should be shipped
and analyzed with each group of samples. The number of samples within a group and/or
time frame should be recorded so that a specified percentage of blanks is obtained for a
given number of indoor air samples. The field blank is treated identically to the samples
except that no air is drawn through the cartridge. The performance criteria described in
Section 9.1 should be met for process blanks.
13.4 Method Precision and Accuracy
13.4.1 At least one duplicate sample or 10% of the field samples, whichever is larger,
should be collected during each sampling episode. Precision for field replication should
be ±20% or better.
13.4.2 Precision for replicate HPLC injections should be ± 10% or better, day to day,
for calibration standards.
13.43 At least one sample spike with analyte of interest or 10% of the field samples,
whichever is larger, should be collected.
13.4.4 Before initial use of the method, each laboratory should generate triplicate spiked
samples at a minimum of three concentration levels, bracketing the range of interest for
each compound. Triplicate nonspiked samples must also be processed. Spike recoveries
of >80 ± 10% and blank levels as outlined in Section 9.1 should be achieved.
14. Detection of Other Aldehydes and Ketones
Note: The procedure outlined above has been written specifically for the sampling and
analysis of formaldehyde in indoor air using an adsorbent cartridge and HPLC. Indoor air
contains other aldehydes and ketones. Optimizing chromatographic conditions by using two
Zorbax ODS columns in series and varying the mobile phase composition through a
gradient program will enable the analysis of other aldehydes and ketones in indoor air.
14.1 Sampling Procedures
The sampling procedures for other aldehydes and ketones are the same as in Section 10.
14.2 HPLC Analysis
142.1 The HPLC system is assembled and calibrated as described in Section 11. The
operating parameters are as follows:
Column - Zorbax ODS, two columns in series
Mobile Phase - Acetonitrile/water, linear gradient
Detector - Ultraviolet, operating at 360 nm
Flow Rate - 1.0 mL/min
Sample Injection Volume - 25 pL
Step 1 - 60-75% acetonitrile/40-25% water in 30 minutes
Step 2 - 75-100% acetonitrile/25-0% water in 20 minutes
Step 3 - 100% acetonitrile for 5 minutes
Revised 9/30/89 Page 20
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Method IP-6A Formaldehyde
Step 4 - 60% acetonitrile/40% water reverse gradient in 1 minute
Step 5 - 60% acetonitrile/40% water, isocratic, for 15 minutes
14.2.2 The gradient program allows for optimization of chromatographic conditions to
separate acrolein, acetone, propionaldehyde, and other higher molecular weight aldehydes
and ketones in an analysis time of about one hour. Table 1 illustrates the sensitivity for
selected aldehydes and ketones in ambient air that have been identified using two Zorbax
ODS columns in series.
1423 The chromatographic conditions described herein have been optimized for a
gradient HPLC (Varian Model 5000, or equivalent) system equipped with a UV detector
(ISCO Model 1840 variable wavelength, or equivalent), an automatic sampler with a 25-
liL loop injector and two DuPont Zorbax ODS columns (4.6 x 250 mm), a recorder, and an
electronic integrator. Analysts are advised to experiment with their HPLC systems to
optimize chromatographic conditions for their particular analytical needs. Highest
chromatographic resolution and sensitivity are desirable but may not be achieved. The
separation of acrolein, acetone, and propionaldehyde should be a minimum goal of the
optimization.
142.4 The carbonyl compounds in the sample are identified and quantified by comparing
their retention times and area counts with those of standard DNPH derivatives.
Formaldehyde, acetaldehyde, acetone, propionaldehyde, crotonaldehyde, benzaldehyde and
o-, m-, p-tolualdehydes can be identified with a high degree of confidence. The
identification of butyraldehyde is less certain because it coelutes with isobutyraldehyde and
methyl ethyl ketone under the stated chromatographic conditions. Figure 12 illustrates a
typical chromatogram obtained with the gradient HPLC system.
142.5 The concentrations of individual carbonyl compounds are determined as outlined
in Section 12.
142.6 Performance criteria and quality assurance activities should meet those
requirements outlined in Section 13.
15. References
1. Riggin, R. M., Compendium of Methods for the Determination of Toxic Organic
Compounds in Ambient Air, EPA-600/4-84-041, U.S. Environmental Protection Agency,
Research Triangle Park, NC, April, 1984.
2. Tejada, S. B., "Standard Operating Procedure for DNPH-Coated Silica Cartridges for
Sampling Carbonyl Compounds in Air and Analysis by High-Performance Liquid
Chromatography," Unpublished, U.S. Environmental Protection Agency, Research Triangle
Park, NC, March 1986.
3. Tejada, S. B., "Evaluation of Silica Gel Cartridges Coated in situ with Acidified 2,4-
Dinitrophenylhydrazine for Sampling Aldehydes and Ketones in Air," Intern. J. Environ.
Anal Chem., 26:167-185, 1986.
Revised 9/30/89 Page 21
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Method IP-6A Formaldehyde
4. Quality Assurance Handbook for Air Pollution Measurement Systems, Volume II - Ambient
Air Specific Methods, EPA-600/4-77-027A, U.S. Environmental Protection Agency, Research
Triangle Park, NC, July 1979.
5. Levin, J. O., et al., "Determination of Sub-Part-Per-Million Levels of Formaldehyde in
Air Using Active or Passive Sampling on 2,4-Dinitrophenylhydrazine-Coated Glass Fiber
Filters and High-Performance Liquid Chromatography," XnoZ. Chem., 57:1032-1035, 1985.
6. Sigsby, J. E., Jr., et al., "Volatile Organic Compound Emissions from 46 In-Use
Passenger Cars," U.S. Environmental Protection Agency, Research Triangle Park, NC, 1984,
Unpublished.
7. Tejada, S. B., and Ray, W. D., "Aldehyde Concentration in Indoor Atmosphere of Some
Residential Homes," U.S. Environmental Protection Agency, Research Triangle Park, NC,
1982, Unpublished.
8. Perez, J. M., Lipari, F., and Seizinger, D. E., "Cooperative Development of Analytical
Methods for Diesel Emissions and Particulates - Solvent Extractions, Aldehydes and Sulfate
Methods," Presented at The Society of Automotive Engineers International Congress and
Exposition, Detroit, MI, February-March 1984.
9. Riggin, R. M., Technical Assistance Document for Sampling and Analysis of Toxic Organic
Compounds in Ambient Air, EPA-600/4-83-027, U.S. Environmental Protection Agency,
Research Triangle Park, NC, June, 1983.
10. Kring, E. V., et al., "Sampling for Formaldehyde in Workplace and Ambient Air
Environments - Additional Laboratory Validation and Field Verification of a Passive Air
Monitoring Device Compared with Conventional Sampling Methods," /. Am. Ind. Hyg.
Assoc., 45:318-324, 1984.
11. Ahonen, I., Priha, E., and Aijala, M-L, "Specificity of Analytical Methods Used to
Determine the Concentration of Formaldehyde in Workroom Air," Chemosphere, 13:521-
525, 1984.
12. Bufalmi, J. J., and Brubaker, K. L., "The Photooxidation of Formaldehyde at Low
Pressures," In: Chemical Reaction in Urban Atmospheres, American Elsevier Publishing
Co., New York, pp. 225-240, 1971.
13. Formaldehyde and Other Aldehydes, Committee on Aldehydes, Board of Toxicology
and Environmental Hazards, National Research Council, National Academy Press,
Washington, DC, 1981.
14. Nagda, N. L., Rector, H. E., and Koontz, M. D., Guidelines for Monitoring Indoor Air
Quality, Hemisphere Publishing Company, New York, 1987.
15. Arnts, R. R. and Tejada, S. B., "2,4-Dinitrophenylhydrazine Coated Silica Gel Cartridge
Method for Determination of Formaldehyde in Air: Identification of Ozone Interference,"
U.S. Environmental Protection Agency, Research Triangle Park, NC, unpublished.
Revised 9/30/89 Page 22
-------
Method IP-6A Formaldehyde
16. Allen, R. J., Wadder. R. A., and Ross, E. D., "Characterization of Potential Indoor
Sources of Ozone," Am. Ind. Hyg. Assoc. /., 39:466-471, 1986.
17. Selway, M. D., Allen, R. J., and Wadden, R. A., "Ozone Emissions from Photocopying
Machines," Am. Ind. Hyg. Assoc. /., 41:455-459, 1980.
Revised 9/30/89 Page 23
SO I
-------
Method IP-6A
Formaldehyde
Table 1. Sensitivity (ppb, v/v) of Sampling/Analysis Using
Adsorbent Cartridge Followed by HPLC
Sample Volume, L
Compound
Formaldehyde
Acetaldehyde
Acrolein
Acetone
Propionaldehyde
Crotonaldehyde
Butyraldehyde
Benzaldehyde
IsovaleraIdehyde
Valeraldehyde
o-toluaIdehyde
m-toluaIdehyde
p-toluaIdehyde
HexanaIdehyde
2,5-dimethyIbenzaIdehyde
12 2030 4050 100200300400500 1000
1.45
1.36
1.29
1.28
1.28
1.22
1.21
1.07
1.15
1.15
1.02
1.02
1.02
1.09
0.97
0.73
0.68
0.65
0.64
0.64
0.61
0.61
0.53
0.57
0.57
0.51
0.51
0.51
0.55
0.49
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.48
.45
.43
.43
.43
.41
.40
.36
.38
.38
.34
.34
.34
.36
.32
0.36
0.34
0.32
0.32
0.32
0.31
0.30
0.27
0.29
0.29
0.25
0.25
0.25
0.27
0.24
0.29
0.27
0.26
0.26
0.26
0.24
0.24
0.21
0.23
0.23
0.20
0.20
0.20
0.22
0.19
0.15
0.14
0.13
0.13
0.13
0.12
0.12
0.11
0.11
0.11
0.10
0.10
0.10
0.11
0.10
0.07
0.07
0.06
0.06
0.06
0.06
0.06
0.05
0.06
0.06
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.04
0.04
0.04
0.04
0.04
0.04
0.04
0.04
0.03
0.03
0.03
0.04
0.03
0.04
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.02
0.03
0.03
0.03
0.03
0.03
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
Note: ppb values are measured at 1 atm and 25'C; sample cartridge is eluted with 5 ml acetonitrile,
and 25 ml are injected onto HPLC column.
Note: Maximum sampling flow through a DNPH-coated Sep-PAK* cartridge is about 1.5 L per minute.
Revised 9/30/89
Page 24
-------
Method IP-6A
Formaldehyde
Table 2. Typical Performance Specifications for Formaldehyde Analyzer
Standard Range:
Low Level Range:
Reproducibility:
Minimum Detection:
Nonlinearity:
Zero Drift:
Span Drift:
Airflow Drift:
Zero Noise:
Lag Time:
Rise Time:
Fall Time:
Air Sample Flow Rate:
Optimum Temperature Range:
Relative Humidity Range:
0-5 ppm (adjustable from 0-0.25 up to 0-10 ppm
full scale)
0-250 ppb
1%
0.003 ppm (3 ppb) at 0-0.25 ppm full scale or 1%
of full scale
Less than 2% up to 2.5 ppm
Less than 2% per 24 hours
Less than 2% per 24 hours
Less than 1% per 24 hours
±0.3%
4-1/2 minutes (8 1/2 minutes with double coil)
(90%) 4-1/2 minutes
(90%) 4-1/2 minutes
0.5 liters per minute
60' to 80*F. Useable at 40° to 120*F.
5 to 95%
Revised 9/30/89
Page 25
-------
Method IP-6A
Formaldehyde
-------
Method IP-6A
Formaldehyde
DNPH-coated Sep-PAK®
Adsorbent Cartridge
Figure 2. Portable Sampling System for Adsorbent Cartridges
Revised 9/30/89
Page 27
-------
Method IP-6A
Formaldehyde
MASS FLOW
CONTROLLERS
OIL-LESS
PUMP
VENT
Couplings to
connect
DNPH-coated Sep-PAK®
Adsorbent Cartridges
(a) MASS FLOW CONTROL
ROTAMETER
VENT
DRY
TEST
METER
MM
—
•
•^
PUMP
\7
*
NEEDLE
VALVE
(DRY TEST METER SHOULD NOT BE USED
FOR FLOW OF LESS THAN 500 ml/minute)
Coupling to
connect
DNPH-coated
Sep-PAK®
Adsorbent
Cartridges
(b) NEEDLE VALVE/DRY TEST METER
Figure 3. Typical Sampling System Configurations
Revised 9/30/89
Page 28
56k
-------
Method IP-6A
Formaldehyde
n
Adsorbent
Tube
Vent
Figure 4. Diagram of Adsorbent Sampling Device for Airborne Aldehydes
Revised 9/30/89
Page 29
-------
Method IP-6A
Formaldehyde
Guard Analytical
Column Column
• Helium
Variable
Wavelength
UV/Fluorescence
Detector
Water Reservoir High
with Filter Pump
Binary
Proportioning
Valve
D
O
n
DD
n
D
— '""T*' — ~^
\
J
Data System
and Recorder
Acetonltrlle Reservoir
wHh Finer
Figure 5. Typical HPLC System
Revised 9/30/89
Page 30
-------
Method IP-6A
Formaldehyde
10 ml Glass
Syringe
Adsorbent
Tube
jfe^
£
Test!
Rac
Wast<
(a) RACK FOR COATING CARTRIDGES
Luer-Lok
Fitting ~"
Waste
Via!
IT
^_ _N2 Gas Stream
Adsorbent
Tubes
jj
I I
(b) RACK FOR DRYING DNPH-COATED CARTRIDGES
Figure 6. Syringe Rack for Coating and Drying Sample Cartridges
Revised 9/30/89
Page 31
-------
Method IP-6A
Formaldehyde
DIMPH Reagent
Solvent Front
10
20
30
40
TIME, min
Figure 7. Impurity Level of DNPH after Reciystallization
Revised 9/30/89
Page 32
-------
Method IP-6A
Formaldehyde
SAMPLING DATA SHEET
(One Sample per Data Sheet)
PROJECT:
SITE:
LOCATION:
INSTRUMENT MODEL NO:
PUMP SERIAL NO:
ADSORBENT CARTRIDGE INFORMATION:
Type:
Adsorbent:
SAMPLING DATA:
Start Time:
DATE(S) SAMPLED:
TIME PERIOD SAMPLED:
OPERATOR:
CALIBRATED BY:
Serial Number:.
Sample Number:.
Stop Time:
Time
Avq.
Dry Gas
Meter
Readinq
Rotameter
Readinq
Flow
Rate (Q)*,
mL/min
Indoor
Temperature,
•c
Barometric
Pressure,
mm Hq
Relative
Humiditv.%
Comments
* Flow rate from rotameter or soap bubble calibrator (specify which)
Total Volume Data (V ) (use data from dry gas meter, if available)
= (Final - Initial) Dry Gas Meter Reading, or
„ QI + Q2 + Q3 • • • QN x i__
Liters
Liters
N
1000 x (Sampling Time in Minutes)
Figure 8. Example Sampling Data Sheet
Revised 9/30/89
Page 33
-------
Method IP-6A
Formaldehyde
OPERATING PARAMETERS
HPLC
Column: Zorbax ODS or C-18 RP
Mobile Phase: 60% Acetonitrile/40% Water
Detector: Ultraviolet, operating at 360 nm
Flow Rate: 1 mL/min.
Retention Time: - 7 minutes for formaldehyde
Sample Injection Volume: 25 uL
m
o
I
10
TIME, min
20
Figure 9. Chromatogram of DNPH-Formaldehyde Derivative
Revised 9/30/89
Page 34
-------
Method IP-6A
Formaldehyde
OPERATING PARAMETERS
HPLC
Column: Zorbax ODS or C-18 RP
Mobile Phase: 60% Acetonitrile/40% Water
Detector: Ulltraviolet, operating at 360 nm
Flow Rate: 1 mL/min.
Retention Time: — 7 minutes for formaldehyde
Sample Injection Volume: 25 uL /a\
T
b
TIME-*
0.61 ug/mL
T
b
UJ
TIME-*
1.23ug/mL
UJ
-3
TIME-*
6.16ug/mL
CONG
.61 ug/mL
1 .23 ug/mL
6.16 ug/mL
12.32ug/mL
1 8.48 ug/mL
AREA
COUNTS
226541
452166
2257271
4711408
6953812
(d)
(e)
T
b
UJ
-3
TIME-*
12.32 ug/mL
TIME-*
18.48 ug/mL
Figure 10. HPLC Chromatogram of Varying Concentrations of
DNPH-Formaldehyde Derivative
Revised 9/30/89
Page 35
-------
Method IP-6A
Formaldehyde
o
o
to
o
o
in
o
o
h-
z>
o
O
s
< s
o
o
CM
O
o
CORRELATION COEFFICIENT:
0.9999
OPERATING PARAMETERS
HPLC
Column: Zorbax ODS or C-18 RP
Mobile Phase: 60% Acetonitriie/40% Water
Detector: Ultraviolet, operating at 360 nm
Flow Rate: 1 mL/min
Retention Time: - 7 minutes for formaldehyde
Sample Injection Volume: 25 uL
3 6 9 12 15 18
DNPH-Formaldehyde Derivative (ug/mL)
Figure 11. Typical Calibration Curve for Formaldehyde
Revised 9/30/89
Page 36
5JV
501
-------
Method IP-6A
Formaldehyde
DNPH
\J
PEAK IDENTIFICATION
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
IS
Coin pound
Formaldehyde
Acetaldehyde
Acroleln
Acetone
Propional dehyde
Crotonaldehyde
Butyraldehyde
Dental dehyde
Isovaleraldehyde
Valeraldehyde
o-Tolual dehyde
m-Toltul dehyde
p-Tolualdehyde
Hexal dehyde.
2,4-Olaethylben-
zal dehyde
Concentration,
ng/mL
1.140
1.000
1.000
1.000
1.000
1.000
0.90S
1.000
0.450
0.485
0.51S
0.505
0.510
1.000
0.510
14
13
15
I
10
20 30
TIME, min
40
Figure 12. Chromatographic Separation of DNPH Derivatives
of 15 Carbonyl Standards
Revised 9/30/89
Page 37
-------
Method IP-10A Respirable Particulate
6. Method Limitations and Limits of Detection
6.1. The limitations on the test method are a minimum weight of 20 micro grams of
particles on the filter, and a maximum loading of 600 micro grams/cm and minimum of
20 micro grams/cm2 on the filter.
6.2 The test method may be used at higher loadings if the flow rate can be maintained
constant (± 5%) and degradation of the aerosol preclasifier performance is not adversely
affected.
6.3 The MEM and PEM samplers' limit of detection (LOD) is a function of the weighing
room environment and the precision of the microbalance used to perform mass
measurements.
6.4 Using the recommended equipment specified in this procedure, a 12-hour LOD of 8
/ig/m3 can be achieved for the PEM, and 4 /Jg/m3 for the MEM.
6.5 Overall precision is ± 2 /tg/m3 to ±25 /ig/m3 during dust loading studies (10 to 100
/tg/m3) at a flow rate of 4 L/min. for each sampler.
7. Apparatus Description
7.1 Mieroenvironmental Exposure Monitor (MEM) Description
7.1.1 As illustrated in Figure 2, the MEM is subdivided into four sections: 1) an inlet
section, 2) a three-piece inertial impaction section, 3) the upstream section of the filter
holder; and 4) the downstream section of the filter holder.
7.12 Inlet section - the inlet section has four large, circumferential slots for aerosol
to enter the MEM. These horizontal inlet slots prevent very large particles, perhaps those
greater than 100-/mi aerodynamic diameter, from entering the MEM and placing an
additional particle burden on the downstream impaction plate. The inlet section also acts
as a cover, preventing large particles from entering the MEM by gravity settling. The inlet
section should be shown to be unbiased with respect to the particle size distribution being
sampled.
7.1.3 Impaction section - the impaction section consist of three separate parts: 1) a
nozzle, 2) an impaction plate(s), and 3) a part designed for mounting the impaction plate.
Two versions of the impactor assembly are available. With a one stage impactor plate
assembly, aerodynamic particles of < 10 /mi are allowed to pass around the impactor. plate
and subsequently collected in the lower filter. With the two stage impactor assembly, as
illustrated in Figure 2, those particles <2.5 /mi are collected on the lower filter. A time
share option provides the capability of using two heads with one pumping system. In this
way, the total sampling time can be programmed to two samplers, enabling the collection
of <2.5 /im and <10 fim paniculate matter in the same general environment. These
features could be used to sample in two locations or to collect carbon on quartz filters or
acid aerosols through a unit equipped with an ammonia denuder.
Revised 9/30/89 PaSe 7
75*-
-------
Method IP-6B
DETERMINATION OF FORMALDEHYDE AND OTHER
ALDEHYDES IN INDOOR AIR USING A CONTINUOUS
COLORIMETRIC ANALYZER
1. Scope
1.1 This method describes a procedure for indoor air sampling and analysis of
formaldehyde. The procedure employs an automated wet-chemical colorimetric analyzer
(CEA Instruments, Inc., 16 Chestnut St., P.O. Box 303, Emerson, NJ, 07630, Model TGM
555-FD, or equivalent) with a continuous signal output.
12 This analyzer is fully portable and can be placed on a tabletop or other appropriate
surface for monitoring formaldehyde in indoor air. Both air and liquid formaldehyde
standards can be analyzed.
2. Principle of Operation
2.1 General
2.1.1 The analyzer measures formaldehyde concentrations by monitoring the amount
of color change produced when specific reagents are combined with the air sample. The
au- sample to be analyzed is continuously drawn into the monitor by an internal vacuum
pump.
2.12 Any formaldehyde present in the sample is scrubbed with a sodium
tetrachloromercurate (TCM) solution containing a fixed quantity of sodium sulfite. Acid-
bleached pararosaniline is then added. The sampling lines and connecting tubing are made
of stainless steel, glass, FEP Teflon* or PFA Teflon*. Tygon* tubing or TFE Teflon* should
not be used. The air stream is transported to an absorber separator coil. For formaldehyde
absorption, a two stage liquid/gas separator removes the scrubbed air stream which is then
vented to the atmosphere through a vacuum pump.
2.13 All the glassware including the absorber coil and the liquid air separator are
mounted in an analytical module which is diagrammed in Figure 1. Unreacted reagent is
pumped through the reference cell of the dual beam colorimeter of the analyzer. The
colored reaction product flows through the sample cell. The colorimeter measures
electronically either the difference hi color or light absorption of the reagent before and
after the reaction with the gas, or the formation of the color from the addition of reagents.
2.1.4 Transmission of light through the flow cells is measured by a matched set of
photodetectors at a wavelength of 550 nm. The intensity of the color is directly
proportional to the concentration of the formaldehyde to be measured.
2.1.5 The electrical signal generated hi the colorimeter is amplified and fed to a digital
display, where it is read out as a percentage (%) of full scale.
22 Sample Collection and Analysis
22.1 Air flow - The sample air flow rate must be kept constant at 0.5 L/min for
accurate results. A potentiometer controls the air pump voltage and hence the flow rate.
Revised 9/30/89 . Page 3
5/7
-------
Method IP-6B Formaldehyde
The air flow rate should be periodically checked using a flowmeter. When a long sample
line is used, the flowmeter should be at the inlet of the sample line.
122 Drain system - Reacted solution is drained through a horizontal "tee" to an
appropriate waste container either external or internal to the analyzer.
2.2.3 Liquid pump - The formaldehyde analyzer uses an integral peristaltic-type pump
to transfer reagents to the scrubber and to the reaction and detection systems. The reagent
pump can run "dry" with no damage to the analyzer occurring.
3. Significance
3.1 In the early 1960's, procedures for measuring formaldehyde were being developed. At
a symposium in 1965, Yunghans and Munroe (1) discussed a modified Schiff procedure,
utilizing pararosaniline, developed by Lyles, Downing, and Blanchard (2) as the method of
choice for formaldehyde measurement. The chromotropic acid method of West and Sen
(3) was rejected due to problems associated with the handling of sulfuric acid, as well as
the MBTH procedure developed by Sawicki (4) and modified by Hauser (5) due to the time
needed to complete a preliminary reaction prior to adding the oxidizing agent. The basic
chemistry of the pararosaniline procedure is that formaldehyde is absorbed in a sodium
tetrachloromercurate (II) solution containing a fixed quantity of sulfur dioxide. Acid
bleached pararosaniline is added, and the intensity of the resultant purple dye, measured
at 555 nanometers, is proportional to the formaldehyde present. In 1976, CEA Instruments
(6) adapted this procedure to an automated wet chemical analyzer, to be known as the
Model TGM 555-FD.
32 Recent research has ben conducted which builds on successive modifications of the
pararosaniline method and the Model TGM-155-FD analyzer, eliminates the use of
tetrachloromercurate, and uses only pararosaniline and sodium sulfate based working
reagents. The recent modifications also use several additional time delay coils to increase
the reactants residence time. The analytical module was modified with additional tubing
and glassware and an additional debubbler was added to overcome the increased drag on
the system. Because this method does not use the toxic mercury working reagent, the
potential hazard of using this method in an indoor air testing environment is reduced. For
additional information on the modified pararosaniline method see references 7, 8 and 9.
4. Interferences
The colorimeter measures a chemical reaction electronically. The chemical reaction is
influenced by changes in atmospheric and operating conditions. The following are some
interferences that have been observed during extensive tests of the colorimeter.
4.1 Changes in air pressure and temperature - The flowmeter is calibrated at standard
atmospheric conditions. At low temperatures (40°-45°F) and high barometric pressures the
meter will display a reading which is 3% to 4% lower than the reading at which the unit
was calibrated. At temperatures between 60°F to 90°F, the unit will operate properly. At
temperatures above 90°F, the sensitivity of the unit decreases. At about 90°F, the absorbing
Revised 9/30/89 Page 4
-------
Method IP-6B Formaldehyde
solution becomes saturated. The manufacturer's specifications will provide instructions on
operating the analyzer at temperatures above 90°F.
4.2 Changes in light conditions - If the monitor is operated with the cover removed, the
sensing cells should be shielded from direct sunlight. A leakage of strong collimated light
into the light paths can affect the reading. No effect with scattered light has been observed.
4.3 Optimum responses of the unit will be achieved after running the unit for
approximately an hour. In particular, baseline and span noise will decrease significantly, as
will baseline drift.
4.4 Air bubbles and precipitated colored reactants are responsible for the majority of the
increases in noise and erratic response. Cleaning all lines and pump tubes when needed
will reduce or eliminate these problems. Air bubbles and erratic fluid levels in the sample
cell can be eliminated by flushing the unit with a suitable wetting agent (BRIJ 35 -Fisher
CS-285-2, or equivalent) (5% solution).
Caution: Do not use this wetting agent in conjunction with the reagents! Flush the unit
for half an hour with distilled water. Then flush with the diluted wetting agent solution for
an additional half hour, followed by a minimum of 1 hour of flushing with distilled water.
The unit can then be operated with the reagents.
4.5 The influence of atmospheric conditions on the chemical reaction cannot be changed.
However, if the observer takes into consideration The above interferences and accounts for
fluctuations that affect signal noise and baseline drift, the unit will give accurate results
within these limitations.
5. Reagents and Materials
5.1 Pararosaniline (PRA) chloride - specially purified pararosaniline chloride, 0.2% 1 M
hydrochloric acid must be used (CEA Instruments, Product No. CRP-61A Emerson, NJ or
Eastman Kodak, Product No. A14051, or Fisher Scientific, Pittsburgh, PA, Product No.
14051-A, or equivalent).
52 Sodium sulfite - prepared fresh daily with distilled water (Fisher Scientific, Pittsburgh,
PA, Product No. S-430, or equivalent).
53 Mercuric chloride - ACS grade, or equivalent.
5.4 Sodium chloride - ACS grade, or equivalent.
5.5 Hydrochloric acid - analytical grade, best source.
5.6 Distilled water - analytical grade, best source.
5.7 Permeation tube - permeation rate of approximately 750 ng/min per ppm of range
desired. For example, if the unit is to be calibrated over a full scale range of 0-5 ppm, an
output of about 3750 ng/min (i.e., 5 x 750) is required for proper calibration (Kin-Tek,
Texas City, Texas, or equivalent).
Revised 9/30/89 Page 5
•ov»
-------
Method IP-6B Formaldehyde
5.8 Alpha-polyoxymethylene - for preparation of permeation tubes.
5.9 Formaldehyde - 37% by weight in water, analytical grade,or equivalent.
5.10 Zero gas filter.
5.11 Mohr pipet - 1-mL graduated.
6. Reagent Preparation
6.1 Reagent Preparation and Consumption
6.1.1 Reagent 1 - Reagent 1 is a sodium sulfite solution and is used as part of the
working absorbing solution. This solution is prepared by dissolving 0.35 grams of sodium
sulfite in one liter of distilled water. This reagent must be made fresh daily.
6.1.2 Reagent 2 - Reagent 2 is a sodium tetrachloromercurate solution and is combined
with a fixed quantity of Reagent 1 to form the working absorbing solution. This is prepared
by dissolving 1.36 grams of mercuric chloride and 0.58 grams sodium chloride in
approximately 850 mL of distilled water. Make up to one liter with distilled water.
Caution: This reagent solution is extremely toxic and is readily absorbed through the skin.
6.13 Reagent 3 - Reagent 3 is a modified pararosaniline (PRA) solution and is added
to reagents 1 and 2 for color formation in the sample. This solution is prepared by diluting
50 mL of specially purified PRA to 250 mL with distilled water.
62 Reagent Consumption
This section provides nominal flow rates for reagents through the system.
6.2.1 Reagent 1 - The following flow rates for the reagent 1 solution (i.e., sodium
sulfite solution) are recommended for successful operation of the analyzer: 20 mL per hour
of continuous operation, 0.8 liters per 40 hours, and 3.4 liters per 168 hours.
622 Reagent 2 - The following flow rates for the reagent 2 solution (i.e., working
TCM solution) are recommended for successful operation of the analyzer: 20 mL per hour
of continuous operation, 0.8 liters per 40 hours, and 3.4 liters per 168 hours.
6.2.3 Reagent 3 - The following flow rates for the reagent 3 solution (i.e., working
PRA solution) are recommended for successful operation of the analyzer: 20 mL per hour
of continuous operation, 0.8 liters per 40 hours, and 3.4 liters per 168 hours.
7. Analyzer Calibration
The analyzer should undergo the following calibration procedures on a weekly basis, and
additionally when the lamp assembly and pump tubing are replaced.
7.1 Gaseous Formaldehyde Standards
7.1.1 The most reliable means of calibrating the formaldehyde analyzer is with certified
permeation tubes. Tubes prepared from alpha-polyoxymethylene should be used.
Note: The use of paraformaldehyde permeation tubes is not recommended due to their
apparent unstability and lack of reproducibility.
Revised 9/30/89 Page 6
-------
Method IP-6B Formaldehyde
7.1.2 For 0-5 ppm full scale using a gaseous standard of 2.5 ppm, adjust the analyzer
to read 50%. A calibration curve should be prepared using concentrations of 1, 2, 3,4 and
5 ppm. For ranges of 3 ppm or less, use standards equal to 0, 20, 40, 60, 80 and 100% of
full scale. The calibration of the unit should be checked at least once a month.
7.1.3 If a suitable permeation tube is used hi conjunction with an accurate controllable
calibrator (CEA Instruments, SC-100, or equivalent), consistently accurate and reliable
calibration of the analyzer for the analysis of HCHO can be achieved.
12 Liquid Formaldehyde Standards
7.2.1 As an alternate procedure, liquid standards can be prepared that can be
correlated to gaseous standards.
Note: When calibrating with liquid standards, the zero gas filter must be connected. The
exact weight and actual assay value of the formaldehyde solution, as well as the precise
pump tube flow rate of reagent 2, must be used in all calculations.
7.22 The stock solution is prepared by diluting 2.4 grams of formaldehyde that is 37%
by weight in water with one liter distilled water. The solution is approximately 888 mg/L.
Dilute 10 mL of the stock solution to 100 mL with distilled water. Dilute 5 mL of the this
solution to 100 mL with the working TCM solution. This dilution results in a liquid standard
equivalent to approximately 3.6 /il (i.e., 1 /Jg HCHO = 0.815 fiL) of formaldehyde.
Note: This solution is stable for at least three months.
723 Connect the zero gas filter to the air sample intake, and place reagent 2 line into
the standard solution to be analyzed. At the 0-5 ppm range, the calibration curve is only
linear up to approximately 3 ppm. The 2.5 ppm standard should be run and after
equilibrium achieved, adjust the digital readout to 50% of full scale. Using the diluted
stock standard solution without the TCM, dilute 8 mL to 100 mL with working TCM
solution. Repeat using 10 mL. Run the above 4 and 5 ppm liquid standards and prepare
a five point calibration curve using 0, 2.5, 4 and 5 ppm.
7.2.4 If the air sample flow rate (ASFR), absorption efficiency (AE), and liquid
standards flow rates (LSFR) are known, a liquid standard value can be expressed in an
equivalent gaseous standard for formaldehyde. The conversion formula is as follows under
the stated conditions:
Std. Concentration/ASFR X LSFR/AE = ppm
The liquid standard pump tube flow rate must be calibrated by placing a one mL Mohr
pipet graduated in 0.1 mL divisions in the line between the reagent container and the
pump. Lift the end of the reagent line out of solution, and allow an air bubble twice the
diameter of the pipet bore to enter. Time the air bubble through the pipet and determine
the exact flow rate, mL/min. Use this flow rate in calculating the equivalent gaseous
standard for formaldehyde in air.
Note: Dilute standards are not stable longer than 12 hours, and should therefore be freshly
prepared prior to use.
Revised 9/30/89 Page 7
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Method IP-6B Formaldehyde
8. Using the Analyzer
Operation of the analyzer consists of the following three basic steps: 1) pumping working
reagents through the system, 2) zeroing the unit, and 3) adjusting the span control. This
section is provided to familiarize the operator with performing those functions.
8.1 Pumping Reagents Through System
8.1.1 Attach the zero gas filter to the sample air inlet. The filter removes interfering
gases from the air and generates "zero air" for establishing a zero baseline.
8.1.2 Connect drain line to bottom of drain "tee." If desired, connect a suitable vent
line from air pump.
8.13 Place pump tubes in position around reagent pump rollers.
8.1.4 Ensure that tubing between reagent pump, analytical module, and reagent
containers is in accordance with the flow diagram provided in Figure 2.
8.1.5 Turn on power and activate air and reagent pumps. Place reagent feed lines one
at a time into distilled water and observe the liquid flow within the unit. Water should not
accumulate in the liquid air separator. Liquid should be pulled out of the separator faster
than it is pumped into the absorber coil. Thus the tube leaving the separator should have
slugs of liquid alternated with an ah- bubble. During start up, the liquid level in the sample
cell may rise into the upper bulb portion. This is due to a blockage in the drain line from
the sample cell. Pinch or clamp the tubing on top of the sample cell for a few moments
and the liquid level will drop. Repeat as necessary. If the drain still fails to operate
properly, check for kinks or blockages.
8.1.6 The liquid level in the sample cell should stabilize at the point where the square
glass begins to flare out into the bulb portion. The level is determined by the vertical height
of the drain "tee."
8.1.7 Once it is determined that all the liquid flows are normal (i.e., all pump tubes
pumping, no leaks or build-ups and sample cell level is regulating), remove reagent lines
from the distilled water and allow the reagent pump to pump out as much water as
possible. Turn off the unit and slip the pump tubes off the pump brackets so the tubes will
not kink.
8.2 Introducing Reagents and Zeroing The Unit
8.2.1 Prepare reagents 1, 2, and 3 according to Section 6.1. For convenience, reagent
kits may be purchased from some manufacturers (CEA Instruments, or equivalent) that
contain all necessary chemicals to prepare Reagents 1, 2, and 3.
822 If a recorder is used, zero it according to manufacturer's instructions, and attach
it to the analyzer using the recorder cable supplied by the manufacturer.
8.23 For faster start-up, pump out as much distilled water from the system as possible.
Drain any distilled water from the reference cell by removing tubing from bottom and top
fittings of the cell. Allow the water to run into a paper towel or small beaker, replace
tubing.
82.4 Perform Sections 7.2.1 to 7.2.4.
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Method IP-6B Formaldehyde
8.2.5 Place reagent feed lines into appropriate working reagents. Activate air and
liquid pump(s).
82.6 Observe that liquid flows are normal as described in Section 6.2.
8.2.7 Attach air flowmeter and adjust flow rate according to methodology and/or
calibration sheet supplied with the analyzer. Remove flowmeter and replace it with zero
gas filter or other source of zero air.
8.2.8 Set span control, range, and damp switches to settings of last calibration.
8.2.9 Allow the monitor to operate on zero air for approximately 30 minutes. After
the unit is stabilized, adjust zero control if necessary to give a readout of 000.
8.3 Adjusting Span Control With Gaseous Calibration Standards
8.3.1 Zero the unit as described in Section 8.2.
832 Attach source of known calibration gas to analyzer inlet.
8.3.3 The damp switch must be in the low (down) position.
83.4 After reading stabilizes, adjust span control to give appropriate digital readout.
Adjust range switch to standard (up) position or low level range (down) position as
required. Example: To calibrate the instrument for 0-2 ppm full scale with a calibration
gas of 1.5 ppm, adjust the span so that the readout is 075 (i.e., 75% of full scale).
83.5 Remove the calibration gas and replace the zero gas filter. Unit will return to
zero.
83.6 Return damp switch to normal operating position.
9. Formaldehyde Sampling and Analysis
9.1 Indoor Air Monitoring
After the unit has been zeroed and the span adjusted, remove the zero gas filter. The
analyzer is now monitoring the indoor air for formaldehyde.
92 Range Changing
Details for changing the measurement range of the various gas parameters are provided
with the manufacturer's operating instructions. Generally, there are two ways to change the
range: 1) by recalibration with a different gas or liquid standard or 2) by changing the
electronic sensitivity and/or sample air flow rate. This second method is useful for a quick
range change.
93 Shutdown Procedure
93.1 Place all reagent lines into distilled water.
932 Operate monitor until liquid leaving via drain is clear (15-30 minutes). If
necessary, flush out system with appropriate cleaning solution per manufacturer's
instructions.
933 Remove all reagent lines from distilled water and run monitor until all possible
liquid has been pumped out (15-30 minutes).
93.4 Set monitor power and pump power switches to off.
Revised 9/30/89 Page
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Method IP-6B Formaldehyde
93.5 Slip pump tube fittings off the metal slots to relax the pump tubes.
9.3.6 If desired, disconnect electrical and pumping connections at monitor. (External
115-volt AC source should be left connected with DC power switch in "down" position if
internal battery is to be recharged.)
10. Analyzer Maintenance
The analyzer is designed for continuous, long-term operation with a minimum of
maintenance. Periodic inspection of sample cell and glassware for a build-up of foreign
materials is necessary. Solutions should be replenished as required. Daily baseline and
calibration indications should be noted and adjusted as necessary. If excessive variation
occurs, consult the manufacturer's troubleshooting guide. Care must be taken not to scratch
the glass surfaces of the cells, or spill liquid into the sensing block. Reagents must never
be allowed to evaporate or dry out within the system. On any shutdown lasting more than
a few hours, the unit must be flushed with distilled water. Typical performance
specifications of the monitor are provided in Table 1.
10.1 Daily Maintenance
The following should be performed on a daily basis for successful operation of the monitor:
• check instrument air flow and adjust if necessary
• check zero baseline
• check reagent supply and replenish if necessary
10.2 Periodic Maintenance
The following should be performed on a periodic basis for continued proper operation of
the monitor:
• perform optical zero per Section 8.2
• perform dynamic calibrations per Section 8.3
• replace peristaltic pump tubes after 30 days of use
• replace lamp assembly
• clean flow cells
103 Instrument Cleaning
To clean the analyzer, place all reagent lines in distilled water. Run monitor for at least
30 minutes. Replace distilled water with IN nitric acid (i.e., cone. HNO3 cut 10:1 with
distilled water). Allow unit to run for one to two hours only. Flush unit for at least one
hour with distilled water.
11. Performance Criteria and Quality Assurance
11.1 Users should generate Standard Operating Procedures (SOPs) describing the following
activities in their laboratory: 1) assembly, calibration, and operation of the sampling system,
with make, and model of equipment used, 2) preparation, purification, storage, and handling
of sampling reagent and samples, 3) assembly, calibration, and operation of the HPLC
Revised 9/30/89 Page 10
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Method IP-6B Formaldehyde
system, with make and model of equipment used, and 4) all aspects of data recording and
processing, including lists of computer hardware and software used.
112 SOPs should provide specific stepwise instructions and should be readily available to
and understood by the laboratory personnel conducting the work.
12. References
1. Yunghans, S. T., and Munroe, W. A., Automation in Analytical Chemistry, Technicon
Symposium, New York, NY, September 8, 1965.
2. Lyles, G. R., Dowling, F. B., and Blanchard, V. J., Journal Air Pollution Control Assoc.,
Vol. 15:106, 1965.
3. West, P. W., and Sen, B. Z., Analytical Chemistry, Vol. 153:177, 1956.
4. Sawicki, E., Hauser, T. R., Stanley, T. W., and Elbert, W., Analytical Chemistry, Vol.
34:1460 A, 1962.
5. Hauser, T. R., and Cummins, R. L., Analytical Chemistry, Vol. 36:679, 1964.
6. Instrument Manual, CEA-Instruments, Inc., 16 Chestnut St., P.O. Box 303, Emerson,
NJ, 07630, Model TEM. 555-FO.
7. Miksch, R. R., Anthon, D. W., Fanning, L. Z., Hallowell, C. D., Revza, K., and
Glanville, G., "Modified pararosaniline method for the Determination of Formaldehyde in
Aii," Analytical Chemistry, 53(13):2118, 1981.
8. Walters, R. B., "Automated Determination of Formaldehyde in Air Without the Use of
Tetrachloromurcurate (11)," Am. Ind. Hyg. Assoc. J., 44(9):659, 1983.
9. Fortune, C. R., and Daughtrey, Jr., E. H., (NSI Environmental Science, RTP, NC),
Development of a Portable Continuous Monitor for Trace Levels of Formaldehyde in Air,
for presentation at the Air and Waste Management Association annual meeting, 1989.
Revised 9/30/89 Page 11
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Method IP-6B
Formaldehyde
Table 1. Typical Performance Specifications for Formaldehyde Analyzer
Standard Range:
Low Level Range:
Reproducibility:
Minimum Detection:
scale or 1% of full scale
Nonlinearity:
Zero Drift:
Span Drift:
Air Flow Drift:
Zero Noise:
Lag Time:
double
Rise Time:
Fall Time:
Air Sample Flow Rate:
Optimum Temperature Range:
Relative Humidity Range:
0-5 ppm
0-250 ppb (adjustable from 0-0.25 fpn
full scale or 1% of full scale)
1%
0.003 ppm (3 ppb) at 0-0.25 ppm full
Less than 2% up to 2.5 ppm
Less than 2% per 24 hours
Less than 2% per 24 hours
Less than 1% per 24 hours
± 0.3%
4-1/2 minutes (8-1/2 minutes with
coil)
(90%) 4-1/2 minutes
(90%) 4-1/2 minutes
0.5 liters per minute
60* to 80'F. Usable at 40° to 120°F.
5 to 95%
Revised 9/30/89
Page 12
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Method IP-6B
Formaldehyde
Vent
Vacuum
Pump
Reagent
Pump
Reagents
Recorder
Pararosaniline
Reference
Cell
Light
Source
Sample
Cell
T
Drain
Electronics
Solution
Hy///////////////////-
TSne Delay
CoD
Scrubbed
AT
Air Flow
Meter
Sample
Kt
Inlet
*v
Analytical Module
Absorber/
Separator
Figure 1. Flow Diagram of Formaldehyde Analyzer
Revised 9/30/89
Page 13
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Method IP-6B
Formaldehyde
To Top of Drain Tee
Top
Bottom
Figure 2. Flow Diagram of Reagents Through Analyzer
Revised 9/30/89
Page 14
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Method IP-6C
DETERMINATION OF FORMALDEHYDE AND OTHER
ALDEHYDES IN INDOOR AIR USING
PASSIVE SAMPLING DEVICE
1. Scope
2. Summary of Method
3. Significance and Use
4. Equipment
5. Reagents and Materials
6. Preparation, Purification And Application of Glass Fiber
Filters
6.1 Filter Preparation
6.2 Filter Treatment
6.3 Purification of 2,4-Dinitropenylhydrazine (DNPH)
6.4 Preparation of DNPH-Formaldehyde Derivative
6.5 Preparation of DNPH-Formaldehyde Standards
7. PSD Assembly
8. Sampling Procedure
9. Sample Analysis
9.1 Sample Preparation
9.2 HPLC Analysis
9.3 HPLC Calibration
10. Calculations
11. Performances Criteria and Quality Assurance
11.1 Standard Operating Procedures (SOP)
11.2 HPLC System Performance
11.3 Process Blanks
11.4 Method Precision and Accuracy
12. Detection of Other Aldehydes and Ketones
13. Evaluation of the Formaldehyde-PSD System
14. References
Revised 9/30/89 Page 1
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Method IP-6C
DETERMINATION OF FORMALDEHYDE AND OTHER
ALDEHYDES IN INDOOR AIR USING
PASSIVE SAMPLING DEVICE
1. Scope
1.1 In the past, active sampling devices have been the method of choice for the collection
of formaldehyde (CH2O) in indoor air. Active sampling devices are flowthrough devices
that require a mechanical means (pump) to move the sample to the collection medium.
More specifically, Compendium Method IP-6A describes a solid adsorbent procedure
wherein 2,4-dinitrophenylhydrazine (DNPH) is impregnated on commercially purchased
Sep-PAK* silica gel cartridges to capture formaldehyde and other aldehydes during active
sampling. After exposure to the indoor air, the cartridges are returned to the laboratory
for analysis utilizing high performance liquid chromatography (HPLC) analysis. These
solvent free sampling methods constitute a greater improvement over the impinger
techniques (1-5). Likewise, Compendium Method IP-6B utilizes a real time monitor for
detecting formaldehyde in indoor air.
«
12 In recent years (6-10) interest has been increasing in the use of diffusion-based passive
sampling devices (PSDs) for the collection of formaldehyde in indoor air. PSDs are more
attractive for indoor air because of their characteristics of small size, quiet operation (no
pump), and low unit cost. Diffusion sampling has been recognized as an efficient
alternative to pump based sampling.
13 Most importantly, epidemiologists believe that to determine health effects of aldehydes
on humans, the sampler must be either worn by people or be in close proximity to where
people spend most of their time indoors.
1.4 Since most people do not wish to carry noisy pump samplers on their person or have
them near their work, sleep, eat or play areas, passive samplers are ideal for personal
monitoring.
1.5 In recent years several diffusion samplers for formaldehyde have been extensively
validated for occupational monitoring in the Threshold Limit Value (TLV) range (11).
The DuPont Pro-TeK Badge (12), the 3-M (13) Formaldehyde Monitor 3750/51, the
modified Palmes (14) tube and the Air Quality Research PF-20 passive workplace monitors
have all been widely used in occupational monitoring. The National Institute of
Occupational Health has recently completed studies involving a simplified diffusion sampler
for detecting formaldehyde (15-16).
1.6 Since most diffusion samplers have low sampling rates, sampling times of five to ten
days or more are needed to quantitatively detect formaldehyde below the 0.1 ppm level.
Consequently, a more sensitive diffusion method is needed to measure formaldehyde levels
over a shorter period, typically a few hours.
1.7 To address the sensitivity issue, the USEPA has developed a passive sampling device
for monitoring indoor levels of formaldehyde (17).
Revised 9/30/89 Page 3
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Method IP-6C Formaldehyde
2. Summary of Method
2.1 The passive sampling method involves loading 2,4-dinitrophenylhydrazine on glass fiber
filters and placing them behind sets of diffusion barriers on each side of a containment
cavity of a PSD.
22 Formaldehyde and other aldehydes diffuse to the PSD sampler and react specifically
with the DNPH treated filters in the presence of an acid to form a stable DNPH-derivative
according to Picks first law of diffusion:
M = D (A/L) (C. - C0)
where:
M = mass flow, cm3/min
D = diffusion coefficient, cm2/min
A = cross sectional area of diffusion channel, cm2
L = length of diffusion channel, cm
C« = concentration of formaldehyde in air surrounding the PSD
C0 = concentration of formaldehyde at surface of the treated filter
2.3 After sampling is complete, the PSD sampler is capped, returned to the laboratory,
disassembled under a nitrogen blanket, extracted with acetonitrile and analyzed by high
performance liquid chromatography (HPLC).
2.4 Recent field studies (17) involving "Sick Building Syndrome (SBS)" have compared the
PSD method (Compendium IP-6C) with the established pump-based DNPH-coated
Sep-Pak* method (Compendium IP-6A). The results of the collocated samplers are shown
in Table 1. The agreement between the two sampling methods was shown to be good, and
the PSDs were found to be more convenient to use and less obtrusive than the pumped-
based samplers.
3. Significance and Use
3.1 Since the analysis of the indoor environment is influenced by many factors except the
method of sampling, an effort should be made to minimize interfering factors and maintain
air at normal conditions in the vicinity of the passive monitor.
32 Passive detection provides for time-integrated measurements. Passive monitors are
usually placed in an indoor environment over a sampling period of from 3 days to 1 year.
Due to the length of time involved with sampling, interfering factors should be anticipated
and eliminated where possible.
33 Placement and recovery of the monitors can be performed by unskilled personnel with
suitable instruction (even an occupant). Appendix C-3 of this compendium contains
guidance on procedures for placement of stationary passive monitors in the indoor
environment.
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Method IP-6C Formaldehyde
4. Equipment
4.1 Passive sampling device (PSD) - Scientific Instrumentation Specialists, P.O. Box 8941,
Moscow, ID, 83843, (see Figure 1).
42 Treated glass fiber filters - Whatman GF/B Glass Microfibre*, Whatman Inc., 9
Bridgwell Place, Clifton, NJ, 07014.
5. Reagents and Materials
5.1 2,4-Dinitrophenylhydrazine (DNPH)- Aldrich Chemical or J.T. Baker, reagent grade
or equivalent. Recrystallize at least twice with UV grade acetonitrile before use.
52 Acetonitrile - UV grade, Burdick and Jackson "distilled in glass," or equivalent.
5.3 Deionized-distilled water - charcoal filtered.
5.4 Perchloric Acid - analytical grade, best source.
5.5 Hydrochloric acid - analytical grade, best source.
5.6 Formaldehyde - analytical grade, best source.
5.7 Aldehydes and ketones - analytical grade, best source, used for preparation of DNPH
derivative standards (optional).
5.8 Ethanol or methanol - analytical grade, best source.
5.9 Nitrogen - high purity grade, best source.
5.10 Charcoal - granular, best source.
5.11 Helium - high purity grade, best source.
6. Preparation, Purification and Application of Glass Fiber Filters
6.1 Filter Preparation
6.1.1 Upon receipt of the 8"xlO" filter paper, inspect surfaces for soiling and abrasions.
6.12 Place the filter sheet on a marble slab.
6.1.3 Using a wooden mallet and a 33-mm circular diameter stainless steel die, cut the
desired number of filters needed for completion of the project objectives.
Note: One can purchase commercially available 37 mm Whatman GF/B Microfibre filter
and cut to the 33 mm size.
6.1.4 To prepare the filters for treatment, place five at a time in a Buchner funnel and
rinse with five 100 mL volumes of charcoal-filtered deionized water.
6.1.5 Remove the filters from the funnel and place in a vacuum oven at 60°C for 1
hour.
6.1.6 After drying, remove from the oven and store in a desiccator containing anhydrous
calcium sulfate until cooled to room temperature.
Revised 9/30/89 Page 5
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Method IP-6C Formaldehyde
62 Filter Treatment
Note: Formaldehyde contamination of the DNPH reagent is a frequently encountered
problem. The DNPH must be purified by multiple recrystallizations in UV grade
acetonitrile. Recrystallization is accomplished at 40-60^C by slow evaporation of the solvent
to maximize crystal size. The purified DNPH crystals are stored under UV grade
acetonitrile until use. Impurity levels of carbonyl compounds in the DNPH are determined
by HPLC prior to use and should be less than 0.025 mg/mL.
62.1 Remove five clean filters from the desiccator and place hi a glove box under a
nitrogen atmosphere.
622 Using a syringe add 0.5 mL of the purified (recrystallized) 2,4-
dinitrophenylhydrazine to the center of each filter.
623 Allow to equilibrate in the nitrogen atmosphere for 40 minutes. This will allow
the solution to diffuse completely throughout the filter.
62A After 40 minutes, remove from the glove box, place in a vacuum desiccator and
dry at room temperature (23°C) and 0.5 kPa for an additional 40 minutes.
62.5 After vacuum drying, place the filters in a sealed glass Petrie dish and store under
activated charcoal in metal cans with compression-sealed lids (paint cans) until use.
63 Purification of 2,4- Dinitrophenylhydrazine (DNPH)
Note: This procedure should be performed under a properly ventilated hood.
63.1 Prepare a supersaturated solution of DNPH by boiling excess DNPH in 200 mL
of acetonitrile for approximately one hour.
632 After one hour, remove and transfer the supernatant to a covered beaker on a
hot plate and allow gradual cooling to 40-60°C.
633 Maintain the solution at this temperature (40-60°C) until 95% of solvent has
evaporated.
63.4 Decant solution to waste, and rinse crystals twice with three times their apparent
volume of acetonitrile.
Note: Various health effects result from the inhalation of acetonitrile. At 500 ppm in air,
brief inhalation has produced nose and throat irritation. At 160 ppm, inhalation for 4 hours
has caused flushing of the face (2 hour delay after exposure) and bronchial tightness (5 hour
delay). Heavier exposures have produced systemic effects with symptoms ranging from
headache, nausea, and lassitude to vomiting, chest or abdominal pain, respiratory
depression, extreme weakness, stupor, convulsions and death (dependent upon concentration
and time).
63.5 Transfer crystals to another clean beaker, add 200 mL of acetonitrile, heat to
boiling, and again let crystals grow slowly at 40-60°C until 95% of the solvent has
evaporated.
63.6 Repeat rinsing process as described in Section 63.4.
63.7 Take an aliquot of the second rinse, dilute 10 times with acetonitrile, acidify with
1 mL of 3.8 M perchloric acid per 100 mL of DNPH solution,and analyze by HPLC.
Revised 9/30/89 Page 6
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Method IP-6C Formaldehyde
63.8 The chromatogram illustrated in Figure 2 represents an acceptable impurity level
of < 0.025 /Jg/mL of formaldehyde in recrystallized DNPH reagent. If the impurity level
is not acceptable for intended sampling application, repeat recrystallization.
63.9 Transfer the purified crystals to an all-glass reagent bottle, stopper, shake gently,
and let stand overnight. Analyze supernatant by HPLC according to Section 9. The
impurity level should be comparable to that shown in Figure 2.
6.3.10 If the impurity level is not satisfactory, pipet off the solution to waste, then add
25 mL of acetonitrile to the purified crystals. Rinsing should be repeated with 20 mL
portions of acetonitrile until a satisfactorily low impurity level in the supernatant is
confirmed by HPLC analysis. An impurity level of 40.025 mg/mL formaldehyde should
be achieved, as illustrated in Figure 2.
6.3.11 If the impurity level is satisfactory, add another 25 mL of acetonitrile, stopper
and shake the reagent bottle, then set aside. The saturated solution above the purified
crystals is the stock DNPH reagent.
63.12 Maintain only a minimum volume of saturated solution adequate for day to day
operation. This will minimize waste of purified reagent should it ever become necessary
to re-rinse the crystals to decrease the level of impurity for applications requiring more
stringent purity specifications.
63.13 Use clean pipets when removing saturated DNPH stock solution for any analytical
applications. Do not pour the stock solution from the reagent bottle.
6.4 Preparation of DNPH-Formaldehyde Derivative
6.4.1 Titrate a saturated solution of DNPH in 2N HC1 with formaldehyde (other
aldehydes or ketones may be used if their detection is desired).
6.4.2 Filter the colored precipitate, wash with 2N HC1 and water, and allow precipitate
to air dry.
6.43 Check the purity of the DNPH-formaldehyde derivative by melting point
determination or HPLC analysis. If the impurity level is not acceptable, recrystallize the
derivative in ethanol. Repeat purity check and recrystallization as necessary until
acceptable level of purity (e.g., 99%) is achieved.
6.5 Preparation of DNPH-Formaldehyde Standards
6.5.1 Prepare a standard stock solution of the DNPH-formaldehyde derivative by
dissolving accurately weighed amounts in acetonitrile.
6.52 Prepare a working calibration standard mix from the standard stock solution. The
concentration of the DNPH-formaldehyde compound in the standard mix solutions should
be adjusted to reflect relative distribution in a real sample.
Note: Individual stock solutions of approximately 100 mg/L are prepared by dissolving 10
mg of the solid derivative in 100 mL of acetonitrile. The individual solution is used to
prepare calibration standards containing the derivative of interest at concentrations of 0.5-20
ug/L, which spans the concentration of interest for most indoor air work.
6.53 Store all standard solutions in a refrigerator. They should be stable for several
months.
Revised 9/30/89 Page 7
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Method IP-6C Formaldehyde
7. Personal Sampling Device (PSD) Assembly
7.1 The PSD is a dual-faced sampler made up from a series of diffusion barriers placed
on either side of a cavity, as illustrated in Figure 3. This PSD is 3.8 cm in diameter, 1.2
cm in depth and weighs 36 grams.
7.1.1 With the aid of a glove box with a flow of nitrogen, remove the treated 2,4-
dinitrophenylhydrazine filter papers from the Petrie dish and place behind each set of
diffusion barriers of the PSD.
7.1.2 Reassemble the PSD, attach the protecting caps and place in small (0.5 pt) can.
12 For further protection from exposure, place the small cans into a large (1 gal.) can
containing activated charcoal until use.
8. Sampling Procedures
8.1 Take the PSD out of its protective shipping can and label properly with the start date,
time and sampling location identification.
8.2 Place the PSD in the appropriate area to be sampled.
Note: Representative sampling must be considered; therefore, placement of the PSD should
be determined with considerable planning.
83 Appropriate time and placement of the PSD should follow the following guidelines:
83.1 Avoid sampling when seasonal alterations in insulation or building tightness are
occurring or will occur during the sampling period.
$33 Avoid sampling if remodeling or redecorating is occurring. During the sampling
period there should be no changes in furnishings or appliances such as: carpeting, stoves,
HVAC systems, etc.
833 Open and close doors in a usual manner and keep windows closed if possible.
83.4 Ventilation should not be altered in any way during sampling.
83.5 Air Conditioning and heating should not be altered from normal use.
83.6 Humidifiers and dehumidifiers should not be used where sampling is being
performed.
83.7 Normal occupancy and activity should continue.
83.8 The placement of the sampler should not obstruct normal occupancy or activity.
83.9 Avoid locations near sinks, tubs, showers, washers.
83.10 Avoid locations near heating elements such as: direct sunlight, furnaces, electric
lights or electrically operated devices.
83.11 Avoid locations where a known draft or pressure differential occurs areas near
furnace vents, HVAC intake/exhaust, computer cooling fans and appliance fans.
8.4 Placement of the sampler should ideally be at least 8 inches below the ceiling, 20
inches above the floor and 6 inches from a wall.
Note: Outside walls should not be used, and suspension from the ceiling may be suitable.
Revised 9/30/89 Page 8
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Method IP-6C Formaldehyde
8.5 Remove the caps from the PSD. Sampling commences immediately. Place sampler at
predetermined location. Fill out needed information on Field Test Data Sheet.
8.6 Re-cap the PSD when the sampling time is complete.
8.7 Record the final time and date on the PSD label and the Field Test Data Sheet. Store
the PSD in a 1 gallon can containing activated charcoal at room temperature until analysis
is performed.
9. Sample Analysis
9.1 Sample Preparation
9.1.1 After exposure, the PSDs are returned to the lab in the labeled cans containing
activated charcoal.
9.1.2 Under a nitrogen blanket in a glove box, remove the PSD's from the can and
disassemble the filter cassette.
9.13 Place the exposed filters in a 35 mL screw-capped polypropylene bottle.
9.1.4 Add 5 mL of acetonitrile to the bottle, tightly cap and place in a sonification bath
at room temperature for 30 minutes.
9.1.5 At the end of 30 minutes, remove the polypropylene bottle from the sonification
bath, filter the anion extract through a Gelman Acrodisc disposable filter assembly into a
5 mL volumetric flask. Dilute to the 5 mL mark with acetonitrile. Label the flask with
sample identification. Pipet two aliquots into sample vials with Teflon-lined septa.
Analyze the first aliquot for the derivative carbonyls by HPLC. Store the second aliquot
in the refrigerator until sample analysis.
92 High Pressure Liquid Chromotography (HPLC) Analysis
9.2.1 The HPLC system is assembled and calibrated as described in Section 11.3 of
Compendium Method IP-6A. Before each analysis, the detector baseline is checked to
ensure stable conditions. The operating parameters are as follows:
Column - Zorbax ODS (4.6 mm inner diameter 25 cm), or equivalent
Mobile Phase - 60% acetonitrile/40% water, isocratic
Detector - Ultraviolet, operating at 360 nm
Flow Rate - 1.0 mL/min
Retention Time - Seven minutes for formaldehyde with one Zorbax ODS column. Thirteen
minutes for formaldehyde with two Zorbax ODS columns
Sample Injection Volume - 25 juL
922 The HPLC mobile phase is prepared according to Section 11.3.2 of Compendium
Method IP-6A, pump-based Sep-PAK DNPH-coated cartridge procedure.
923 The mobile phase is placed in the HPLC solvent reservoir and the pump is set at
a flow rate of 1.0 mL/min and allowed to pump for 20-30 minutes before the first analysis.
The detector is switched on at least 30 minutes before the first analysis, and the detector
output is displayed on a strip chart recorder or similar output device.
Revised 9/30/89 Page 9
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Method IP-6C Formaldehyde
9.2.4 A100-0L aliquot of the sample is drawn into a clean HPLC injection syringe. The
sample injection loop (25 ML) is loaded and an injection is made. The data system, if
available, is activated simultaneously with the injection, and the point of injection is marked
on the strip chart recorder.
9.2.5 After approximately one minute, the injection valve is returned to the "inject"
position and the syringe and valve are rinsed or flushed with acetonitrile/water mixture in
preparation for the next sample analysis.
Note: The flush/rinse solvent should not pass through the sample loop during flushing. The
loop is clean while the valve is in the "inject" mode.
92.6 After elution of the DNPH-formaldehyde derivative, data acquisition is terminated
and the component concentrations are calculated as described in Section 10.
9.2.7 After a stable baseline is achieved, the system can be used for further sample as
described above.
Note: After several PSD analyses, buildup on the column may be removed by flushing
with several column volumes of 100% acetonitrile.
9.2.8 If the concentration of analyte exceeds the linear range of the instrument, the
sample should be diluted with mobile phase, or a smaller volume can be injected into the
HPLC.
92.9 If the retention time is not duplicated (± 10%), as determined by the calibration
curve, the acetonitrile/water ratio may be increased or decreased to obtain the correct
elution time. If the elution time is too long, increase the ratio; if it is too short, decrease
the ratio.
Note: The chromatographic conditions described here have been optimized for the
detection of formaldehyde. Analysts are advised to experiment with their HPLC system
to optimize chromatographic conditions for their particular analytical needs.
9.3 HPLC Calibration
9 J.I Calibration standards are prepared in acetonitrile from the DNPH-formaldehyde
derivative. Individual stock solutions of 100 mg/L are prepared by dissolving 10 mg of
solid derivative in 100 mL of mobile phase. These individual solutions are used to prepare
calibration standards at concentrations spanning the range of interest
932 Each calibration standard (at least five levels) is analyzed three times and area
response is tabulated against mass injected. All calibration runs are performed as described
for sample analyses in Section 9.2. Using the UV detector, a linear response range of
approximately 0.05-20 /Jg/L should be achieved for 25-fiL injection volumes. The results
may be used to prepare a calibration curve. Linear response is indicated where a
correlation coefficient of at least 0.999 for a linear least-squares fit of the data
(concentration versus area response) is obtained. The retention times for each analyte
should agree within 2%.
933 Once linear response has been documented, an intermediate concentration
standard near the anticipated levels of each component, but at least 10 times the detection
limit, should be chosen for daily calibration. The day to day response for the various
components should be within 10% for analyte concentrations 1 Mg/mL or greater and within
Revised 9/30/89 Page 10
-------
Method IP-6C Formaldehyde
15-20% for analyte concentrations near 0.5 /-tg/mL. If greater variability is observed,
recalibratiion may be required or a new calibration curve must be developed from fresh
standards.
9.3.4 The response for each component in the daily calibration standard is used to
calculate a response factor according to the following equation:
RF = (Cc x V,)/RC
where:
RFC = response factor (usually area counts) for the component of interest, nanogram
injected/response unit
Cc = concentration of analyte in the daily calibration standard, mg/L
Vj = volume of calibration standard injected, fiL
Rc = response for analyte in the calibration standard, area counts
10. Calculations
10.1 The total mass of analyte (DNPH-formaldehyde) is calculated for each sample using
the following equation:
Wd = RFC x Rd x (VE/V,)
where:
Wd = total quantity of analyte in the sample, /tg
RFC = response factor calculated in Section 9.3.4
Rd = response for analyte in sample extract, blank corrected, (area counts or other
response units)
= [(As) (VD/VA) - (Ab)(Vb/Vs)]
where:
As = area counts, sample
A,, = area counts, blank
Vb = volume, blank, mL
Vs = volume, sample, mL
VD = redilution volume (if sample was rediluted)
VA = aliquot used for redilution (if sample was rediluted)
VE = final volume of sample extract, mL
Vj = volume of extract injected into the HPLC system, fiL
10.2 The concentration of formaldehyde in the original sample is calculated from the
following equation:
CA - Wd/[Vm (or Vs)] x 1000
where:
CA = concentration of analyte in the original sample, ng/L
Wd = total quantity of analyte in sample, blank corrected, /Jg
Revised 9/30/89 Page 11
-------
Method IP-6C Formaldehyde
Vm = total sample volume under ambient conditions*, L
Vs = total sample volume at 25°C and 760 mm Hg, L
* Based on sampling rate of 103 cm3/min.
The analyte concentrations can be converted to ppbv using the following equation:
CA (ppbv) = CA (ng/L) x (24.4/MWA)
where:
CA(ppbv) = concentration of analyte in parts per billion by volume. CA (ng/L) is calculated
using Vs.
MWA = molecular weight of analyte
11. Performance Criteria and Quality Assurance
Note: This section summarizes required quality assurance measures and provides guidance
concerning performance criteria that should be achieved within each laboratory.
11.1 Standard Operating Procedures (SOPs)
11.1.1 Users should generate SOPs describing the following activities in their laboratory:
1) assembly, calibration and operation of the sampling system, with make and model of
equipment used; 2) preparation, purification, storage, and handling of sampling reagent and
samples; 3) assembly, calibration, and operation of the HPLC system, with make and model
of equipment used; and 4) all aspects of data recording and processing, including lists of
computer hardware and software used.
11.1.2 SOPs should provide specific stepwise instructions and should be readily available
to and understood by the laboratory personnel conducting the work.
11.2 HPLC System Performance
112.1 The general appearance of the HPLC system should be similar to that illustrated
in Figure 4.
11.2.2 HPLC system efficiency is calculated according to the following equation:
N = 5.54 (tr/W1/2)2 x 1000
where:
N = column efficiency (theoretical plates)
tr = retention time of analyte, seconds
W1/2 = width of component peak at half height, seconds. A column efficiency of > 5,000
theoretical plates should be obtained.
11.2.3 Precision of response for replicate HPLC injections should be ± 10% or less day
to day, for analyte calibration standards at 1 /ig/mL or greater levels. At 0.5 /Jg/mL level
and below, precision of replicate analyses could vary up to 25%. Precision of retention
times should be ±2% on a given day.
Revised 9/30/89 Page 12
-------
Method IP-6C Formaldehyde
11.3 Process Blanks
1L3.1 At least one field blank or 10% of the field samples, whichever is larger, should
be shipped and analyzed with each group of samples. The number of samples within a
group and/or time frame should be recorded so that a specified percentage of blanks is
obtained for a given number of field samples.
1132 The field blank is not opened in the field, but is otherwise treated identically to
the samples. The performance criteria described in Section 63 should be met for process
blanks.
11.4 Method Precision and Accuracy
11.4.1 At least one duplicate sample or 10% of the field samples, whichever is larger,
should be collected during each sampling episode. Precision for field replication should
be ±20% or better.
11.4.2 Precision for replicate HPLC injections should be ± 10% or better, day to day,
for calibration standards.
11.4.3 At least one sample spike with analyte of interest or 10% of the field samples,
whichever is larger, should be collected.
11.4.4 Before initial use of the method, each laboratory should generate triplicate spiked
samples at a minimum of three concentration levels, bracketing the range of interest for
each compound. Triplicate nonspiked samples must also be processed. Spike recoveries
of >80 ± 10% and blank levels as outlined in Section 63 should be achieved.
12. Detection of other Aldehydes and Ketones
Note: The procedure outlined above has been written specifically for the sampling and
analysis of formaldehyde in ambient air using PSDs followed by HPLC analysis. Indoor
air contains other aldehydes and ketones. Optimizing chromatographic conditions by using
two Zorbax ODS columns in series and varying the mobile phase composition through a
gradient program will enable the analysis of other aldehydes and ketones. However, the
extended analytical finish discussed here and as part of Compendium Method EP-6A.
Section 14, has not been fully investigated using the PSD, but has using the Sep-Pak
adsorbent cartridge.
12.1 Sampling Procedures
The sampling procedure for other aldehydes and ketones is the same as in Section 8.
122 HPLC Analysis
12.2.1 The HPLC system is assembled and calibrated as described in Section 93. The
operating parameters are as follows:
Column - Zorbax ODS, two columns in series
Mobile Phase - Acetonitrile/water, linear gradient
Detector - Ultraviolet, operating at 360 nm
Flow Rate - 1.0 mL/min
Revised 9/30/89 Page 13
-------
Method IP-6C Formaldehyde
Sample Injection Vol. - 25 /iL
Step 1 - 60-75% acetonitrile/40-25% water in 30 minutes
Step 2 - 75-100% acetonitrile/25-0% water in 20 minutes
Step 3 - 100% acetonitrile for 5 minutes
Step 4 - 60% acetonitrile/40% water reverse gradient in 1 minute
Step 5 - 60% acetonitrile/40% water, isocratic for 15 minutes
12.2.2 The gradient program allows for optimization of chromatographic conditions to
separate acrolein, acetone, propionaldehyde, and other higher molecular weight aldehydes
and ketones in an analysis time of about one hour.
1223 The chromatographic conditions described herein have been optimized for a
gradient HPLC (Varian Model 5000) system with a UV detector (ISCO Model 1840
variable wavelength), an automatic sampler with a 25-0L loop injector and two DuPont
Zorbax ODS columns (4.6 x 250 mm), a recorder, and an electronic integrator. Analysts
are advised to experiment with their HPLC systems to optimize chromatographic conditions
for their particular analytical needs. Highest chromatographic resolution and sensitivity are
desirable but may not be achieved. The separation of acrolein, acetone, and
propionaldehyde should be a minimum goal of the optimization.
122.4 The carbonyl compounds in the sample are identified and quantified by
comparing their retention times and area counts with those of standard DNPH derivatives.
Formaldehyde, acetaldehyde, acetone, propionaldehyde, crotonaldehyde, and o-, m-,
p-tolualdehydes can be identified with a high degree of confidence. The identification of
butyraldehyde is less certain because it coelutes with isobutyraldehyde and methyl ethyl
ketone under the stated chromatographic conditions. Figure 5 illustrates the chromatogram
utilizing this system.
13. Evaluation of the Formaldehyde-PSD System
13.1 In a recent incident of "Sick Building Syndrome (SBS)," an indoor air quality study
was completed for samples and analysis of formaldehyde. In the study, formaldehyde PSDs
were placed next to the established Sep-PAK® DNPH-coated cartridges (17).
122 The results of the collected samples are illustrated in Table 1. The agreement
between the two sampling methods was shown to be good, and the PSD were found to be
more convenient than the pump-based Sep-PAK* DNPH-coated cartridges.
Note: Outdoor measurements are given for reference.
133 The formaldehyde levels determined were not atypical for older office buildings.
14. References
1. Andersson, K., Andersson, G., Nilsson, C.-A., and Levin, J.-O., "Chemosorption of
Formaldehyde on Amberlite XAD-2 Coated with 2,4-dinitrophenylhydrazine," Chemosphere,
Vol. 8:823, 1979.
Revised 9/30/89 Page 14
-------
Method IP-6C Formaldehyde
2. Beasley, R. K., Hoffman, C. E., Rueppel, M. L, and Worley, J. W., "Sampling of
Formaldehyde in Air with Coated Solid Sorbent and Determination by High Performance
Liquid Chromatography," AnaL Chem., Vol. 52:1110, 1980.
3. Matthews, T. G., and Howell, T. C, "Solid Sorbent for Formaldehyde Monitoring," AnaL
Chem., Vol. 54:1459, 1982.
4. Kennedy, E. R., and Hill Jr, R. H., "Determination of Formaldehyde in Air as an
Oxazolidine Derivative By Capillary Gas Chromatography.M/iai Chem., Vol. 54:1739,1982.
5. Levin, J.-O., Andersson, K., Lindahl, R., and Nilsson, C.-A,, "Determination of Sub-
Part-PerTMillion Levels of Formaldehyde in Air Using Active or Passive Sampling on 2,4-
dinitrophenylhydrazine-coated Glass Fiber Filters and High Performance Liquid
Chromatography," Anal Chem., Vol. 57:1032, 1985.
6. Kring, E. V., Thornley, G. D., Dessenberger, C, Lautenberger, W. J., and Ansul, G. R.,
"A New Passive Colorimetric Air Monitoring Badge for Sampling Formaldehyde in Air,"
Am. Ind. Hyg. Assoc. J., Vol. 43:786, 1982.
7. Kennedy, E. R., and Hull, R. D., "Evaluation of the Du Pont Pro-Tek Formaldehyde
Badge and the 3M Formaldehyde Monitor," Am. Ind. Hyg. Assoc. J., Vol. 47:94, 1986.
8. Stewart, P. A., Cubit, D. A., Blair, A., and Spirtas, R., "Performance of Two
Formaldehyde Passive Dosimeters," Appl Ind. Hyg., Vol. 2:61, 1987.
9. Geisling, K. L., Tashima, M. K., Girman, J. R., Miksch, R. R., and Rappaport, S. M., "A
Passive Sampling Device for Determining Formaldehyde in Indoor Air," Envim. Int., Vol.
8:153, 1982.
10. Levin, J.-O., Lindall, R., and Anderson, K., "Monitoring of Parts-Per-Billion Levels of
Formaldehyde Using a Diffusion Sampler," JAPCA, Vol. 39:44-47, 1989.
11. Hart, R. W., Terturro, A., and Neimeth, L., eds., "Report on the Consensus Workshop
on Formaldehyde," Environ. Health Perspect., Vol. 58:323, 1984.
12. Kring, E. V., Thornley, G. D., Dessenberger, C, Lautenberger, W. J., and Ansul, G.
R., "A New Passive Colorimetric Air Monitoring Badge for Sampling Formaldehyde in Air,"
Am. Ind, Hyg. Assoc. J., Vol. 43:786, 1982.
13. Kennedy, E. R., and Hull, R. D., "Evaluation of the Du Pont Pro-Tek Formaldehyde
Badge and the 3M Formaldehyde Monitor," Am. Ind. Hyg. Assoc. J., Vol. 47:94, 1986.
14. Stewart, P. A., Cubit, D. A., Blair, A., and Spirtas, R., "Performance of Two
Formaldehyde Passive Dosimeters," Appl Ind. Hyg., Vol. 2:61, 1987.
15. Geisling, K. L., Tashima, M. K., Girman, J. R., Miksch, R. R., and Rappaport, S. M.,
"A Passive Sampling Device for Determining Formaldehyde in Indoor Air," Envim. Int., Vol.
8:153, 1982.
Revised 9/30/89 Page 15
-------
Method IP-6C Formaldehyde
16. Gammage, R. B., and Hawthorne, A. R., "Current Status of Measurement Techniques
and Concentrations of Formaldehyde in Residences," Formaldehyde-Analytical Chemistry
and Toxicology, Advances in Chemistry Series 210, American Chemical Society, Washington,
1985, p. 117.
17. Mulik, J. D., Lewis, R. G., and McClenny, W. A., "Modification of a High-Efficiency
Passive Sampler to Determine Nitgrogen Dioxide or Formaldehyde in Mr," Anal Chem,,
Vol. 61(2):187-189, 1989.
Revised 9/30/89 Page 16
-------
Method IP-6C
Formaldehyde
Table 1. Comparative Study of the PSD Sampler With the
Active Sep-PAK® Cartridge Sampler
Concentration3, /ig/m3
Day 1
Office Method
1
2
3
4
PSD1
Sep-PAK®2
PSD
Sep-PAK®
PSD
Sep-PAK®
PSD
Sep-PAK®
0700- 1900
21.2,
32.8,
22.0
24.
25.
26.
20.
.5
.5
.6
.4
27.2"
33.2
1900- 0700
38.4,
38.8,
28.6
31.8
29.1
31.8
30.6
38.4
41.0
28.2
Daj
0700- 1900
28.7
22.0
19.9
30.8
30.6
22.4
26.2
Mean
29.8
33.
24,
25.
28.
29.
24.
27.2
Outdoors,
roof Sep-PAK®
4.2
4.9
1.8
3.6
53)
1 Compendium Method IP-6A
2 Compendium Method IP-6C
3 Average room temperature of 25"C
4 Paired values represent collocated samples
Revised 9/30/89
Page 17
-------
Method IP-6C
Formaldehyde
Figure 1. Passive Sampling Device (PSD) for Monitoring Formaldehyde
Revised 9/30/89
Page 18
-------
Method IP-6C
Formaldehyde
DNPH Reagent
n
Solvent
Front
JL
JL
0
10 20 30 40
TIME, min
Figure 2. Impurity Level of DNPH After Recrystallization
Revised 9/30/89
Page 19
-------
Method 1P-6C
Formaldehyde
Protective Cap
Internal 'C* Clip
Perforated Plate
200 Mesh Diffusion Screen
Internal 'C' Clip
Perforated Plate
200 Mesh Diffusion Screen
Treated Filter
Body
Treated Filter
200 Mesh Diffusion Screen
Perforated Plate
Internal 'C' Clip
Perforated Plate
200 Mesh Diffusion Screen
Internal 'C Clip
Protective Cap
Figure 3. Exploded View of the Passive Sampling Device (PSD)
Revised 9/30/89
Page 20
-------
Method IP-6C
Formaldehyde
Guard Analytical
Column Column
Water Reservoir High Pressre
with Filter Pump
Data System
and Recorder
•Mixer
UV/Fluorescence
Detector
Binary
Proportioning
Valve
Helium
Acetonltrlle Reservoir
with FlHer
Figure 4. Typical Configuration Associated with a
High Performance Liquid Chromatographic Analytical System
Revised 9/30/89
Page 21
-------
Method IP-6C
Formaldehyde
PEAK IDENTIFICATION
DNPH
\J
u
VJ
Number
I
2
3
4
5
S
7
8
9
10
11
12
13
14
15
Compound
Fornal dehyde
Ace til dehyde
Acrolein
Acetone
Propionaldehyde
Cro tonal dehyde
Butyral dehyde
Benzaldehyde
Isovaleraldehyde
Valeraldthyde
o-Tolual dehyde
•-Tolual dehyde
p-Toluil dehyde
Hexaldehydc.
2.4-01«ethylben-
zal dehyde
Concentration,
ug/mt
1.140
1.000
1.000
1.000
1.000
1.000
0.905
1.000
0.4SO
0.485
0.515
0.505
0.510
1.000
0.510
10
20
30
40
TIME, min
Figure 5. Chromatographic Separation of DNPH Derivatives of 15 Carbonyl Standards
Revised 9/30/89
Page 22
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Chapter IP-7
DETERMINATION OF BENZO(a)PYRENE [B(a)P] AND OTHER
POLYNUCLEAR AROMATIC HYDROCARBONS (PAHs) IN INDOOR AIR
1. Scope
1.1 Polynuclear aromatic hydrocarbons (PAHs) have received increased attention in recent
years in indoor air pollution studies because some of these compounds are highly
carcinogenic or mutagenic. In particular, benzo[a]pyrene (B[a]P) has been identified as
being highly carcinogenic. To understand the extent of human exposure to B[a]P and other
PAHs, reliable sampling and analytical methods are necessary. This document describes
a sampling and analysis procedure for B[a]P and other PAHs involving a combination
quartz filter/adsorbent cartridge with subsequent analysis by gas chromatography (GC) with
flame ionization (FI) and mass spectrometry (MS) detection (GC-FI and GC-MS) or high
performance liquid chromatography (HPLC).
2. Significance
2.1 Only limited information is currently available on the quality of indoor air. Since most
of the population spends a major part of each day indoors, the indoor air quality may be
a more important component of the risk to which the public is subjected than is the outdoor
air quality. Recent trends towards energy-efficient building construction typically result in
significant reductions in the indoor-outdoor air exchange rate. This fact, coupled with the
increasing use of alternative heating sources in homes, results in a potential for
concentrations of PAHs to reach undesirable levels.
2.2 Many research and monitoring efforts have focused on assessing and improving the
quality of indoor air. Several studies have demonstrated that some PAHs and nitrated PAH
found in indoor air are potent carcinogens, mutagens, or both. Because people spend more
than 80% of their time indoors, there is increasing concern over human exposure to these
and other semivolatile organic compounds in homes, workplaces, and schools.
2.3 Historically, sampling techniques have been categorized according to sampling flow
rates. Traditionally, these categories are:
Sampling Nominal Flow Rate, Compendium
Approach L/min Method
High volume > 100 IP-7
Medium volume 10 - 100 IP-9, IP-7
Low volume < 10 IP-10, IP-8, IP-6,
IP-5, IP-1, IP-2
Current sampling techniques for semivolatile organic compounds require a large volume of
air to be sampled in order to reach needed detection limits. Traditionally this has been
accomplished utilizing the high volume air sampler. The use of available high volume air
samplers in occupied residences is not practicable due to the noise they emit, the very high
flow rates they employ, and their size. Due to these and other limitations, a medium
Revised 9/30/89 ~ Page i
-------
volume air sampling system (20 Lpm) suitable for use in residential environments has been
developed and evaluated. The flow rate achievable with this device is adequate for at least
24 hour time resolution of typical concentrations of most PAHs of interest. The system is
quiet, transportable, and relatively unobtrusive, making it attractive for use in sampling in
occupied residences or workplaces.
Revised 9/30/89 Page ii
-------
Method IP-7
DETERMINATION OF BENZO(a)PYRENE [B(a)P] AND OTHER
POLYNUCLEAR AROMATIC HYDROCARBONS (PAHs) IN INDOOR AIR
1. Scope
2. Applicable Documents
3. Summary of Method
4. Significance
5. Definitions
6. Interferences
7. Safety
8. Apparatus
8.1 Sample Collection
8.2 Sample Clean-up and Concentration
8.3 Sample Analysis
8.3.1 Gas Chromatography (GC) with Flame
lonization Detection (FID)
8.3.2 GC with Mass Spectroscopy Detection
Coupled with Data Processing System
(GC-MS-DS)
8.3.3 High Performance Liquid Chromatography
(HPLC) System
9. Reagents and Materials
9.1 Sample Collection
9.2 Sample Clean-up and Concentration
9.2.1 Soxhlet Extraction
9.2.2 Solvent Exchange
9.2.3 Column Clean-up
9.3 Sample Analysis
9.3.1 Gas Chromatography Detection
9.3.2 High Performance Liquid Chromatography
Detection
10. Preparation of Sampling Filter and Adsorbent
10.1 Sampling Head Configuration
10.2 Glass Fiber Filter Preparation
10.3 XAD-2 Adsorbent Preparation
10.4 PUF Sampling Cartridge Preparation
11. Sample Collection
11.1 Description of Sampling Apparatus
11.2 Calibration of Sampling System
11.3 Sample Collection
113.1 Monitor Placement
11.3.2 Sample Module Loading
11.3.3 Powering Medium Volume Sampling Unit
11.3.4 Data Logger Unit Start-Up
Revised 9/30/89 ~~~ PageT
F>
-------
Method IP-7 PAHs
11.3.5 Sampling
11.3.6 Sample Retrieval
12. Sample Clean-up and Concentration
12.1 Sample Identification
12.2 Soxhlet Extraction and Concentration
12.3 Solvent Exchange
12.4 Sample Clean-up by Solid Phase Exchange
12.4.1 Method 610 Clean-up Procedure
12.4.2 Lobar Prepacked Column Procedure
12.4.3 Aminosilane Column Procedure
13. Gas Chromatography with Flame lonization Detection
13.1 Analytical Techniques
13.2 Analytical Sensitivity
13.3 Analytical Assembly
13.4 GC Calibration
13.4.1 External Standard Calibration Procedure
13.4.2 Internal Standard Calibration Procedure
13.5 Retention Time Windows Determination
13.6 Sample Analysis
14. Gas Chromatography with Mass Spectroscopy Detection
14.1 Analytical System
14.2 Operation Parameters
14.3 Calibration Techniques
14.3.1 External Standard Calibration Procedure
14.3.2 Internal Standard Calibration Procedure
14.4 Sample Analysis
14.5 GC-MS Performance Tests
14.5.1 Daily DFTPP Tuning
14.5.2 Daily Single-Point Initial Calibration Check
14.5.3 12-hour Calibration Verification
14.5.4 Surrogate Recovery
15. High Performance Liquid Chromatography (HPLC)
Detection
15.1 Introduction
15.2 Solvent Exchange to Acetonitrile
15.3 HPLC Assembly
15.4 HPLC Calibration
15.5 Sample Analysis
15.6 HPLC System Performance
15.7 HPLC Method Modification
Revised 9/30/89 Page 2
-------
Method IP-7 PAHs
16. Quality Assurance/Quality Control (QA/QC)
16.1 General System QA/QC
16.2 Process, Field and Solvent Blanks
16.3 Gas Chromatography with Flame lonization
Detection
16.4 Gas Chromatography with Mass Spectroscopy
Detection
16.5 High Performance Liquid Chromatography
Detection
17. Calculations
17.1 Sample Volume
17.2 Sample Concentration
17.2.1 Gas Chromatography with Flame lonization
Detection
172.2 Gas Chromatography with Mass
Spectroscopy Detection
17.2.3 High Performance Liquid Chromatography
Detection
17.3 Sample Conversion from ng/m3 to ppbv
18. Acknowledgements
19. References
Revised 9/30/89 Page 3
-------
Method IP-7
DETERMINATION OF BENZO(a)PYRENE [B(a)P] AND OTHER
POLYNUCLEAR AROMATIC HYDROCARBONS (PAHs) IN INDOOR AIR
1. Scope
1.1 Polynuclear aromatic hydrocarbons (PAHs) have received increased attention in recent
years in indoor air pollution studies because some of these compounds are highly
carcinogenic or mutagenic. In particular, benzo[a]pyrene (B[a]P) has been identified as
being highly carcinogenic. To understand the extent of human exposure to B[a]P and other
PAHs, reliable sampling and analytical methods are necessary. This document describes
a sampling and analysis procedure for B[a]P and other PAHs involving a combination
quartz filter/adsorbent cartridge with subsequent analysis by gas chromatography (GC) with
flame ionization (FI) and mass spectrometry (MS) detection (GC-FI and GC-MS) or high
performance liquid chromatography (HPLC). The analytical methods are modifications of
EPA Test Method 610 and 625, Methods for Organic Chemical Analysis of Municipal and
Industrial Wastewater, and Methods 8000, 8270, and 8310, Test Methods for Evaluation of
Solid Waste.
1.2 Fluorescence methods were among the very first methods used for detection of B[a]P
and other PAHs as carcinogenic constituents of coal tar (1-7). Fluorescence methods are
capable of measuring subnanogram quantities of PAHs, but tend to be fairly non-selective.
The normal spectra obtained are often intense and lack resolution. Efforts to overcome
this difficulty led to the use of ultraviolet (UV) absorption spectroscopy (8) as the detection
method coupled with pre-speciated techniques involving liquid chromatography (LC) and
thin layer chromatography (TLC) to isolate specific PAHs, particularly B[a]P. As with
fluorescence spectroscopy, the individual spectra for various PAHs are unique, although
portions of spectra for different compounds may be the same. As with fluorescence
techniques, the possibility of spectra overlap requires complete separation of sample
components to insure accurate measurement of component levels. Hence, the use of UV
absorption coupled with pre-speciation involving LC and TLC and fluorescence spectroscopy
has declined and is now being replaced with the more sensitive high performance liquid
chromatography (9) with UV/fluorescence detection or highly sensitive and specific gas
chromatography with either flame ionization or mass spectroscopy (10-11) detection.
1.3 The choice of GC and HPLC as the recommended procedures for analysis of B[a]P
and other PAHs are influenced by then- sensitivity and selectivity, along with their ability
to analyze complex samples. This method provides for both GC and HPLC approaches
to the determination of B[a]P and other PAHs in the extracted sample.
1.4 The analytical methodology is well defined, but the sampling procedures can reduce
the validity of the analytical results. Recent studies (12-15) have indicated that nonvolatile
PAHs (vapor pressure < 10"8 mm Hg) may be trapped on the filter, but post-collection
volatilization problems may distribute the PAHs downstream of the filter to the back-up
adsorbent. A wide variety of adsorbents such as Tenax®, XAD-2 and polyurethane foam
(PUF) have been used to sample B[a]P and other PAH vapors. All adsorbents have
demonstrated high collection efficiency for B[a]P in particular. In general, XAD-2 resin has
Revised 9/30/89 Page 5
-------
Method IP-7 PAHs
a higher collection efficiency (16-17) for volatile PAHs than PUF, as well as a higher
retention efficiency. However, PUF cartridges are easier to handle in the field and
maintain better flow characteristics during sampling. Likewise, PUF has demonstrated its
capability in sampling organochlorine pesticides, polychlorinated biphenyls (18) and
polychlorinated dibenzo-p-dioxins (19). However, PUF has demonstrated a lower recovery
efficiency and storage capability for naphthalene and B[a]P, respectively, than XAD-2.
There have been no significant losses of PAHs up to 30 days of storage at room
temperature (23°C) using XAD-2. It also appears that XAD-2 resin has a higher collection
efficiency for volatile PAHs than PUF, as well as a higher retention efficiency for both
volatile and reactive PAHs. Consequently, while the literature cites weaknesses and
strengths of using either XAD-2 or PUF, this method covers both the utilization of XAD-
2 and PUF as the adsorbent to address post collection volatilization problems associated
with B[a]P and other reactive PAHs.
1.5 This method covers the determination of B[a]P specifically by both GC and HPLC and
enables the qualitative and quantitative analysis of other PAHs (see Figure 1). They are:
Acenaphthene Benzo(k)fluoranthene*
Acenaphthylene Chrysene
Anthracene Dibenzo(a,h)anthracene
Benzo(a)anthracene Fluoranthene
Benzo(a)pyrene Fluorene
Benzo(b)fluoranthene* Indeno(l,2,3-cd)pyrene
Benzo(e)pyrene Naphthalene
Benzo(g,h,i)perylene Phenanthrene
Pyrene
* Not well resolved by GC. Typically the identified benzo(k)fluoranthene is a mixture of
benzo(k)fluoranthene and benzofluoranthene.
The GC and HPLC methods are applicable to the determination of PAHs compounds
involving two member rings or higher. Nitro-PAHs have not been fully evaluated using this
procedure; therefore, they are not included in this method. When either of the methods
is used to analyze unfamiliar samples for any or all of the compounds listed above,
compound identification should be supported by both techniques.
1.6 With careful attention to reagent purity and optimized analytical conditions, the
detection limits for GC and HPLC methods range from 1 ng to 10 pg which represents
detection of B[a]P and other PAHs in filtered air at 120 pg/m3.
2. Applicable Documents
2.1 ASTM Standards
2.1.1 Method D1356 - Definitions of Terms Relating to Atmospheric Sampling and
Analysis.
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Method IP-7 PAHs
2.12 Method E260 - Recommended Practice for General Gas Chromatography
Procedures.
2.1.3 Method E355 - Practice for Gas Chromatography Terms and Relationships.
2.1.4 Method E682 - Practice for liquid Chromatography Terms and Relationships.
2.1.5 Method D-1605-60 - Standard Recommended Practices for Sampling Atmospheres
for Analysis of Gases and Vapors.
22 Other Documents
2.2.1 Existing Procedures (19-28).
222 Air Studies (29-31).
223 U.S. EPA Technical Assistance Document (32).
22 A General Metal Works Operating Procedures for Model PS 1 Sampler, General Metal
Works, Inc., Village of Cleves, Ohio.
3. Summary of Method
3.1 Filters and adsorbent cartridges (containing XAD-2 or PUF) are cleaned in solvents
and vacuum dried. The filters and adsorbent cartridges are stored in screw-capped jars
wrapped in aluminum foil (or otherwise protected from light) before careful installation
on the sampler.
Note: Insure that the cleaned filters and adsorbent cartridges have all traces of solvent
removed. Specifically, residual dichloromethane has been a contributor to larger than
expected indoor concentrations of dichloromethane due to residuals on the filter and
adsorbent cartridges after cleaning.
32 Approximately 30 m3 of indoor air is drawn through the filter and adsorbent cartridge
using a medium flow rate indoor air sampler or equivalent (breakthrough of less than 10%
of target compounds at a flow rate of 20 Lpm has not been a problem with a total sample
volume of 30 m3).
3.3 The amount of air sampled through the filter and adsorbent cartridge is recorded, and
the filter and cartridge are placed in an appropriately labeled container and shipped along
with blank filter and adsorbent cartridges to the analytical laboratory for analysis.
3.4 The filters and adsorbent cartridge are extracted by Soxhlet extraction with appropriate
solvent. The extract is concentrated by Kuderna-Danish (K-D) evaporator, followed by
silica gel cleanup using column Chromatography to remove potential interferences prior to
analysis by either GC-FID or HPLC.
Note: If GC-MS is the chosen analytical scheme, cleanup may not be necessary for most
indoor air samples.
3.5 The eluent is further concentrated by K-D evaporation, then analyzed by either GC
equipped with FI or MS detection or HPLC. The analytical system is verified to be
operating properly and calibrated with five concentration calibration solutions, each
analyzed in triplicate.
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Method IP-7 PAHs
3.6 A preliminary analysis of the sample extract is performed to check the system
performance and to ensure that the samples are within the calibration range of the
instrument. If necessary, recalibrate the instrument, adjust the amount of the sample
injected, adjust the calibration solution concentration, and adjust the data processing system
to reflect observed retention times, etc.
3.7 The samples and the blanks are analyzed and used (along with the amount of air
sampled) to calculate the concentration of B[a]P in indoor air.
3.8 Other PAHs can be determined both qualitatively and quantitatively through
optimization of the GC or HPLC procedures.
4. Significance
4.1 Only limited information is currently available on the quality of indoor air. Since most
of the population spends a major part of each day indoors, the indoor air quality may be
a more important component of the risk to which the public is subjected than is the outdoor
air quality. Recent trends towards energy-efficient building construction typically result in
significant reductions in the indoor-outdoor air exchange rate. This fact, coupled with the
increasing use of alternative heating sources in homes, results in a potential for
concentrations of PAHs to reach undesirable levels.
4 2 Many research and monitoring efforts have focused on assessing and improving the
quality of indoor air. Several studies (33-41) have demonstrated that some PAH's and
nitrated PAH found in indoor air are potent carcinogens, mutagens, or both. Because
people spend more than 80% of their time indoors, there is increasing concern over human
exposure to these and other semivolatile organic compounds in homes, workplaces, and
schools.
4.3 Current sampling and analytical techniques for these semivolatile organic compounds
require a large volume of air to be sampled in order to reach needed detection limits.
Traditionally this has been accomplished utilizing the high volume (1400 Lpm) air sampler,
as outlined in Compendium Method TO-13, Compendium of Methods for the Determination
of Toxic Organic Compounds in Ambient Air (18). The use of available high volume air
samplers in occupied residences is not practicable due to the noise they emit, the very high
flow rates they employ, and their size. Due to these and other limitations, a lower flow (224
Lpm) acoustically enclosed high volume sampling system (see Figure 2) suitable for use hi
residential environments has been developed and evaluated (42). The flow rate achievable
with this device is adequate for at least eight hour time resolution of typical concentrations
of most PAHs of interest. The system is quiet, transportable, and relatively unobtrusive.
The acoustic insulation of the sampler allows it to meet a noise criterion of 35, roughly the
sound level in a quiet conference room. Operation of the sampler with its exhaust both
vented (see Figure 3) and not vented showed that the sampler itself does not contribute
significantly to the levels of PAHs in indoor air, therefore making it unnecessary to vent the
exhaust outdoors during indoor air sampling for these compounds. Thus, the effect of the
sampler on the house air exchange rate is minimized.
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Method IP-7 PAHs
The attractive features of this sampler are:
• PM-10 inlet - The sampler can be adapted with an optional PM-10 aerodynamic
aerosol inlet cut-point design which is insensitive to small variations in sampling flow
rate (see Figure 2).
• Annular denuder - The sampler can be adapted with an optional annular denuder
system to assist in gaseous/particle separation studies (see Figure 2), as detailed in
Compendium Method IP-9.
• Tripod sampling head - The sampler can be modified to incorporate the sampling
head containing the filter and adsorbent on a tripod (see Figure 3) with meter box
assembly, with the exhaust vented external or internal to the room.
• Sorbent bed - The sampler is capable of collecting adequate samples on the adsorbent
bed for limited time resolution of species of interest at the design flow rate.
• Acoustic performance - Acoustic insulation of the sampler allows it to meet a noise
criterion of 35, roughly the sound level in a quiet conference room.
• Sampler operation - Operation of the sampler in a house with its exhaust both vented
and not vented showed that it does not contribute significantly to indoor levels of
PAH's and has minimal affect on the air exchange rate.
• Biological testing - Operation of the sampler at 224 Lpm for a 24-hour test period
enables sufficient quantity for bioassay analysis if biological screening is part of the
sampling protocol.
However, if at these flowrates the sampler disturbs the air exchange in the indoor
environment, then it becomes part of the test, not independent of it. Due to these and
other limitations, a medium (20 Lpm) volume air sampling system (see Figure 4) was
developed by Battelle-Columbus Laboratory. The amount of mass required for accurate
chemical analysis is considerable smaller than that needed for bioassays, so the air volume
which needs to be sampled for chemical analyses alone could be correspondingly smaller.
This reduction in the sample volume permits significant reduction of the sampler size and
weight and therefore permits use of a more portable and more easily produced sampler.
Therefore, a sampler with a constant sample flow rate of approximately 20 Lpm,
compatibility with filter and/or XAD sorbent bed sampling media as well as small-scale
optional denuder, and operating noise level (<35 noise criteria) consistent with indoor use
(see Figure 5), was developed.
4.4 The flow rate requirements for the indoor sampling system are determined primarily
by the quantity of material needed for organic chemical analysis and/or bioassays. The
system must collect sufficient sample so that organic pollutant levels prevalent in indoor
air may be determined by chemical analysis GC, combined GC-MS, or HPLC. In addition,
collection of an adequate-sized sample should be achieved over a time interval that permits
resolution of pollutant levels originating from specific sources or activities such as cooking
or fireplace use in a residence. On one hand, these requirements dictate that the sampling
rate be as high as possible. Considerations such as noise level, size of the sampler, and
effects on air exchange require a compromise in the sampler flow rate. The latter
consideration is important since the sampling could affect the natural air flow between the
outside and inside of a residence and between rooms within the dwelling, if the exhaust is
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Method IP-7 PAHs
vented in a different location from collection. All of these considerations were taken into
account in the development of the 20 Lpm medium volume sampler. However, in its present
design, specific considerations should be noted. They are:
• If sampler is placed in a location that exceeds 85°F, the user may want to add a
thermal protection cutoff switch to protect electrical components and to maintain
integrity of data logger and other electrical components.
• If high paniculate loading is anticipated, the user may want to add a filter in front of
the pump for protection.
• The sampler has been evaluated in test homes, but not in areas where cigarette smoke
was predominant. If using sampler for an extended test period (7-days), then cigarette
smoke may enhance sample loss due to volatility and reaction of PAHs on the
collection media.
• Losses, apparently due to reaction of anthracene, benzo[a]pyrene and acenaphthylene
were observed during 7-day testing period.
Overall, the evaluation (42-43) of this sampler indicates that it is quiet, portable, relatively
small and easy to operate, making it attractive for use in sampling in occupied residences
or workplaces. Testing demonstrates the combination of filter and sorbent media is suitable
for collection of semi-volatile organic compounds. Breakthrough volume of the target
compounds (see Table 1) with the total sample volume of 28 m3 was not significant
(<10%), thus providing sufficient mass for chemical analysis of most of the target
compounds.
5. Definitions
Note: Definitions used in this document and hi any user-prepared standard operating
procedures (SOPs) should be consistent with ASTM Methods D1356, D1605-60, E260, and
E255. All abbreviations and symbols are defined within this document at point of use.
5.1 Breakthrough volume (VB) - Ability of the sampling medium to trap vapors of interest.
%VB is the percentage of the analyte of interest collected and retained by the sampling
medium when it is introduced into the air sampler and the sampler is operated under
normal conditions for a period of time equal to or greater than that required for the
intended use.
52 Retention time (RT) - Tune to elute a specific chemical from a chromatographic
column. For a specific carrier gas flow rate, RT is measured from the time the chemical
is injected into the gas stream until it appears at the detector.
5.3 High performance liquid chromatography (HPLC) - An analytical method based on
separation of compounds of a liquid mixture through a liquid chromatographic column and
measurement of the separated components with a suitable detector.
5.4 Gradient elution - Defined as increasing the strength of the mobile phase during a
HPLC analysis. The net effect of gradient elution is to shorten the retention time of
compounds strongly retained on the analytical column. Gradient elution may be stepwise
or continuous.
Revised 9/30/89 Page 10
51?
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Method IP-7 PAHs
5.5 Method detection limit (MDL) - The minimum concentration of a substance that can
be measured and reported with confidence and that the value is above zero.
5.6 Kuderna-Danish apparatus - The Kuderna-Danish (KD) apparatus is a system for
concentrating materials dissolved in volatile solvents.
5.7 Reverse phase liquid chromatography - Reverse phase liquid chromatography involves
a nonpolar absorbent (C-18,ODS) coupled with a polar solvent to separate nonpolar
compounds.
5.8 Guard column - Guard columns in HPLC are usually short (5 cm) columns attached
after the injection port and before the analytical column to prevent particles and strongly
retained compounds from accumulating on the analytical column. The guard column
should always be the same stationary phase as the analytical column and is used to extend
the life of the analytical column.
5.9 MS-SIM - The GC is coupled to a select ion mode (SIM) detector where the
instrument is programmed to acquire data for only the target compounds and to disregard
all others. This is performed using SIM coupled to retention time discriminators. The SIM
analysis procedure provides quantitative results.
5.10 Sublimation - Sublimation is the direct passage of a substance from the solid state to
the gaseous state and back into the solid form without at any time appearing in the liquid
state. Also applied to the conversion of solid to vapor without the later return to solid
state, and to a conversion directly from the vapor phase to the solid state.
5.11 Surrogate standard - A surrogate standard is a chemically inert compound (not
expected to occur in the environmental sample) which is added to each sample, blank and
matrix spiked sample before extraction and analysis. The recovery of the surrogate standard
is used to monitor unusual matrix effects, gross sample processing errors, etc. Surrogate
recovery is evaluated for acceptance by determining whether the measured concentration
falls within acceptable limits.
5.12 Retention time window - Retention time window is determined for each analyte of
interest and is the time from injection to elution of a specific chemical from a
chromatographic column. The window is determined by three injections of a single
component standard over a 72 hour period as plus or minus three times the standard
deviation of the absolute retention time for that analyte.
6. Interferences
6.1 Method interferences may be caused by contaminants in solvents, reagents, glassware,
and other sample processing hardware that result in discrete artifacts and/or elevated
baselines in the detector profiles. All of these materials must be routinely demonstrated
to be free from interferences under the conditions of the analysis by running laboratory
reagent blanks.
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Method IP-7 PAHs
6.1.1 Glassware must be scrupulously cleaned (44). Clean all glassware as soon as
possible after use by rinsing with the last solvent used in it. This should be followed by
detergent washing with hot water and rinsing with tap water and reagent water. It should
then be drained dry, solvent rinsed with acetone and spectrographic grade hexane. After
drying and rinsing, glassware should be sealed and stored in a clean environment to prevent
any accumulation of dust or other contaminants. Glassware should be stored inverted or
capped with aluminum foil.
Note: The glassware may be further cleaned by placing in a muffle furnace at 450°C for
8 hours to remove trace organics.
6.12 The use of high purity water, reagents and solvents helps to minimize interference
problems. Purification of solvents by distillation in all-glass systems may be required.
6.1.3 Matrix interferences may be caused by contaminants that are coextracted from the
sample. Additional clean-up by column chromatography may be required (see Section
12.4).
62 The extent of interferences that may be encountered using liquid chromatographic
techniques has not been fully assessed. Although GC and HPLC conditions described allow
for unique resolution of the specific PAH compounds covered by this method, other PAH
compounds may interfere. The use of column chromatography for sample clean-up prior
to GC or HPLC analysis will eliminate most of these interferences. The analytical system
must, however, be routinely demonstrated to be free of internal contaminants such as
contaminated solvents, glassware, or other reagents which may lead to method interferences.
A laboratory reagent blank is run for each batch of reagents used to determine if reagents
are contaminant-free.
6.3 Although HPLC separations have been improved by recent advances in column
technology and instrumentation, problems may occur with baseline noise, baseline drift,
peak resolution and changes in sensitivity. Problems affecting overall system performance
can arise (45). The user is encouraged to develop a standard operating procedure (SOP)
manual specific for his laboratory to minimize problems affecting overall system
performance.
6.4 Concern during sample transport and analysis is mentioned. Heat, ozone, NO2 and
ultraviolet (UV) light may cause sample degradation. These problems should be addressed
as part of the user-prepared SOP manual. Where possible, incandescent or UV-shielded
fluorescent lighting should be used during analysis.
7. Safety
7.1 The toxicity or carcinogenicity of each reagent used in this method has not been
precisely defined; however, each chemical compound should be treated as a potential
health hazard. From this viewpoint, exposure to these chemicals must be reduced to the
lowest possible level by whatever means available. The laboratory is responsible for
maintaining a current awareness file of Occupational Safety and Health Administration
regulations regarding the safe handling of the chemicals specified in this method. A
reference file of material data handling sheets should also be made available to all
Revised 9/30/89 Page 12
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Method IP-7 PAHs
personnel involved in the chemical analysis. Additional references to laboratory safety are
available and have been identified for the analyst (46-48).
12 B[a]P has been tentatively classified as a known or suspected, human or mammalian
carcinogen. Many of the other PAHs have been classified as carcinogens. Care must be
exercised when working with these substances. This method does not purport to address
all of the safety problems associated with its use. It is the responsibility of whoever uses
this method to consult and establish appropriate safety and health practices and determine
the applicability of regulatory limitations prior to use. The user should be thoroughly
familiar with the chemical and physical properties of targeted substances (see Table 1 and
Figure 1).
73 Treat all PAHs as carcinogens. Neat compounds should be weighed in a glove box.
Spent samples and unused standards are toxic waste and should be disposed according to
regulations. Regularly check counter tops and equipment with "black light" for fluorescence
as an indicator of contamination.
7.4 Because the sampling configuration (filter and backup adsorbent), the collection
efficiency for treated PAHs has been demonstrated to be greater than 95% (except for
naphthalene), no field recovery evaluation will occur as part of this procedure.
Note: Naphthalene has demonstrated significant breakthrough using PUF cartridges,
especially at summer ambient temperatures.
8. Apparatus
8.1 Sample Collection (see Figure 4)
8.1.1 Acoustically enclosed sampling case - Cabbage Cases, Inc., 1166-C Steelwood
Road, Columbus, OH, 43212-1356, 614-486-2495.
8.12 Vacuum pump - Gast Inc., P.O. Box 97, Benton Harbor, MI, 49022, 616-926-6171,
Model 1531-107B-6288X.
8.13 Flow sensor - R. D. McMillan Co., 1301 Sparrow Trail, Copperas Cove, TX, 76522,
817-547-2555, Model 100-10.
8.1.4 Data logger with DOS-PRONTO program and supporting cables - Rustrak, Inc.,
Route 2 and Middle Road, East Greenwich, RI, 02818-0962,401-884-6800, Rustrak Ranger
Model RR-400, 0-5V.
8.1.5 Programmable timer, seven day - Micronta Inc., Radio Shack, a Division of Tandy
Corp., Fort Worth, TX, 76102, Cat. No. 63-889.
8.1.6 Fan - McLean Fans, 70 K. Washington Road, Princeton Junction, NJ, 08550, 609-
799-0100.
8.1.7 Tripod ring stand with sample cartridge and filter assembly - General Metal Works,
Inc. (GMW), 145 South Miami Avenue, Village of Cleves, OH, 45002, Model PS-1
Assembly, 800-543-7412.
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Method IP-7 PAHs
83 Sample Clean-up and Concentration (see Figure 6)
8.2.1 Soxhlet extractors capable of extracting GMW Model PS-1 filter and adsorbent
cartridges (2.3" x 5" length), 500 mL flask, and condenser, best source.
8.2.2 Pyrex glass tube furnace system for activating silica gel at 180°C under purified
nitrogen gas purge for an hour, with capability of raising temperature gradually, best source.
8 23 Glass vial, 40 mL, best source.
8.2.4 Erlenmeyer flask, 50 nrU best source.
Note: Reuse of glassware should be minimized to avoid the risk of crosscontamination.
All glassware that is used, especially glassware that is reused, must be scrupulously cleaned
as soon as possible after use. Rinse glassware with the last solvent used in it and then with
high-purity acetone and hexane. Wash with hot water containing detergent. Rinse with
copious amount of tap water and several portions of distilled water. Drain, dry, and heat
in a muffle furnace at 400°C for 4 hours. Volumetric glassware must not be heated in a
muffle furnace; rather, it should be rinsed with high-purity acetone and hexane. After the
glassware is dry and cool, rinse it with hexane, and store it inverted or capped with solvent-
rinsed aluminum foil in a clean environment.
8.2.5 White cotton gloves for handling cartridges and filters, best source.
8.2.6 Minivials, 2 mL, borosilicate glass, with conical reservoir and screw caps lined with
Teflon* -faced silicone disks, and a vial holder, best source.
$2.7 Teflon* -coated stainless steel spatulas and spoons, best source.
8.2.8 Kuderna-Danish (KD) apparatus - 500 mL evaporation flask (Kontes K-570001-
500 or equivalent), 10 mL graduated concentrator tubes (Kontes K-570050-1025 or
equivalent) with ground-glass stoppers, and 3-ball macro Snyder Column (Kontes K-
5700010500, K-50300-0121, and K-569001-219, or equivalent), best source.
8.2.9 Adsorption columns for column chromatography - 1 cm x 10 cm with stands.
8.2.10 Glove box for working with extremely toxic standards and reagents with explosion-
proof hood for venting fumes from solvents, reagents, etc.
82.11 Vacuum oven - Vacuum drying oven system capable of maintaining a vacuum
at 240 torr (flushed with nitrogen) overnight.
82.12 Concentrator tubes and a nitrogen evaporation apparatus with variable flow rate,
best source.
82.13 Laboratory refrigerator, best source.
8.2.14 Boiling chips - solvent extracted, 10/40 mesh silicon carbide or equivalent, best
source.
82.15 Water bath - heated, with concentric ring cover, capable of +_ 5°C temperature
control, best source.
82.16 Vortex evaporator (optional).
83 Sample Analysis
8.3.1 Gas Chromatography with Flame lonization Detection (GC-FID)
8.3.1.1 Gas chromatography - Analytical system complete with gas chromatography
suitable for on-column injections and all required accessories, including detectors, column
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Method IP-7 PAHs
supplies, recorder, gases, and syringes (see Figure 7). A data system for measuring peak
areas and/or peak heights is recommended.
83.12 Packed column - 1.8 m x 2 mm ID glass column packed with 3% OV-17 on
Chromosorb W-AW-DMCS (100/120 mesh) or equivalent - Supelco Inc., Supelco Park,
Bellefonte, PA, Supelco SPB-5.
8.3.1.3 Capillary column - 30 m x 0.25 mm ID fused silica DB-5 column coated with
0.25 /im thickness 5% phenyl, 90% methyl siloxane - Alltech Associates, 2051 Waukegan
Road, Deerfield, IL, 60015, 312-948-8600.
83.1.4 Detector - Flame lonization
8.3.2 Gas Chromatography with Mass Spectroscopy Detection (see Figure 7) Coupled
with Data Processing System (GC-MS-DS)
8.32.1 The gas chromatograph must be equipped for temperature programming,
and all required accessories must be available, including syringes, gases, and a capillary
column. The gas chromatograph injection port must be designed for capillary columns. The
use of splitless injection techniques is recommended. On-column injection techniques can
be used but they may severely reduce column lifetime for nonchemically bonded columns.
In this protocol, a 1-3 fiL injection volume is used consistently. With some gas
chromatograph injection ports, however, 1 /iL injections may produce some improvement
hi precision and chromatographic separation. A 1 /iL injection volume may be used if
adequate sensitivity and precision can be achieved.
Note: If 1 /iL is used as the injection volume, the injection volumes for all extracts, blanks,
calibration solutions and performance check samples must be 1 /iL.
83.2.2 Gas chromatograph-mass spectrometer interface - The gas chromatograph is
usually coupled directly to the MS source. The interface may include a diverter valve for
shunting the column effluent and isolating the mass spectrometer source. All components
of the interface should be glass or glass-lined stainless steel. The interface components
should be compatible with 320°C temperatures. Cold spots and/or active surfaces
(adsorption sites) hi the GC-MS interface can cause peak tailing and peak broadening. It
is recommended that the gas chromatograph column be fitted directly into the MS source.
Graphite ferrules should be avoided in the gas chromatograph injection area since they may
adsorb PAHs. Vespel* or equivalent ferrules are recommended.
8323 Mass spectrometer - The mass spectrometer should be operated in the selected
ion mode (SIM) with a total cycle time (including voltage reset time) of one second or less
(see Section 14.2).
832.4 Mass spectrometer - Capable of scanning from 35 to 500 amu every 1 sec or
less, using 70 volts (nominal) electron energy hi the electron impact ionization mode. The
mass spectrometer must be capable of producing a mass spectrum for decafluorotriphenyl
phosphine (DFTPP) which meets all of the criteria (see Section 145.1).
832.5 Data system - A dedicated computer data system is employed to control the
rapid multiple ion monitoring process and to acquire the data. Quantification data (peak
areas or peak heights) and multi-ion detector (MID) traces (displays of intensities of each
m/z being monitored as a function of time) must be acquired during the analyses.
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Method IP-7 PAHs
Quantifications may be reported based upon computer generated peak areas or upon
measured peak heights (chart recording). The detector zero setting must allow peak-to-
peak measurement of the noise on the baseline.
8.32.6 Gas chromatograph column - A fused silica column (30 m x 0.25 mm I.D.)
DB-5 crosslinked 5% phenyl methylsilicone, 0.25 jim film thickness (Alltech Associates, 2051
Waukegan Rd., Deerfield, IL, 60015, 312-948-9600) is utilized to separate individual PAHs.
Other columns may be used for determination of PAHs. Minimum acceptance criteria must
be determined as per Section 14.2. At the beginning of each 12-hour period (after mass
resolution has been demonstrated) during which sample extracts or concentration calibration
solutions will be analyzed, column operating conditions must be attained for the required
separation on the column to be used for samples.
83 2.1 Balance - Mettler balance or equivalent.
8.3.2.8 All required syringes, gases, and other pertinent supplies to operate the GC-
MS system.
8.3.2.9 Pipettes, micropipettes, syringes, burets, etc., to make calibration and spiking
solutions, dilute samples if necessary, etc., including syringes for accurately measuring
volumes such as 25 iiL and 100
83 .3 High Performance Liquid Chromatography (HPLC) System (see Figure 8)
83.3.1 Gradient HPLC system - consisting of acetonitrile and water phase reservoirs;
mixing chamber; a high pressure pump; an injection valve (automatic sampler with an
optional 25 pL loop injector); a Vydac C-18-bonded reverse phase (RP) column, (The
Separations Group, P.O. Box 867, Hesperia, CA, 92345) or equivalent (25 cm x 4.6 mm
ID); an UV (A = 254 nm) adsorbent detector (Spectre Physics 8440 or equivalent) and a
data system or printer plotter.
8.3.3.2 Guard column - 5 cm guard column pack with Vydac reverse phase C-18
material.
83.33 Reverse phase analytical column - Vydac or equivalent, C-18 bonded RP
column (The Separation Group, P.O. Box 867, Hesperia, CA, 92345), 4.6 mm x 25 cm, 5
micron particle diameter.
833.4 LS-4 fluorescence spectrometer, Perkin Elmer, separate excitation and
emission, monochromator positioned by separate microprocessor-controlled flow cell and
wavelength programming ability (optional).
833.5 UV/visible detector, Spectra Physics 8440, deuterium lamp, capable of
programmable wavelengths (optional).
833.6 Dual channel, Spectra Physics 4200, computing integrator, measures peak
areas and retention times from recorded chromatographs. IBM PC XT with Spectra Physics
Labnet system for data collection and storage (optional).
8.4 Flow Calibration
8.4.1 Tripod ring stand with sample cartridge and filter assembly - General Metal Works,
Inc. (GMW), 145 South Miami Avenue, Village of Cleves, OH, 45002, Model PS-1
Assembly, 800-543-7412.
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Method IP-7 PAHs
8.42 Wet test meter - VWR Scientific, P.O. Box 7900, San Francisco, CA, 94120, 415-
468-7150, Cat. No. 32598-063.
9. Reagents and Materials
9.1 Sample Collection
9.1.1 Acid-washed quartz fiber filter - 105 mm micro quartz fiber binderless filter,
General Metal Works, Inc., Cat No. GMW QMA-4, 145 South Miami Ave., Village of
Cleves, OH, 45002, 800-543-7412, or Supelco Inc., Cat. No. 1-62, Supelco Park, Bellefonte,
PA, 16823-0048.
9.12 Acid-washed quartz fiber filter - 37 mm micro quartz fiber binderless filter, best
source.
9.1 J Polyurethane foam (PUF) - 3 inch thick sheet stock, polyether type (density 0.022
g/cm3) used hi furniture upholstering, General Metal Works, Inc., Cat. No. PS-1-16, 145
South Miami Ave., Village of Cleves, OH, 45002, 800-543-7412, or Supelco Inc., Cat. No.
1-63, Supelco Park, Bellefonte, PA, 16823-0048.
9.1.4 XAD-2 resin - Supelco Inc., Cat. No. 2-02-79, Supelco Park, Bellefonte, PA, 16823-
0048.
9.1.5 Aluminum foil, best source.
9.1.6 Hexane, reagent grade, best source.
93 Sample Clean-up and Concentration
9.2.1 Soxhlet Extraction
92.1.1 Methylene chloride - chromatographic grade, glass-distilled, best source.
92.12 Sodium sulfate-anhydrous (ACS), granular (purified by washing with methylene
chloride followed by heating at 400°C for 4 hrs in a shallow tray).
92.13 Boiling chips - solvent extracted or heated in a muffle furnace at 450°C for
2 hours, approximately 10/40 mesh (silicon carbide or equivalent).
92.1.4 Nitrogen - high purity grade, best source.
92.1.5 Ether - chromatographic grade, glass-distilled, best source.
92.1.6 Hexane - chromatographic grade, glass-distilled, best source.
92.1.7 Dibromobiphenyl - chromatographic grade, best source. Used for internal
standard.
92.1.8 Decafluorobiphenyl - chromatographic grade, best source. Used for internal
standard.
922 Solvent Exchange
922.1 Cyclohexane - chromatographic grade, glass-distilled, best source.
923 Column Clean-up
Revised 9/30/89 Page 17
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Method IP-7 PAHs
Method 610
9.2.3.1 Silica gel - high purity grade, type 60, 70-230 mesh; extracted in a Soxhlet
apparatus with methylene chloride for 6 hours (minimum of 3 cycles per hour) and
activated by heating in a foil-covered glass container for 24 hours at 130°C.
9232 Sodium sulfate-anhydrous (ACS), granular (see Section 9.2.1.2).
Note: Put in an oven at 450°C for 8 hours prior to use to activate.
92 33 Pentane - chromatographic grade, glass-distilled, best source.
Lobar Prepacked Column
923.4 Silica gel Lobar prepacked column - E. Merck, Darmstadt, Germany [size
A(240-10) Lichroprep Si (40-63 /mi)].
923.5 Precolumn containing sodium sulfate - (ACS) granular anhydrous (purified
by washing with methylene chloride followed by heating at 400°C for 4 hours in a shallow
tray).
923.6 Hexane - chromatographic grade, glass-distilled, best source.
92.3.7 Methylene chloride - chromatographic grade, glass-distilled, best source.
92.3.8 Methanol - chromatographic grade, glass-distilled, best source.
9.3 Sample Analysis
93.1 Gas Chromatography Detection
93.1.1 Gas cylinders of hydrogen and helium - ultra high purity, best source.
93.12 Combustion air - ultra high purity, best source.
93.13 Zero air - Zero air may be obtained from a cylinder or zero-grade compressed
air scrubbed with Drierite® or silica gel and 5A molecular sieve or activated charcoal, or
by catalytic cleanup of ambient air. All zero air should be passed through a liquid argon
cold trap for final cleanup.
9.3.1.4 Chromatographic-grade stainless steel tubing and stainless steel fittings - for
interconnections, Alltech Applied Science, 2051 Waukegan Road, Deerfield, IL, 60015,
312-948-8600, or equivalent.
Note: All such materials in contact with the sample, analyte, or support gases prior to
analysis should be stainless steel or other inert metal. Do not use plastic or Teflon* tubing
or fittings.
93.1.5 Native and isotopically labeled PAHs isomers for calibration and spiking
standards, Cambridge Isotopes, 20 Commerce Way, Woburn, MA, 01801, 617-547-1818.
Suggested isotopically labeled PAH isomers are:
• perylene-d12, chrysene-d12, acenaphthene-d10,
• naphthalene d8, phenanthrene-d10.
93.1.6 Decafluorotriphenylphosphine (DFTPP), best source (used for tuning GC-MS).
9.32 High Performance Liquid Chromatography Detection
932.1 Acetonitrile - chromatographic grade, glass-distilled, best source.
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Method IP-7 PAHs
9.33.2 Boiling chips - solvent extracted, approximately 10/40 mesh (silicon carbide or
equivalent).
93.2.3 Water - HPLC grade. Water must not have an interference that is observed
at the minimum detectable limit (MDL) of each parameter of interest.
93.2.4 Decafluorobiphenyl - HPLC grade, best source (used for internal standard).
10. Preparation of Sample Filter and Adsorbent
10.1 Sampling Head Configuration
10.1.1 The sampling head (see Figure 9) consists of a filter holder compartment followed
by a glass cartridge for retaining the adsorbent. The present method is written using the
standard GMW PS-1 sampling head. However, Battelle-Columbus Laboratory has
investigated (43) the use of a smaller sampling head, as illustrated in Figure 10. The basic
difference is that the Battelle head uses a 47 mm filter followed by the adsorbent.
Approximately the same amount of XAD-2 (50 - 60 grams) is used in both sampling heads.
The idea of going to a smaller head was to reduce the size of the Soxhlet extraction
apparatus, consequently the volume of solvent used from 500 mL to 200 mL during the
extraction procedure. All preparation steps for cleaning the filters and adsorbents are the
same, no matter which size filter is used.
10.1.2 Before field use, both the filter and adsorbent must be cleaned to <10
ng/apparatus of B[a]P or other PAHs.
Note: Recent studies have determined that naphthalene levels may be greater than 10 ng
per apparatus even after successive cleaning procedures.
10.2 Glass Fiber Filter Preparation
102.1 The quartz fiber filters are baked at 600°C for five hours before use. To insure
acceptable filters, they are extracted with methylene chloride in a Soxhlet apparatus, similar
to the cleaning of the XAD-2 resin (see Section 103).
10.2.2 The extract is concentrated and analyzed by either GC or HPLC. A filter blank
of < 10 ng/filter of B[a]P or other PAHs is considered acceptable for field use.
103 XAD-2 Adsorbent Preparation
103.1 For initial cleanup of the XAD-2, a batch of XAD-2 (approximately 50-60 grams)
is placed in a Soxhlet apparatus [see Figure 6 (a)] and extracted with methylene chloride
for 16 hours at approximately 4 cycles per hour.
1032 At the end of the initial Soxhlet extraction, the spent methylene chloride is
discarded and replaced with fresh reagent. The XAD-2 resin is once again extracted for 16
hours at approximately 4 cycles per hour.
1033 The XAD-2 resin is removed from the Soxhlet apparatus, placed in a vacuum
oven connected to an ultra-pure nitrogen gas stream and dried at room temperature for
approximately 2-4 hours (until no solvent odor is detected).
Note: Alternatively, the XAD-2 resin is placed in a Pyrex® column (10 cm x 600 cm),
allowing sufficient space for fluidizing. The column is wrapped with heat tape, maintained
at 40°C, during the drying process. High purity air, scrubbed through a charcoal trap, is
Revised 9/30/89 Page 19
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Method IP-7 PAHs
forced through the resin bed, fluidizing the bed while generating a minimum load at the exit
of the column.
10.3.4 A nickel or stainless steel screen (mesh size 200/200) is fitted to the bottom and
the top of a hexane-rinsed glass sampling cartridge to retain the XAD-2 resin.
10.3.5 The Soxhlet-extracted, vacuum dried XAD-2 resin is placed into the sampling
cartridge (using clean white cotton gloves) to a depth of approximately 2 inches. This
should require between 50 and 60 grams of adsorbent.
103.6 The glass module containing the XAD-2 adsorbent is wrapped with hexane-rinsed
aluminum foil, placed in a labeled container and tightly sealed with Teflon* tape.
Note: The aluminum foil should be baked in an oven overnight at 500°C to insure no
residuals remain after rinsing with hexane.
An alternative method for cleaning XAD-2 resin is summarized as follows:
• In a 600 g batch, XAD-2 resin is Soxhlet-extracted with dichloromethane for 16 hours.
• After extracting, the resin is transferred to a clean drying column. Then the resin is
dried with high-purity nitrogen using Teflon* tubing from the nitrogen cylinder with
a charcoal tube in the line.
• Approximately 60 g of dried resin is packed into each precleaned PS-1 glass sampling
cartridge and held in place with stainless steel screens and glass wool.
• The packed cartridge is wrapped and placed in a wide-mouth screw-cap glass jar.
10.3.7 At least one assembled cartridge from each batch must be analyzed as a
laboratory blank, using the procedures described in Section 13, before the batch is
considered acceptable for field use. A blank of <10 ng of B[a]P or other PAHs is
considered acceptable.
10.4 PUF Sampling Cartridge Preparation
10.4.1 The PUF adsorbent is a polyether-type polyurethane foam (density 0.0225 g/cm3)
used for furniture upholstery.
10.4.2 The PUF inserts are 6.0 cm diameter cylindrical plugs cut from 3 inch sheet
stock and should fit with slight compression in the glass cartridge,supported by the wire
screen (see Figure 9). During cutting, the die is rotated at high speed (e.g.,in a drill press)
and continuously lubricated with water.
10.4.3 For initial cleanup, the PUF plug is placed in a Soxhlet apparatus [see Figure
6(a)] and extracted with acetone for 14-24 hours at approximately 4 cycles per hour. When
cartridges are reused, 5% diethyl ether in n-hexane can be used as the cleanup solvent.
Note: A modified PUF cleanup procedure can remove the unknown interference
components and the mutagenicity of the PUF blank. This method consists of compressed
rinsing 50 times with toluene, acetone and 5% diethyl ether/hexane and followed by Soxhlet
extraction.
10.4.4 The extracted PUF is placed in a vacuum oven connected to a water aspirator
and dried at room temperature for approximately 2-4 hours (until no solvent odor is
detected).
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557
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Method IP-7
10.4.5 The PUF is placed into the glass sampling cartridge using polyester gloves. The
module is wrapped with hexane-rinsed aluminum foil, placed in a labeled container, and
tightly sealed.
10.4.6 At least one assembled cartridge from each batch must be analyzed as a
laboratory blank, using the procedures described in Section 13, before the batch is
considered acceptable for field use. A blank level of < 10 ng/plug for single compounds
is considered to be acceptable.
11. Sample Collection
11.1 Description of Sampling Apparatus
11.1.1 Traditionally, the sampling of PAHs has been accomplished utilizing the high
volume air sampler. The use of high volume air samplers in occupied residences, however,
is not practicable due to the noises that they emit, the high flow rates that they employ and
their size. To address these limitations, this method utilizes an acoustically insulated
medium volume sampler (see Figure 4) meeting a noise criterion of 35 (see Figure 5). The
flow rate achievable with this device is adequate for at least 24 hour time resolution of
typical concentrations of most PAHs of interest.
11.12 The sampling module consists of a glass sampling cartridge and an air-tight metal
cartridge holder, as outlined in Section 10.1. The adsorbent (XAD-2 or PUF) is retained
in the glass sampling cartridge.
112 Calibration of Sampling System
Note: Each sampler is to be calibrated: 1) when new, 2) after major repairs or
maintenance, 3) whenever any audit point deviates from the calibration curve by more than
7%, 4) when a different sample collection media, other than that which the sampler was
originally calibrated to, will be used for sampling, 5) at the frequency specified in the user
Standard Operating Procedure (SOP) manual in which the samplers are utilized, and 6)
before and after each test series.
11.2.1 Assemble the calibration system as illustrated in Figure 11.
1122 Level the wet test meter. Adjust the meter until the bubble is exactly centered
in the level [see Figure 11 (a)].
1123 Fill the wet test meter with distilled water until the water just covers the pointer
[see Figure 11 (b)].
11.2.4 Connect the wet test meter to the vacuum source. Attach one end of the hose
to the wet test meter outlet, as identified on the meter casing. Attach the other hose to
the outlet of the flow sensor and connect to the inlet of the wet test meter.
Note: Best results are obtained if the complete sampling system is calibrated as a system.
112.5 Connect the sampling cartridge containing a "dummy" filter/PUF assembly to
the inlet of the flow sensor.
112.6 Insure the flow sensor and data logger are properly connected.
112.7 Turn the data logger on and insure 0 volts as sensed by the flow sensor. Adjust
to zero if necessary as displayed by the data logger.
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Method IP-7 PAHs
112.8 Turn the vacuum pump on and adjust to 2.0 volts as displayed by the data logger.
Use the flow control needle valve to make this adjustment.
112.9 Allow the system to equilibrate from approximately 10 revolutions of the wet
test meter's large pointer.
11.2.10 As the wet test meter pointer passes zero, begin timing with a precision
stopwatch. As the wet test meter pointer passes the three-quarter revolution mark, read
and record on Flow Sensor Calibration Data Sheet (see Figure 12) the displayed volts.
1U.11 As the wet test meter pointer passes the starting point, stop the stopwatch and
record elapsed time on the Flow Sensor Calibration Sheet
112.12 Record the volume of air passed through the wet test meter in column headed
by Vm.
112.13 Record wet test meter fluid temperature (TJ in °K, barometric pressure (Pb)
in mm Hg, and the vapor pressure of the wet test meter's water in mm Hg as acquired
from a saturation vapor pressure over water table (Handbook of Chemistry and Physics).
112.14 Calculate actual volume (Va):
V = V x CF
va - vm A «^.r.
where:
Va = actual volume of wet test meter, L
Vm = volume of wet test meter, L
C.F. = wet test meter's correction factor, dimensionless
112.15 Calculate Vs from Pm, pv. Tm and Va and record on the Calibration Data Sheet.
vs = (va) x (p. - Pv/ps) x ciyrj
where:
Vs = volume corrected to standard temperature and pressure, L
Va = defined in Section 11.2.14
Pm = barometric pressure (Pb) corrected for internal meter pressure - Ap in mm Hg
= Pb-Ap
pv = vapor pressure of wet test meter's water, mm Hg
Ps = standard pressure, 760 mm Hg
Ts = standard temperature, 25°C + 273.16, 298.16°K
Tm = temperature of meter, °C + 273.16, °K
112.16 Calculate standard flow rate (Qs) from Vs and 8 and record.
Qs = vs/e
where:
Qs = volumetric flow rates corrected to standard temperature and pressure, L/min
6 = time, minutes
112.17 Convert Qs (L/min) to Qs (m3/min) by multiplying by 1.00 x 10"3 to be used in
Section 17.1.2.
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Method IP-7 PAHs
11.2.18 Plot Qs (L/min) versus mass flow meter readings on linear graph paper. Repeat
Section 11.2.10 through Section 112.16 for three other flow rates within the range of the
flow sensor.
11.2.19 Construct a best fit curve for the points generated and use this relationship for
future work employing the flow sensor device.
11.2.20 Place calibration curve in sample for use in setting sampling flows during
collection.
11.2.21 Retrieve the data logger and transport to a computer site while still under
battery power. It is then cable-connected to the personal computer for the playback
operational phase through a serial I/O port on the computer from the "output/recharge"
port on the data logger. The playback menu permits you to transfer your recorded data
from the data logger to your personal computer. Playback permits all recording sessions
to be loaded into computer memory in the form of raw data for filing, review, analysis, and
printout. The playback operation of the Rustrak Ranger is coordinated between the data
logger and the personal computer, driven by the PRONTO application software.
112 22 You can now start playback. Use the SELECT and ENTER keys as required,
and increment the menu as follows:
• Select PLAYBACK from the main menu; the readout shows a flashing PLAYBACK.
• Press ENTER key; the readout shows a steady-state PLAYBACK (stops flashing).
• When computer acknowledges data transmission, the display on the data logger begins
to ripple, indicating that data is being transmitted.
• Display returns to READY upon completing playback.
You have now performed the procedure for sending the collected data hi the data logger
memory to the personal computer.
Note: If the computer is not connected, the data logger will stay in the "wait" condition
(readout shows a steady-state PLAYBACK).
11223 Retrieve volts for individual flow values correction to standard temperature and
pressure (STP). Construct a calibration curve, as illustrated below:
Qs, L/min Volts Qs, L/min
10.86 TJ 17.50
12.16 : :
13.46 : :
14.86 2.0 22.50
16.24
11224 Also place calibration curve in sampler for use in setting flows during sample
collection.
113 Sample Collection
113.1 Monitor Placement
Note: The sampler should be located at ground level on a soft surface (for noise
absorption) if possible. One should take care to not restrict the air circulation vents to
prevent overheating of the unit. The sampling line should be not more than 3 m in length,
Revised 9/30/89 Page 23
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Method IP-7 PAHs
and preferably shorter. The sampler inlet should be located in an area which can be
considered part of the breathing zone of the building occupants. Avoid placing the inlet
on the floor, in corners of rooms, or in the immediate vicinity of a possible source of the
compounds being sampled.
113.1.1 After the sampling system has been assembled and flow checked as described
in Section 11.1 and Section 11.2, it can be used to collect air samples, as described in
Section 11.3.2.
113.1.2 The monitors should be placed at a minimum horizontal distance from an
obstruction that is equivalent to one meter from the obstructing object. In addition, the
sampler intake should be minimum of one meter above floor.
11.3.2 Sample Module Loading
1132.1 With the empty sample module removed from the sampler, rinse all sample
contact areas using ACS grade hexane in a Teflon* squeeze bottle. Allow the hexane to
evaporate from the module before loading the samples.
11322 Detach the lower chamber of the rinsed sampling module. While wearing
disposable clean lint free nylon or powder-free surgical gloves, remove a clean glass
cartridge/sorbent from its container (wide mouthed glass jar with a Teflon* -lined lid) and
unwrap its aluminum foil covering. The foil should be replaced back in the sample
container to be reused after the sample has been collected.
Note: Check glass for cracks prior to installation.
11323 Insert the cartridge into the lower chamber and tightly reattach it to the
module.
1132.4 Using clean Teflon* tipped or metal forceps, carefully place a clean fiber
filter atop the filter holder and secure in place by clamping the filter holder ring over the
filter using the three screw clamps. Insure that all module connections are tightly
assembled.
Note: Failure to do so could result in air flow leaks at poorly sealed locations which could
affect sample representativeness. Ideally, sample module loading and unloading should be
conducted in a controlled environment or at least a centralized sample processing area so
that the sample-handling variables can be minimized.
1132.5 With the module removed from the sampler and the flow control valve fully
open, turn the pump on and allow it to warmup for approximately 5 minutes.
1132.6 Attach a "dummy" sampling module loaded with the exact same type of filter
and sorbent media as that which will be used for sample collection.
1132.7 Turn the sampler on and adjust flow to 20 Lpm using the calibration curve
and as indicated by the flow indicator.
1132.8 Turn the sampler off and remove the "dummy" module. The sampler is now
ready for field use.
1132.9 Room temperature, barometric pressure, elapsed time meter setting, sampler
serial number, filter number, and adsorbent sample number are recorded on the Field Test
Data Sheet (see Figure 13). Attach the loaded sampler module to the sampler.
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Method IP-7 PAHs
1133 Powering Medium Volume Sampling Unit
11.33.1 With the master power switch (the red rocker switch on the 4" x 6" electrical
box in the pump compartment) turned off, connect the 3-prong A.C. power line to the
sampler and a suitable 110 V A.C. outlet.
11332. Ensure that the timer is in the OFF mode-the word OFF will be displayed
on the right hand side of LCD. The timer should be in the MANUAL position. The SET
switch will toggle the power OFF/ON for the 110 V A.C. unit which operates the pump and
cooling fan.
11333 Turn on the master power switch, which should illuminate. This supplies 12
V D.C. power to the data logger, the flow transducer, and the timer.
Note: The timer and data logger do have internal battery backups, but it should be routine
to keep power to them when feasible.
113.4 Data Logger Unit Start-up
113.4.1 After turning the data logger on, READY should flash on the LCD. If not,
press SELECT (S) and ENTER (E) together. Pressing S and E together will always return
the data logger to the start of the menu, as illustrated in Figure 14.
Note: S takes you down through the menu tree (or cycles you through available options).
E moves you to the right through the tree (or accepts the displayed option), as illustrated
in Figure 14. Press S to get to DEFINE, then E for SENSOR.
113.42 To indicate the type sensor in use (Type 13), at the SENSOR prompt press
E, then S to cycle to I/P NO. 4. This assumes that you are connected to I/P Port 4 on the
data logger, as illustrated in Figure 14.
113.43 Next, press S when the CALIBRATE prompt appears.
113.4.4 Return to DEFINE mode and define the recording time to be long enough
to cover the entire period of interest. If, for example, you select 7 days, you need to specify
7 days, 00 hours, 00 minutes, 00 seconds to enable the data logger to function as you desire.
113.4.5 After the sensor and recording times are displayed, press S and E to obtain
READY prompt, then S, S, to get to RECORD mode. Press E to obtain START prompt,
then E again to begin recording. When data are being recorded the LCD will flash an R
on the left side to the display, and the data will appear to the right.
113.4.6 During a recording session, press E at any time to place an event market in
the recorded file. This is recommended when the sampling flow is started or interrupted
for sample changing. Pressing S and E together terminates recording. (It can be restarted.)
113.4.7 When data have been recorded, asterisks will appear on left of the flashing
READY. Do not turn the data logger power switch off until the data have been
downloaded to a PC.
Note: Turning off the data logger will erase all stored data and functions programmed.
The data logger is returned to a tabula rasa by means of the switch on its left side.
113.5 Sampling
113.5.1 After the logger is recording data, the timer can be used to turn on the pump
and begin the sampling period.
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Method IP-7 PAHs
113.5.2 The flow reading is recorded at the beginning, end and every six hours during
the sampling period for sampling durations of 24 hours or longer. Room temperature,
barometric pressure, and elapsed time readings are recorded at the beginning and end of
the sampling period.
113.6 Sample Retrieval
113.6.1 At the end of the desired sampling period, the power is turned off. Carefully
remove the sampling head containing the filter and adsorbent cartridge to a clean area.
113.6.2 While wearing disposable lint free cotton or surgical gloves, remove the
sorbent cartridge from the lower module chamber and place it on the retained aluminum
foil in which the sample was originally wrapped.
Note: Do not lay cartridge in a horizontal position if XAD-2 is used as the back-up
adsorbent. Loss of adsorbent or contamination may occur.
113.6.3 Carefully remove the glass fiber filter from the upper chamber using clean
Teflon* tipped forceps.
113.6.4 Fold the filter in half twice (sample side inward) and place it in the glass
cartridge atop the sorbent.
Note: The filter may be separated from the PUF cartridge and placed in a glass watch
glass or petri dish for shipment to the laboratory.
113.6.5 Wrap the combined samples in aluminum foil and place them in their original
glass sample container. A sample label should be completed and affixed to the sample
container. Chain-of-custody should be maintained for all samples.
113.6.6 The glass containers should be stored with dry ice packs or blue ice and
protected from light to prevent possible photo decomposition of collected analytes. If the
time span between sample collection and laboratory analysis is to exceed 24 hours, samples
must be kept refrigerated.
Note: Recent studies (13,16) have indicated that during storage, PUF does not retain B[a]P
as effectively as XAD-2. Therefore, sample holding time should not exceed 20 days.
113.6.7 A final sample flow check is performed using the dummy cartridge, as
described in Section 11.3.2. If calibration deviates by more than 10% from the initial
reading, the flow data for that sample must be marked as suspect and the sampler should
be inspected and/or removed from service.
113.6.8 At least one field filter/adsorbent blank should be returned to the laboratory
with each group of samples (-10 samples). A field blank is treated exactly as a sample
except that no air is drawn through the filter/adsorbent cartridge assembly.
113..6.9 Samples should be stored with frozen ice until receipt at the analytical
laboratory, after which they are refrigerated at 4°C.
Note: If ice is used to preserve collected samples, safeguards must be used to prevent
water seepage into the sample jars.
12. Sample Clean-up and Concentration
Note: The following sample extraction, concentration, solvent exchange and analysis
procedures are outlined for user convenience in Figure 15.
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Method IP-7
12.1 Sample Identification
12.1.1 The samples are returned to the laboratory with dry ice in the glass sample
container containing the filter and adsorbent.
12.1.2 The samples are logged in the laboratory logbook according to sample location,
filter and adsorbent cartridge number identification and total air volume sampled
(unconnected).
12.13 If the time span between sample registration and analysis is greater than 24 hrs.,
then the samples must be kept refrigerated. Minimize exposure of samples to fluorescent
light. All samples should be extracted within one week after sampling.
12.2 Soxhlet Extraction and Concentration
12.2.1 Assemble the Soxhlet apparatus [see Figure 6(a)]. Immediately before use, charge
the Soxhlet apparatus with 800 mL of methylene chloride and reflux for 2 hours. Let the
apparatus cool, disassemble it, transfer the methylene chloride to a clean glass container,
and retain it as a blank for later analysis, if required. Place the adsorbent and filter together
in the Soxhlet apparatus (the use of an extraction thimble is optional) if using XAD-2
adsorbent in the sampling module.
Note: The filter and adsorbent are analyzed together in order to reach detection limits,
avoid questionable interpretation of the data, and minimize cost. Since methylene chloride
is not a suitable solvent for PUF, 10% ether in hexane is employed to extract the PAHs
from the PUF resin bed separate from the methylene chloride extraction of the
accompanying filter, rather than methylene chloride for the extraction of the XAD-2
cartridge.
122.1.1 Prior to extraction, add a surrogate standard to the Soxhlet solvent. A
surrogate standard (i.e., a chemically inert compound not expected to occur in an
environmental sample) should be added to each sample, blank,and matrix spike sample just
prior to extraction or processing. The recovery of the surrogate standard is used to monitor
for unusual matrix effects, gross sample processing errors, etc. Surrogate recovery is
evaluated for acceptance by determining whether the measured concentration falls within
the acceptance limits. The following surrogate standards have been successfully utilized in
determining matrix effects, sample process errors, etc. utilizing GC-FID, GC-MS or HPLC
analysis.
Surrogate Analytical
Standard Concentration Technique
Dibromobiphenyl 50 ng//zL GC-FID
Dibromobiphenyl 50 ng//*L GC-MS
Deuterated Standards 50 ng//xL GC-MS
Decafluorobiphenyl 50 ng//iL HPLC
Note: The deuterated standards will be added in Section 14.3.2. Deuterated analogs of
selective PAHs cannot be used as surrogates for HPLC analysis due to coelution problems.
Add the surrogate standard to the Soxhlet solvent.
Revised 9/30/89 Page 27
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Method IP-7 PAHs
122.13, For the XAD-2 and filter extracted together, add 800 mL of methylene
chloride to the apparatus and reflux for 18 hours at a rate of at least 3 cycles per hour.
122.13 For the PUF extraction separate from the filter, add 800 mL of 10% ether
in hexane to the apparatus and reflux for 18 hours at a rate of at least 3 cycles per hour.
122.1.4 For the filter extraction, add 300 mL of methylene chloride to the apparatus
and reflux for 18 hours at a rate of at least 3 cycles per hour.
1222 Dry the extract from the Soxhlet extraction by passing it through a drying column
containing about 10 grams of anhydrous sodium sulfate.
Note: If water is observed in the Soxhlet extract, the drying process is mandatory, especially
if the Field Test Data Sheet indicates rain or snow during sampling period. Collect the
dried extract in a Kuderna-Danish (K-D) concentrator assembly. Wash the extractor flask
and sodium sulfate column with 100-125 mL of methylene chloride to complete the
quantitative transfer.
1223 Assemble a Kuderna-Danish concentrator [see Figure 6(b)] by attaching a 10
mL concentrator tube to a 500 mL evaporative flask.
Note: Other concentration devices (vortex evaporator) or techniques may be used in place
of the K-D as long as qualitative and quantitative recovery can be demonstrated.
122.4 Add at least two boiling chips, attach a three-ball macro-Snyder column to the
K-D flask, and concentrate the extract using a hot water bath at 60°C to 65°C. Place the
K-D apparatus in the water bath so that the concentrator tube is about half immersed in
the water and the entire rounded surface of the flask is bathed with water vapor. Adjust
the vertical position of the apparatus and the water temperature as required to complete
the concentration in one hour. At the proper rate of distillation, the balls of the column
actively chatter but the chambers do not flood. When the liquid has reached an
approximate volume of 5 mL, remove the K-D apparatus from the water bath and allow the
solvent to drain for at least 5 minutes while cooling.
122.5 Remove the .Snyder column and rinse the flask and its lower joint into the
concentrator tube with 5 mL of cyclohexane.
123 Solvent Exchange
123.1 Replace the K-D apparatus equipped with a Snyder column back on the water
bath.
1232 Increase the temperature of the hot water bath to 95-100°C. Momentarily remove
the Snyder column, add a new boiling chip, and attach a two-ball micro-Snyder column.
Prewet the Snyder column, using 1 mL of cyclohexane. Place the K-D apparatus on the
water bath so that the concentrator tube is partially immersed in the hot water. Adjust
the vertical position of the apparatus and the water temperature, as required, to complete
concentration in 15-20 minutes. At the proper rate of distillation, the balls of the column
will actively chatter, but the chambers will not flood. When the apparent volume of liquid
reaches 0.5 mL, remove the K-D apparatus and allow it to drain and cool for at least 10
minutes.
1233 When the apparatus is cool, remove the micro-Snyder column and rinse its lower
joint into the concentrator tube with about 0.2 mL of cyclohexane.
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Method IP-7 PAHs
Note: A 5 mL syringe is recommended for this operation. Adjust the extract volume to
exactly 1.0 mL with cyclohexane. Stopper the concentrator tube and store refrigerated at
4°C, if further processing will not be performed immediately. If the extract will be stored
longer than 24 hours, it should be transferred to a Teflon*-sealed screw-cap vial.
12.4 Sample Cleanup by Solid Phase Exchange
Cleanup procedures may not be needed for relatively clean matrix samples. If the extract
in Section 123.3 is clear, cleanup may not be necessary. If cleanup is not necessary, the
cyclohexane extract (1 mL) can be analyzed directly by GC-FI detection, except the initial
oven temperature begins at 30°C rather than 80°C for cleanup samples (see Section 13.3),
or solvent exchange to acetonitrile for HPLC analysis. More specifically, if GC-MS is
employed as the analytical finish, then clean-up is not necessary to determine PAHs. If
cleanup is required, the procedures are presented using either a handpack silica gel column
as outlined in Method 610 (20,24), a Lobar prepacked silica gel column, or an aminosilane
column for PAH concentration and separation. The user has the option to use any of the
outlined solid phase exchange methods.
Note: The user may be wise to use an UV lamp during the chromatographic concentration
and separation procedure to detect the eluting PAHs from the column.
12.4.1 Method 610 Cleanup Procedure [see Figure 6(c)]
12.4.1.1 Pack a 6 inch disposable Pasteur pipette (10 mm ID x 7 cm length) with a
piece of glass wool. Push the wool to the neck of the disposable pipette. Add 10 grams
of activated silica gel in methylene chloride slurry to the disposable pipette. Gently tap
the column to settle the silica gel and elute the methylene chloride. Add 1 gram of
anhydrous sodium sulfate to the top of the silica gel column.
12.4.12 Prior to initial use, rinse the column with methylene chloride at 1 mL/min
for 1 hr to remove any trace of contaminants. Pre-elute the column with 40 mL of pentane.
Discard the eluate and just prior to exposure of the sodium sulfate layer to the air, transfer
the 1 mL of the cyclohexane sample extract onto the column, using an additional 2 mL of
cyclohexane to complete the transfer. Allow to elute through the column.
12.4.1.3 Just prior to exposure of the sodium sulfate layer to the air, add 25 mL of
pentane and continue elution of the column. Save the pentane eluate in case that the silica
gel was not 100% activated and some PAHs may collect in this fraction.
Note: The pentane fraction contains the aliphatic hydrocarbons collected on the
filter/adsorbent combination. If interested, this fraction may be analyzed for specific
aliphatic organics. Elute the column with 25 mL of methylene chloride/pentane (4:6 v/v)
and collect the eluate in a 500 mL K-D flask equipped with a 10 mL concentrator tube.
Note: This fraction contains the B[a]P and other moderately polar PAHs. The use of a
UV lamp will assist in observing the PAHs as they elute from the mL/min.
12.4.1.4 Concentrate the collected fraction to less than 10 mL by the K-D technique,
as illustrated in Section 12.3 using pentane to rinse the walls of the glassware. The extract
is now ready for HPLC or GC analysis.
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Method IP-7 PAHs
Note: An additional elution through the column with 25 mL of methanol will collect highly
polar oxygenated PAHs with more than one functional group. This fraction may be
analyzed for specific polar PAHs. However, additional cleanup by solid phase extraction
may be required to obtain both qualitative and quantitative data due to complexity of the
eluant.
12.4.2 Lobar Prepacked Column Procedure
12.42.1 The setup using the Lobar prepacked column consists of an injection port,
septum, pump, pre-column containing sodium sulfate, Lobar prepacked column and solvent
reservoir.
12.42.2 The column is cleaned and activated according to the following cleanup
sequence:
Fraction Solvent Composition Volume (mL)
1 100% Hexane 20
2 80% Hexane/20% Methylene Chloride 10
3 50% Hexane/50% Methylene Chloride 10
4 100% Methylene Chloride 10
5 95% Methylene Chloride/5% Methanol 10
6 80% Methylene Chloride/20% Methanol 10
12.423 Reverse the sequence at the end of the run and run to the 100% hexane
fraction in order to activate the column. Discard all fractions.
12.42.4 Pre-elute the column with 40 mL of hexane, which is also discharged.
12.42.5 Inject 1 mL of the cyclohexane sample extract, followed by 1 mL injection of
blank cyclohexane.
12.42.6 Continue elution of the column with 20 mL of hexane, which is also
discharged.
12.42.7 Now elute the column with 180 mL of a 40/60 mixture of methylene
chloride/hexane respectively.
12.42.8 Collect approximately 180 mL of the 40/60 methylene chloride/hexane
mixture in a K-D concentrator assembly.
12.42.9 Concentrate to less than 10 mL with the K-D assembly as discussed in
Section 12.2.
12.42.10 The extract is now ready for either HPLC or GC analysis.
12.43 Aminosilane Column Procedure
12.43.1 While silica gel (Method 610) and Lobar prepacked columns have effectively
fractionated PAHs into their respective groups, a fi Bondapak NH2 (Waters Associates,
Milford, MA) aminosilane column (300 x 8 mm ID) using 3% methylene chloride in hexane
as the mobile phase, is also available.
12.432 Normal phase liquid chromatography is used in the /i Bondapak NH2
fractionating scheme.
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Method IP-7 PAHs
12.4.3.3 As with other techniques, a UV lamp is used to detect eluting PAHs to better
identify characteristic PAHs.
13. Gas Chromatography Analysis with Flame lonization Detection
13.1 Gas chromatography (GC) is a quantitative analytical technique useful for PAH
identification. This method provides the user the flexibility of column selection (packed or
capillary) and detector [flame ionization (FT) or mass spectrometer (MS)] selection. The
mass spectrometer provides for specific identification of B(a)P; however, with system
optimization, other PAHs may be qualitatively and quantitatively detected using MS (see
Section 14.0). This procedure provides for common GC separation of the PAHs with
subsequent detection by either FI or MS (see Figure 7). The following PAHs have been
quantified by GC separation with either Fl or MS detection:
Acenaphthene Chrysene
Acenaphthylene Dibenzo(a,h)anthracene
Anthracene Fluoranthene
Benzo(a)anthracene Fluorene
Benzo(a)pyrene Indeno( l,2,3-cd)pyrene
Benzo(b)fluoranthene* Naphthalene
Benzo(e)pyrene Phenanthrene
Benzo(g,h,i)perylene Pyrene
Benzo(k)fluoranthene*
* May not be completely resolved by GC
The packed column gas chromatographic method described here can not adequately resolve
the following four pairs of compounds: anthracene and phenanthrene; chrysene and
benzo(a)anthracene; benzo(b)fluoranthene and benzo(k)fluoranthene; and dibenzo(a,h)
anthracene and indeno(l,2,3-cd)pyrene. The use of a capillary column instead of the
packed column, also described in this method, should adequately resolve these PAHs.
However, unless the purpose of the analysis can be served by reporting a quantitative sum
for an unresolved PAH pair, either capillary GC-MS (see Section 14.0) or HPLC (see
Section 15.0) should be used for these compounds. This section will address the use of GC-
FI detection using packed or capillary columns.
13.2 To achieve maximum sensitivity with the GC-FI method, the extract must be
concentrated to 1.0 mL, if not already concentrated to 1 mL. If not already concentrated
to 1 mT,, add a clean boiling chip to the methylene chloride extract in the concentrator
tube. Concentrate the extract using a two-ball micro-Snyder column attached to a K-D
apparatus according to Section 12.2.4. When the apparent volume of liquid reaches 0.5 mU
remove the K-D apparatus. Drain and cool for at least 10 minutes. Remove the micro-
Snyder column and rinse its lower joint into the concentrator tube with a small volume of
methylene chloride. Adjust the final volume to 1.0 mL and stopper the concentrator tube.
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Method IP-7
PAHs
133 Assemble and establish the following operating parameters for the GC equipped with
an FI detector:
(A)
Capillary
Identification
Dimensions
Carrier Gas
Carrier Gas
Row Rate
Column
Program
Detector
DB-5 fused silica
capillary, 0.25 /an
5% phenyl, methyl
siloxane bonded
30 m x 025 mm ID
Helium
28-30 cm/sec
(1 cm/minute)
40°C for 1 min;
program at 15°C/min
to 200°C; program at
3°C/min to 300°C
Flame lonization
SPB-5 fused silica
capillary, 0.25 /im
5% phenyl, methyl
siloxane bonded
30 mx 0.25 mm ID
Helium
28-30 cm/sec
(1 cm/minute)
80°C for 2 min;
program at 8°C/min
to 280°C and hold
for 12 minutes
Flame lonization
Packed
ChromosorbW-AW-DMCS
(100/120 mesh)
coated with
3% OV-17
1.8 m x 2 mm ID
Nitrogen
30-40 cm/minute
Hold at 100°C for
4 minutes; program
at 8°C/min to 280°C
and hold for 15
minutes
Flame lonization
(A) Without column cleanup (see Section 12.4)
(B) With column cleanup (see Section 12.4.1)
13.4 Prepare and calibrate the chromatographic system using either the external standard
technique (see Section 13.4.1) or the internal standard technique (see Section 13.4.2).
Figure 16 outlines the following sequence involving GC calibration and retention time
window determination.
13.4.1 External standard calibration procedure - For each analyte of interest, including
surrogate compounds for spiking (if used) prepare calibration standards at a minimum of
five concentration levels by adding volumes of one or more stock standards to a volumetric
flask and diluting to volume with methylene chloride.
Note: All calibration standards of interest involving selected PAHs of the same
concentration can be prepared in the same flask.
13.4.1.1 Prepare stock standard solutions at a concentration of 0.1 ng/fiL by dissolving
0.0100 gram of assayed PAH material in methylene chloride and diluting to volume in a 100
mL volumetric flask.
Note: Larger volumes can be used at the convenience of the analyst.
13.4.1.2 When compound purity is assayed to be 98% or greater, the weight can be
used without correction to calculate the concentration of the stock standard.
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Page 32
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Method IP-7 PAHs
Note: Commercially prepared stock standards can be used at any concentration if they are
certified by the manufacturer or by an independent source. Transfer the stock standard
solutions into Teflon* -sealed screw-cap bottles.
13.4.1.3 Store at -20°C and protect from light. Stock standards should be checked
frequently for signs of degradation or evaporation, especially just prior to preparing
calibration standards from them. Stock standard solutions must be replaced after one year,
or sooner if comparison with check standards indicates a problem.
13.4.1.4 Calibration standards at a minimum of five concentration levels should be
prepared through dilution of the stock standards with methylene chloride. One of the
concentration levels should be at a concentration near, but above, the method detection
limit. The remaining concentration levels should correspond to the expected range of
concentrations found in real samples or should define the working range of the GC.
Note: Calibration solutions must be replaced after six months, or sooner if comparison with
a check standard indicates a problem.
13.4.1.5 Inject each calibration standard using the technique that will be used to
introduce the actual samples into the gas chromatograph (e.g., 1- to 3-pL injections).
Note: The same amount must be injected each time.
13.4.1.6 Tabulate peak height or area responses against the mass injected. The results
can be used to prepare a calibration curve for each analyte.
Note: Alternatively, for samples that are introduced into the gas chromatograph using a
syringe, the ratio of the response to the amount injected, defined as the calibration factor
(CF), can be calculated for each analyte at each standard concentration by the following
equation:
Calibration factor (CF) = Total Area of Peak
Mass injected (in nanograms)
If the percent relative standard deviation (%RSD) of the calibration factor is less than 20%
over the working range, linearity through the origin can be assumed, and the average
calibration factor can be used in place of a calibration curve.
13.4.1.7 The working calibration curve or calibration factor must be verified on each
working day by the injection of one or more calibration standards. If the response for any
analyte varies from the predicted response by more than ±20%, a new calibration curve
must be prepared for that analyte. Calculate the percent variance by the following
equation:
Percent variance = (R2 - R^/Ri x 100
where:
R2 = calibration factor from succeeding analysis, and
R! = calibration factor from first analysis.
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Method IP-7 PAHs
13.42 Internal standard calibration procedure - To use this approach, the analyst must
select one or more internal standards that are similar in analytical behavior to the
compounds of interest. The analyst must further demonstrate that the measurement of the
internal standard is not affected by method or matrix interferences. Due to these
limitations, no internal standard applicable to all samples can be suggested.
Note: It is recommended that the internal standard approach be used only when the GC-
MS procedure is employed due to coeluting species.
13.4.2.1 Prepare calibration standards at a minimum of five concentration levels for
each analyte of interest by adding volumes of one or more stock standards to a volumetric
flask.
13.4.2.2 To each calibration standard, add a known constant amount of one or more
internal standard and dilute to volume with methylene chloride.
Note: One of the standards should be at a concentration near, but above, the method
detection limit. The other concentrations should correspond to the expected range of
concentrations found in real samples or should define the working range of the detector.
13.4.2.3 Inject each calibration standard using the same introduction technique that
will be applied to the actual samples (e.g., 1 to 3 fiL injection).
13.4.2.4 Tabulate the peak height or area responses against the concentration of each
compound and internal standard.
13.4.2.5 Calculate response factors (RF) for each compound as follows:
Response Factor (RF) = (AsC1s)/(A1sCs)
where:
As = response for the analyte to be measured, area units or peak height
A1s = response for the internal standard, area units or peak height
C1s = concentration of the internal standard, /Jg/L
Cs = concentration of the analyte to be measured, Hg/L
13.4.2.6 If the RF value over the working range is constant (<20% RSD), the RF can
be assumed to be invariant, and the average RF can be used for calculations.
Note: Alternatively, the results can be used to plot a calibration curve of response ratios,
As/A1s versus RF.
13.4.2.7 The working calibration curve or RF must be verified on each working day
by the measurement of one or more calibration standards.
13.42.8 If the response for any analyte varies from the predicted response by more
than .±.20%, a new calibration curve must be prepared for that compound.
13.5 Retention Time Windows Determination
13.5.1 Before analysis can be performed, the retention time windows must be established
for each analyte.
13.52 Make sure the GC system is within optimum operating conditions.
13.5.3 Make three injections of the standard containing all compounds for retention time
window determination.
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Method IP-7 PAHs
Note: The retention time window must be established for each analyte throughout the
course of a 72 hr period.
13.5.4 The retention window is defined as plus or minus three times the standard
deviation of the absolute retention times for each standard.
13.5.5 Calculate the standard deviation of the three absolute retention times for each
single component standard. In those cases where the standard deviation for a particular
standard is zero, the laboratory must substitute the standard deviation of a close eluting,
similar compound to develop a valid retention time window.
13.5.6 The laboratory must calculate retention time windows for each standard on each
GC column and whenever a new GC column is installed. The data must be noted and
retained in a notebook by the laboratory as part of the user SOP and as a quality assurance
check of the analytical system.
13.6 Sample Analysis
13.6.1 Inject 1 to 3 (iL of the methylene chloride extract from Section 13.2 (however, the
same amount each time) using the splitless injection technique when using capillary column.
Note: Smaller (1.0 /iL) volumes can be injected if automatic devices are employed.
13.6.2 Record the volume injected and the resulting peak size in area units or peak
height.
13.63 Using either the internal or external calibration procedure, determine the identity
and quantity of each component peak in the sample chromatogram through retention time
window and established calibration curve. Table 2 outlines typical retention times for
selected PAHs, using both the packed and capillary column technique coupled with FI
detection, while Figure 17 illustrates typical chromatogram for the capillary column
conditions outlined in Table 2.
13.63.1 If the responses exceed the linear range of the system, dilute the extract and
reanalyze. It is recommended that extracts be diluted so that all peaks are on scale.
Overlapping peaks are not always evident when peaks are off scale. Computer reproduction
of chromatograms, manipulated to ensure all peaks are on scale over a 100-fold range, are
acceptable if linearity is demonstrated. Peak height measurements are recommended over
peak area integration when overlapping peaks cause errors in area integration.
13.6.3.2 Establish daily retention time windows for each analyte. Use the absolute
retention time for each analyte from Section 13.5.4 as the midpoint of the window for that
day. The daily retention time window equals the midpoint +. three times the standard
deviation determined in Section 13.5.4.
13.6.33 Tentative identification of an analyte occurs when a peak from a sample
extract falls within the daily retention time window.
Note: Confirmation may be required on a second GC column, or by GC-MS (if
concentration permits) or by other recognized confirmation techniques if overlap of peaks
occur.
13.63.4 Validation of GC system qualitative performance is performed through the
use of the mid-level standards. If the mid-level standard falls outside its daily retention
Revised 9/30/89 Page 35
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Method IP-7 PAHs
time window, the system is out of control. Determine the cause of the problem and
perform a new calibration sequence (see Section 13.4).
13.63.5 Additional validation of the GC system performance is determined by the
surrogate standard recovery. If the recovery of the surrogate standard deviates from 100%
by not more than 20%, then the sample extraction, concentration, clean-up and analysis is
certified. If it exceeds this value, then determine the cause of the problem and correct.
13.6.4 Determine the concentration of each analyte in the sample according to
Section 17.1 and Section 17.2.1.
14. Gas Chromatography with Mass Spectroscopy Detection
14.1 Analytical System
14.1.1 The analysis of the extracted sample for B[a]P and other PAHs is accomplished
by an electron impact GC-MS (El GC-MS) in the selected ion monitoring (SIM) mode with
a total cycle time (including voltage reset time) of one second or less within each set of
ions.
14.12 The gas chromatograph is equipped with a DB-5 fused silica capillary column (30
m x 0.25 mm ID) with helium carrier gas for analyte separation. The gas chromatograph
column is temperature controlled and interfaced directly to the MS ion source.
143, Operation Parameters
142.1 The laboratory must document that the EI-GC-MS system is properly maintained
through periodic calibration checks.
1422 The GC-MS system should have the following specifications:
Mass range: 35-500 amu
Scan time: 1 sec/scan
Column: 30 m x 0.25 mm ID, DB-5 crosslinked 5% phenyl methyl silicone, 0.25 /im film
thickness, capillary column or equivalent
Initial column temperature and hold time: 60°C for 1 min
Column temperature program: 60°C to 200°C at 15°C/min; 200°C to 310°C at 3°C/mm
Final column temperature hold: 310°C for 15 min (until benzo[g,h,i] perylene has eluted)
Injector temperature: 250-300°C
Transfer line temperature: 250-300°C
Source temperature: According to manufacturer's specifications
Injector: Grob-type, splitless
El Condition: 70 eV
Mass Scan: Follow manufacturer's instructions for selection monitoring (SIM) mode.
Sample volume: 1 nL on-column injection
Carrier gas: Helium at 30 cm/sec
142.3 The GC-MS is tuned using a 1 ng/pL solution of decafluorotriphenylphosphine
(DFTPP). The DFTPP permits the user to tune the mass spectrometer on a daily basis.
Revised 9/30/89 Page 36
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Method IP-7 PAHs
142.4 If properly toned, the DFTPP key ions and ion abundance criteria should be met
as outlined in Table 3.
14.3 Calibration Techniques
Note: The typical GC-MS operating conditions are outlined in Table 4. The GC-MS system
can be calibrated using the external standard technique (see Section 14.3.1) or the internal
standard technique (see Section 14.3.2). Figure 18 outlines the following sequence involving
the GC-MS calibration.
143.1 External Standard Calibration Procedure
143.1.1 Prepare calibration standard of B[a]P or other PAHs at a minimum of five
concentration levels by adding volumes of one Or more stock standards to a volumetric flask
and diluting to volume with methylene chloride. The stock standard solution of B[a]P (0.1
Hg/liL) must be prepared from pure standard materials or purchased as certified solutions.
143.12 Place 0.0100 grams of native B[a]P or other PAHs on a tared aluminum
weighing disk and weigh on a Mettler balance.
143.13 Quantitatively, transfer to a 100 mL volumetric flask. Rinse the weighing disk
with several small portions of methylene chloride. Ensure all material has been transferred.
143.1.4 Dilute to mark with methylene chloride.
143.1.5 The concentration of the stock standard solution of B[a]P or other PAHs in
the flask is 0.1 Hg/liL
Note: Commercially prepared stock standards may be used at any concentration if they are
certified by the manufacturer or by an independent source.
143.1.6 Transfer the stock standard solutions into Teflon*-sealed screw-cap bottles.
Store at 4°C and protect from light. Stock standard solutions should be checked frequently
for signs of degradation or evaporation, especially just prior to preparing calibration
standards from them.
143.1.7 Stock standard solutions must be replaced after 1 yr or sooner if comparison
with quality control check samples indicates a problem.
143.1.8 Calibration standards at a minimum of five concentration levels should be
prepared. Accurately pipette 1.0 mL of the stock solution (0.1 Mg//dL) into 10 mL
volumetric flask, dilute to mark with methylene chloride. This daughter solution contains
10 ng//iL of B[a]P or other PAHs.
Note: One of the calibration standards should be at a concentration near, but above the
method detection limit; the others should correspond to the range of concentrations found
in the sample but should not exceed the working range of the GC-MS system.
143.1.9 Prepare a set of standard solutions by appropriately diluting, with methylene
chloride, accurately measured volumes of the daughter solution (1 ng//iL).
143.1.10 Accurately pipette 100 /zL, 300 pL, 500 fiL, 700 tiL and 1000 /dL of the
daughter solution (10 ng/jdL) into each 10 mL volumetric flask, respectively. To each of
these flasks, add an internal deuterated standard to give a final concentration of 1 ng//iL
of the internal deuterated standard (see Section 143.2.1). Dilute to mark with methylene
chloride.
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Method IP-7 PAHs
14.3.1.11 The concentration of B[a]P in each flask is 0.1 ng/fiL, 0.3 ng//dL> 0.5 ng//iL,
0.7 ng//iL, and 1.0 ng//*L respectively. 'All standards should be stored at -20°C and
protected from fluorescent light and should be freshly prepared once a week or sooner if
standards check indicates a problem.
143.1.12 Analyze a constant volume (1-3 /iL) of each calibration standard by observing
retention time (see Table 5) and tabulate the area responses of the primary characteristic
ion of each standard against the mass injected. The results may be used to prepare a
calibration curve for each compound. Alternatively, if the ratio of response to amount
injected (calibration factor) is a constant over the working range (<20% relative standard
deviation, RSD), linearity through the origin may be assumed and the average ratio or
calibration factor may be used hi place of a calibration curve. Figure 19 illustrates a typical
chromatogram of selected PAHs under conditions outlined in Section 14.2.2.
143.1.13 The working calibration curve or calibration factor must be verified on each
working day by the measurement of one or more calibration standards. If the response for
any parameter varies from the predicted response by more than +. 20%, the rest must be
repeated using a fresh calibration standard. Alternatively, a new calibration curve or
calibration factor must be prepared for that compound.
14.32 Internal Standard Calibration Procedure
1432.1 To use this approach, the analyst must select one or more internal standards
that are similar in analytical behavior to the compounds of interest. For analysis of B[a]P,
the analyst should use perylene-d12. The analyst must further demonstrate that the
measurement of the internal standard is not affected by method or matrix interferences.
The following internal standards are suggested at a concentration of 1 ng//zL for specific
PAHs:
Perylene-d^ Acenaphthene-dif
Benzo(a)pyrene Acenaphthene
Benzo(k)fluoranthene Acenaphthylene
Benzo(g,h,i)perylene Fluorene
Dibenzo(a,h)anthracene
Indeno(l,2,3-cd)pyrene Naphthalene-d8
Naphthalene
Chrysene-di-.
Benzo(a)anthracene Phenanthrene-dtf
Chrysene Anthracene
Pyrene Fluoranthene
Phenanthrene
14322 A mixture of the above deuterated compounds in the appropriate
concentration range are commercially available (see Section 9.3.1.5).
14.323 Use the base peak ion as the primary ion for quantification of the standards.
If interferences are noted, use the next two most intense ions as the secondary ions.
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Method IP-7 PAHs
Note: PAHs have double charge ions that can also be used as secondary ions. The internal
standard is added to all calibration standards and all sample extracts analyzed by GC-MS.
Retention time standards, column performance standards, and a mass spectrometer tuning
standard may be included in the internal standard solution used.
143.2.4 Prepare calibration standards at a minimum of three concentration level for
each parameter of interest by adding appropriate volumes of one or more stock standard
mixture, add a known constant amount of one or more of the internal deuterated standards
to yield a resulting concentration of 1 ng//tL of internal standard and dilute to volume with
methylene chloride. One of the calibration standards should be at a concentration near, but
above, the minimum detection limit (MDL) and the other concentrations should correspond
to the expected range of concentrations found in real samples or should define the working
range of the GC-MS system.
143.2.5 Analyze constant amount (1-3 0L) of each calibration standard and tabulate
the area of the primary characteristic ion against concentration for each compound and
internal standard, and calculate the response factor (RF) for each analyte using the
following equation:
RF = (AsC1s)/(AisCs)
where:
As = area of the characteristic ion for the analyte to be measured, counts
A1s = area of the characteristic ion for the internal standard, counts
C1s = concentration of the internal standard, ng//dL
Cs = concentration of the analyte to be measured, ng/pL
If the RF value over the working range is a constant (<20% RSD), the RF can be assumed
to be invariant and the average RF can be used for calculations. Alternatively, the results
can be used to plot a calibration curve of response ratios, AS/A,,., vs. RF. Table 6 outlines
key ions for selected internal deuterated standards.
143.2.6 The working calibration curve or RF must be verified on each working day
by the measurement of one or more calibration standards. If the response for any
parameter varies from the predicted response by more than +. 20%, the test must be
repeated using a fresh calibration standard. Alternatively, a new calibration curve must be
prepared.
143.2.7 The relative retention times (see Table 5) for each compound in each
calibration run should agree within 0.06 relative retention time units.
14.4 Sample Analysis
14.4.1 It is highly recommended that the extract be screened on a GC-FID or GC-PID
using the same type of capillary column as in the GC-MS procedure. This will minimize
contamination of the GC-MS system from unexpectedly high concentrations of organic
compounds.
14.42 Analyze the 1 mL extract (see Section 13.2) by GC-MS. The recommended GC-
MS operating conditions to be used are specified in Section 14.2. Typical chromatogram
of selected PAHs by GC-MS is illustrated in Figure 19.
Revised 9/30/89 " Page~39
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Method IP-7 PAHs
14.43 If the response for any quantitation ion exceeds the initial calibration curve range
of the GC-MS system, extract dilution must take place. Additional internal standard must
be added to the diluted extract to maintain the required 1 ng/jtL of each internal standard
in the extracted volume. The diluted extract must be reanalyzed.
14.4.4 Perform all qualitative and quantitative measurements described in Section 14.3.
The typical retention time and characteristic ions for selective PAHs are outlined in Table
6. Store the extracts at -20°C, protected from light in screw-cap vials equipped with
unpierced Teflon* liner, for future analysis.
14.4.5 The sample analysis using the GC-MS-SIM is based on a combination of retention
times and relative abundances of selected ions (see Table 5). These qualifiers are stored
on the hard disk of the GC-MS data computer and are applied for identification of each
chromatographic peak. The retention time qualifier is determined to be + 0.10 minute of
the library retention time of the compound. The acceptance level for relative abundance
is determined to be +. 15% of the expected abundance. Three ions are measured for most
of the PAH compounds. When compound identification is made by the computer, any peak
that fails any of the qualifying tests is flagged (e.g., with an *). The data should be
manually examined by the analyst to determine the reason for the flag and whether the
compound should be reported as found. While this adds some subjective judgment to the
analysis, computer generated identification problems can be clarified by an experienced
operator. Manual inspection of the quantitative results should also be performed to verify
concentrations outside the expected range.
14.4.6 Determine the concentration of each analyte in the sample according to Section
17.1 and Section 17.2.2.
14.5 GC-MS Performance Tests
14.5.1 Daily DFTPP Tuning - At the beginning of each day that analyses are to be
performed, the GC-MS system must be checked to see that acceptable performance criteria
are achieved when challenged with a 1 pL injection volume containing 1 ng of
decafluorotriphenylphosphine (DFTPP). The DFTPP key ions and ion abundance criteria
that must be met are illustrated in Table 3. Analysis should not begin until all those criteria
are met. Background subtraction should be straightforward and designed only to eliminate
column bleed or instrument background ions. The GC-MS tuning standard should also be
used to assess GC column performance and injection port inertness. Obtain a background
correction mass spectra of DFTPP and check that all key ions criteria are met. If the
criteria are not achieved, the analyst must retune the mass spectrometer and repeat the test
until all criteria are achieved. The performance criteria must be achieved before any
samples, blanks, or standards are analyzed. If any key ion abundance observed for the daily
DFTPP mass tuning check differs by more than 10% absolute abundance from that
observed during the previous daily tuning, the instrument must be retuned or the sample
and/or calibration solution reanalyzed until the above condition is met.
14.52 Daily Single Point Initial Calibration Check - At the beginning of each work day,
a daily 1-point calibration check is performed by re-evaluating the midscale calibration
standard. This is the same check that is applied during the initial calibration, but one
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Method IP-7
instead of five working standards are evaluated. Analyze the one working standards under
the same conditions the initial calibration curve was evaluated. Analyze 1 /iL of each of
the midscale calibration standard and tabulate the area response of the primary
characteristic ion against mass injected. Calculate the percent difference using the following
equation:
% Difference = (RFC - K/HF,) x 100
where:
RFr = average response factor from initial calibration using mid-scale standard
RFC = response factor from current verification check using mid-scale standard
If the percent difference for the midscale level is greater than 10%, the laboratory should
consider this a warning limit. If the percent difference for the midscale standard is less than
20%, the initial calibration is assumed to be valid. If the criterion is not met (<20%
difference), then corrective action MUST be taken.
Note: Some possible problems are standard mixture degradation, injection port inlet
contamination, contamination at the front end of the analytical column, and active sites in
the column or chromatographic system. This check must be met before analysis begins. If
no source of the problem can be determined after corrective action has been taken, a new
five point calibration MUST be generated. This criterion MUST be met before sample
analysis begins.
14.53 12 hour Calibration Verification - A calibration standard at mid-level
concentration containing B[a]P or other PAHs must be performed every twelve continuous
hours of analysis. Compare the standard every 12 hours with the average response factor
from the initial calibration. If the % difference for the response factor (see Section 14.5.2)
is less than 20%, then the GC-MS system is operative within initial calibration values. If
the criteria is not met (>20% difference), then the source of the problem must be
determined and a new five point curve MUST be generated.
14.5.4 Surrogate Recovery - Additional validation of the GC system performance is
determined by the surrogate standard recovery. If the recovery of the surrogate standard
deviates from 100% by not more than 20%, then the sample extraction, concentration,
clean-up and analysis is certified. If it exceeds this value, then determine the cause of the
problem and correct.
15. High Performance Liquid Chromatography (HPLC) Detection
15.1 Introduction
15.1.1 While GC-FID and GC-MS have been used successfully to measure PAHs in
ambient air, detection of B[a]P by HPLC has become a viable analytical tool in recent
years. The HPLC technique is very sensitive and less expensive than the GC-MS technique.
The use of synchronous fluorescence detection as part of the HPLC system offers several
advantages in terms of improved sensitivity and specificity. Similar to the GC-FID and GC-
MS techniques, the HPLC procedure using either UV and/or synchronous fluorescence
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Method IP-7 PAHs
detection requires column cleanup before analysis. The procedure outlined below has
been written specifically for analysis of B[a]P by HPLC using UV detection. Other PAHs
may also be identified using UV detection but positive identification and quantitation may
be difficult due to poor resolution of eluting peaks. However, optimizing chromatographic
conditions through UV detection (A = 254 nm), coupled with fluorescence detection with
programmable wavelength to change the excitation and emission wavelengths during the
chromatographic analysis will optimize selectivity and/or sensitivity for selective PAHs.
The following PAHs have been quantified using the combined UV and programmable
fluorescence detectors a part of the HPLC system:
Compound Detector1 Compound Detector1
Acenaphthene UV Benzo(k)fluoranthene UV/FL
Acenaphthylene UV Dibenzo(a,h)anthracene UV/FL
Anthracene UV/FL Fluoranthene UV/FL
Benzo(a)anthracene UV/FL Fluorene UV/FL
Benzo(a)pyrene UV/FL Indeno(l,2,3-cd)pyrene UV/FL
Benzo(b)fluoranthene UV/FL Naphthalene UV
Benzo(ghi)perylene UV/FL Phenanthrene UV/FL
1UV= Ultraviolet, FL = Fluorescence
15.1.2 Through the use of column cleanup before HPLC analysis employing UV
detection, B[a]P can be quantitatively identified along with other PAHs. However, it should
be noted that HPLC analysis employing a single detector (UV) does not give unambiguous
results.
15.13 For improved sensitivity and specificity, UV detection coupled with synchronous
fluorescence detection allows the optimization of chromatographic conditions.
152 Solvent Exchange To Acetonitrile
15.2.1 To the extract in the concentrator tube, add 4 mL of acetonitrile and a new
boiling chip; attach a micro-Snyder column to the apparatus.
15.2.2 Increase temperature of the hot water bath to 95 to 100°C
15.2.3 Concentrate the solvent as in Section 12.3.
152.4 After cooling, remove the micro-Snyder column and rinse its lower sections into
the concentration tube with approximately 0.2 mL acetonitrile.
15.2.5 To the cool extract, add an internal standard solution of 7-methylfluoranthene
and/or perylene-d12.
Note: The 7-methylfluoranthene can be obtained from the National Cancer Institute,
Chemical Carcinogen Repository, HT Research Institute, Chicago, HI. and the perylened12
can be obtained from MSD Isotopes, Merck & Co., Rahway, NJ. With this approach, the
most suitable internal standards for each isomeric family would be the predeuterated
analogue of the isomer which elutes first, minimizing the possibility of coelution with alkyl-
substituted PAHs within the specific isomeric group. Thus, the ideal internal standards
would be the perdeuterated fluoranthene, benzo[a]pyrene and benzo[gbi]perylene.
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Method IP-7 PAHs
152.6 After adding the internal standard, adjust the solution in the concentrator tube
to 1.0 mL.
153 HPLC Assembly
153.1 The HPLC system is assembled, as illustrated in Figure 8.
15.3.2 The HPLC system is operated according to the following parameters:
HPLC Operating Parameters
Guard Column VYDAC 201 GCCIOYT
Analytical Column VYDAC 201 TP5415 C-18 RP (0.46 x 25 cm)
Column Temperature 27.0 +. 2°C
Mobile Phase
Solvent Composition Time (Minutes)
40% Acetonitrile/60% water 0
100% Acetonitrile 25
100% Acetonitrile 35
40% Acetonitrile/60% water 45
Linear gradient elution at 1.0 mL/min
Detector Ultraviolet, operating at 254 nm
Flow Rate 1.0 mL/minute
Injection Volume 10 mL
Note: To prevent irreversible absorption due to "dirty" injections and premature loss of
column efficiency, a guard column is installed between the injector and the analytical
column. The guard column is generally packed with identical material as is found in the
analytical column. The guard column is generally replaced with a fresh guard column after
several injections (—50) or when separation between compounds becomes difficult. The
analytical column specified in this procedure has been laboratory evaluated. Other
analytical columns may be used as long as they meet procedure and separation
requirements. Table 8 outlines other columns uses to determine PAHs by HPLC.
153.3 The mobile phases are placed in separate HPLC solvent reservoirs and the pumps
are set to yield a total of 1.0 mL/minute and allowed to pump for 20-30 minutes before
the first analysis.
Note: The chromatographic analysis involves an automated solvent program allowing
unattended instrument operation. The solvent program consists of varying concentrations
of acetonitrile in water with a constant flow rate, a constant column temperature, and a 10-
minute equilibrium time. The detector is switched on at least 30 minutes before the first
analysis. UV detection at 254 nm is generally preferred.
15.3.4 Before each analysis, the detector baseline is checked to ensure stable operation.
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Method IP-7 PAHs
15.4 HPLC Calibration
15.4.1 Prepare stock standard solutions at PAH concentrations of 1.00 (ig/liL by
dissolving 0.0100 grams of assayed material in acetonitrile and diluting to volume in a 10
mL volumetric flask.
Note: Larger volumes can be used at the convenience of the analyst. When compound
purity is assayed to be 98% or greater, the weight can be used without correction to
calculate the concentration of the stock standard. Commercially prepared stock standards
can be used at any concentration if they are certified by the manufacturer or by an
independent source.
15.42 Transfer the stock standard solutions into Teflon*-sealed screw-cap bottles.
Store at 4°C and protect from light. Stock standards should be checked frequently for signs
of degradation or evaporation, especially just prior to preparing calibration standards from
them.
15.43 Stock standard solutions must be replaced after one year, or sooner if comparison
with check standards indicates a problem.
15.4.4 Prepare calibration standards at a minimum of five concentration levels ranging
from 1 ng//dL to 10 ng/^L by first diluting the stock standard 10:1 with acetonitrile, giving
a daughter solution of 0.1 Mg/^L. Accurately pipette 100 pL, 300 /iL, 500 fiL, 700 ML and
1000 liL of the daughter solution (0.1 Mg//tL) into each 10 mL volumetric flask, respectively.
Dilute to mark with acetonitrile. One of the concentration levels should be at a
concentration near, but above, the method detection limit (MDL). The remaining
concentration levels should correspond to the expected range of concentrations found in
real samples or should define the working range of the HPLC.
Note: Calibration standards must be replaced after one year, or sooner if comparison with
check standards indicates a problem.
15.4.5 Analyze each calibration standard (at least five levels) three times. Tabulate
area response vs. mass injected. All calibration runs are performed as described for sample
analysis in Section 15.5.1. Typical retention times for specific PAHs are illustrated in Table
8. Linear response is indicated where a correlation coefficient of at least 0.999 for a linear
least-squares fit of the data (concentration versus area response) is obtained. The retention
times for each analyte should agree within ± 2%.
15.4.6 Once linear response has been documented, an intermediate concentration
standard near the anticipated levels for each component, but at least 10 times the detection
limit, should be chosen for a daily calibration check. The response for the various
components should be within 15% day to day. If greater variability is observed,
recalibration may be required or a new calibration curve must be developed from fresh
standards.
15.4.7 The response for each component in the daily calibration standard is used to
calculate a response factor according to the following equation:
- (cc)
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Method IP-7 PAHs
where:
RFC = response factor (usually area counts) for the component of interest, nanograms
injected/response unit
Cc = concentration of analyte in the daily calibration standard, mg/L
Vj = volume of calibration standard injected, /iL
Rc = response for analyte in the calibration standard, area counts
15.5 Sample Analysis
15.5.1 A 100 liL aliquot of the sample is drawn into a clean HPLC injection syringe.
The sample injection loop (10 /iL) is loaded and an injection is made. The data system,
if available, is activated simultaneously with the injection and the point of injection is
marked on the strip-chart recorded.
15.52 After approximately one minute, the injection valve is returned to the load
position and the syringe and valve are flushed with acetonitrile/water solution (40/60) in
preparation for the next sample analysis.
15.5.3 After elution of the last component of interest, concentrations are calculated as
described in Section 16.2.3.
Note: Table 8 illustrates typical retention times associated with individual PAHs, while
Figure 20 represents a typical chromatogram associated with UV detection.
15.5.4 After the last compound of interest has eluted, establish a stable baseline; the
system can be now used for further sample analyses as described above.
Note: Table 9 illustrates retention time for selective PAHs using other chromatographic
columns.
15.5.5 If the concentration of analyte exceeds the linear range of the instrument, tne
sample should be diluted with mobile phase, or a smaller volume can be injected into the
HPLC. M _ , .
15.5.6 Calculate surrogate standard recovery on all samples, blanks and spikes. Calculate
the percent difference by the following equation:
% difference = [SR - Sj/SJ x 100
where:
Sj = surrogate injected, ng
SR = surrogate recovered, ng
15.5.7 Once a minimum of thirty samples of the same matrix has been analyzed,
calculate the average percent recovery (%R) and standard deviation of the percent recovery
(SD) for the surrogate.
15.5.8 For a given matrix, calculate the upper and lower control limit for method
performance for the surrogate standard. This should be done as follows:
Upper Control Limit (UCL) = (%R) + 3(SD)
Lower Control Limit (LCL) = (%R) - 3(SD)
The surrogate recovery must fall within the control limits. If recovery is not within limits,
the following is required.
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Method IP-7 PAHs
• Check to be sure there are no errors in calculations, surrogate solution, and internal
standards. Also, check instrument performance.
• Recalculate the data and/or reanalyze the extract if any of the above checks reveals
a problem.
• Re-extract and reanalyze the sample if none of the above is a problem or flag the data
as "estimated concentration."
15.5.9 Determine the concentration of each analyte in the sample according to
Section 17.1 and Section 17.2.3.
15.6 HPLC System Performance
15.6.1 The general appearance of the HPLC system should be similar to that illustrated
in Figure 8.
15.62 HPLC system efficiency is calculated according to the following equation:
N = (5.54) (tr)2/ W1/2
where:
N = column efficiency, theoretical plates
tr = retention time of analyte, seconds
W1/2 = width of component peak at half height, seconds
A column efficiency of > 5,000 theoretical plates should be obtained.
15.63 Precision of response for replicate HPLC injections should be ±10% or less, day
to day, for analyte calibration standards at 1 /tg/mL or greater levels. At 0.5 /Jg/mL level
and below, precision of replicate analyses could vary up to 25%. Precision of retention
times should be ±2% on a given day.
15.6.4 From the calibration standards, area responses for each PAH compound can be
used against the concentrations to establish working calibration curves. The calibration
curve must be linear and have a correlation coefficient greater than 0.98 to be acceptable.
15.6.5 The working calibration curve should be checked daily with an analysis of one or
more calibration standards. If the observed response (r0) for any PAH varies by more
than 15% from the predicted response (rp), the test method must be repeated with new
calibration standards. Alternately a new calibration curve must be prepared.
Note: If r0 - rp/rp > 15%, recalibration is necessary.
15.7 HPLC Method Modification
15.7.1 The HPLC procedure has been automated by Acurex Corporation (9) as part of
then: "Standard Operating Procedure for Polynuclear Aromatic Hydrocarbon Analysis by
High Performance Liquid Chromatography Methods".
15.72 The system consists of a Spectra Physics 8100 Liquid Chromatograph, a
microprocessor-controlled HPLC, a ternary gradient generator, and an autosampler (10 /dL
injection loop).
15.7.3 The chromatographic analysis involves an automated solvent program allowing
unattended instrument operation. The solvent program consists of four timed segments
Revised 9/30/89 Page 46
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Method IP-7 PAHs
using varying concentrations of acetonitrile in water with a constant flow rate, a constant
column temperature, and a 10 minute equilibration time, as outlined below.
AUTOMATED HPLC WORKING PARAMETERS
Solvent
Time Composition Temperature Rate
10 minutes 40% Acetonitrile 27.0 ± 2°C 1 mL/min
equilibration 60% Water
T=0 40% Acetonitrile
60% Water
T=25 100% Acetonitrile
T=35 100% Acetonitrile
T=45 40% Acetonitrile
60% Water
Table 9 outlines the associated PAHs with their minimum detection limits (MDL) which
can be detected employing the automated HPLC methodology.
15.7.4 A Vydac or equivalent analytical column packed with a CIS bonded phase is used
for PAH separation with a reverse phase guard column. The optical detection system
consists of a Spectra Physics 8440 Ultraviolet (UV)/Visible (VIS) wavelength detector and
a Perkin Elmer LS-4 Fluorescence Spectrometer. The UV/VIS detector, controlled by
remote programmed commands, contains a deuterium lamp with wavelength selection
between 150 and 600 nanometers. It is set at 254 nanometers with the time constant
(detector response) at 1.0 seconds.
15.7.5 The LS-4 Fluorescence Spectrometer contains separate excitation and emission
monochromators which are positioned by separate microprocessor-controlled stepper
motors. It contains a Xenon discharge lamp, side-on photomultiplier and a 3 microliter
illuminated volume flow cell. It is equipped with a wavelength programming facility to set
the monochromators automatically to a given wavelength position. This greatly enhances
selectivity by changing the fluorescence excitation and emission detection wavelengths to
specific settings during the chromatographic separation in order to optimize the detection
of each PAH. The timed excitation wavelengths range from 230 to 330 nanometers; the
emission wavelengths range from 300 to 500 nanometers. The excitation and emission slits
are both set at 10 nanometers nominal bandpass. The programmable fluorescence detector
allows optimized selectivity and sensitivity for specific compounds. The excitation and
emission wavelength conditions listed below do not necessarily correspond to the excitation
and emission maxima for the PAHs. They were selected to achieve the most selective
response for the analyte compound in the presence of known coeluting compounds. The
program fluorescence detector follows the sequence:
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Method IP-7 PAHs
Excitation Emission
Time, Wavelength, Wavelength, PAH
minutes nm nm Quantitated
0.0 254 300 anthracene
19.2 270 380 benzo[a]anthracene
dibenzo[a,h,]anthracene
benzo[g,h,i]perylene
21.0 285 450 fluoranthene
23.2 330 385 pyrene
24.7 260 400 'crysene
28.0 295 405 phenanthrene,
benzo[k]fluoranthene,
benzo[a]pyrene
benzo[g,h,i]perylene
34.6 300 500 indeno[l,2,3-cd] pyrene
15.7.6 The UV detector is used for detennining naphthalene, acenapthylene and
acenapthene, and the fluorescence detector is used for the remaining PAHs. Table 10
outlines the detection techniques and minimum detection limit (MDL) employing this
HPLC system. A Dual Channel Spectra Physics (SP) 4200 computing integrator, with a
Labnet power supply, provides data analysis and a chromatogram. An IBM PC XT with
a 10 megabyte hard disk provides data storage and reporting. Both the SP4200 and the
IBM PC XT can control all functions of the instruments in the series through the Labnet
system except for the LS-4, whose wavelength program is started with a signal from the
High Performance Liquid Chromatograph autosampler when it injects. All data are
transmitted to the XT and stored on the hard disk. Data files can later be transmitted to
floppy disk storage.
16. Quality Assurance/Quality Control (QA/QC)
16.1 General System QA/QC
16.1.1 Each laboratory that uses these methods is required to operate a formal quality
control program. The minimum requirements of this program consist of an initial
demonstration of laboratory capability and an ongoing analysis of spiked samples to
evaluate and document quality data. The laboratory must maintain records to document
the quality of the data generated. Ongoing data quality checks are compared with
established performance criteria to determine if the results of analyses meet the
performance characteristics of the method. When results of sample spikes indicate a typical
method performance, a quality control check standard must be analyzed to confirm that the
measurements were performed in an in-control mode of operation.
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Method IP-7 PAHs
16.12 Before processing any samples, the analyst should demonstrate, through the
analysis of a reagent solvent blank, that interferences from the analytical system, glassware,
and reagents are under control. Each time a set of samples is extracted or there is a
change in reagents, a reagent solvent blank should be processed as a safeguard against
chronic laboratory contamination. The blank samples should be carried through all stages
of the sample preparation and measurement steps.
16.13 For each analytical batch (up to 20 samples), a reagent blank, matrix spike and
deuterated/surrogate samples must be analyzed (the frequency of the spikes may be
different for different monitoring programs). The blank and spiked samples must be carried
through all stages of the sample preparation and measurement steps.
16.1.4 The experience of the analyst performing GC and HPLC is invaluable to the
success of the methods. Each day that analysis is performed, the daily calibration sample
should be evaluated to determine if the chromatographic system is operating properly.
Questions that should be asked are: Do the peaks look normal? Are the response windows
obtained comparable to the response from previous calibrations? Careful examination of
the standard chromatogram can indicate whether the column is still good, the injector is
leaking, the injector septum needs replacing, etc. If any changes are made to the system
(e.g., column changed), recalibration of the system must take place.
Process, Field, and Solvent Blanks
162.1 One cartridge (XAD-2 or PUF) and filter from each batch of approximately
twenty should be analyzed, without shipment to the field, for the compounds of interest to
serve as a process blank. A blank level of less than 10 ng per cartridge/filter assembly for
a single PAH component is considered to be acceptable.
1622 During each sampling episode at least one cartridge and filter should be shipped
to the field and returned, without drawing air through the sampler, to serve as a field
blank.
1623 During the analysis of each batch of samples at least one solvent process blank
(all steps conducted but no cartridge or filter included) should be carried through the
procedure and analyzed. Blank levels should be less than 10 ng/sample for single
components to be acceptable.
162.4 Because the sampling configuration (filter and backup adsorbent) has been tested
for targeted PAHs in the laboratory in relationship to collection efficiency and has been
demonstrated to be greater than 95% for targeted PAHs (except naphthalene), no field
recovery evaluation will occur as part of the QA/QC program outlined in this section.
163 Gas Chromatography with Flame lonization Detection
163.1 Under the calibration procedures (internal and external), the % RSD of the
calibration factor should be <20% over the linear working range of a five point calibration
curve (see Section 13.4.1.6 and Section 13.4.2.6).
1632 Under the calibration procedures (internal and external), the daily working
calibration curve for each analyte should not vary from the predicted response by more than
±20% (see Section 13.4.1.7 and Section 13.4.2.8).
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Method IP-7 PAHs
16.3.3 For each analyte, the retention time window must be established (see Section
13.5.1), verified on a daily basis (see Section 13.6.3.2) and established for each analyte
throughout the course of a 72 hour period (see Section 13.5.3).
163.4 For each analyte, the mid level standard must fall within the retention time
window on a daily basis as a qualitative performance evaluation of the GC system (see
Section 13.6.3.4).
16.3.5 The surrogate standard recovery must not deviate from 100% by more than 20%
(see Section 13.6.3.5).
16.4 Gas Chromatography with Mass Spectroscopy Detection
16.4.1 Section 14.5.1 requires the mass spectrometer be tuned daily with DFTPP and
meet relative ion abundance requirements outlined in Table 3.
16.42 Section 14.3.1.1 requires a minimum of five concentration levels of each analyte
(plus deuterated internal standards) be prepared to establish a calibration factor to illustrate
<20% variance over the linear working range of the calibration curve.
16.43 Section 14.3.1.13 requires the verification of the working curve each working day
(if using the external standard technique) by the measurement of one or more calibration
standards. The predicted response must not vary by more than ±20%.
16.4.4 Section 14.3.2.6 requires the initial calibration curve be verified each working day
(if using the internal standard technique) by the measurement of one or more calibration
standards. If the response varies by more than +.20% of predicted response, a fresh
calibration curve (five point) must be established.
16.4.5 Section 14.4.5 requires that for sample analysis, the comparison between the
sample and reference spectrum illustrates: The sample analysis using the GC-MS-SIM is
based on a combination of retention times and relative abundances of selected ions (see
Table 5). These qualifiers are stored on the hard disk of the GC-MS data computer and
are applied for identification of each chromatographic peak. The retention time qualifier
is determined to be + 0.10 minute of the library retention time of the compound. The
acceptance level for relative abundance is determined to be ± 15% of the expected
abundance. Three ions are measured for most of the PAH compounds. When compound
identification is made by the computer, any peak that fails any of the qualifying tests is
flagged (e.g., with an *). The data should be manually examined by the analyst to
determine the reason for the flag and whether the compound should be reported as found.
While this adds some subjective judgment to the analysis, computer- generated identification
problems can be clarified by an experienced operator. Manual inspection of the
quantitative results should also be performed to verify concentrations outside the expected
range.
16.4.6 Section 14.5.3 requires that initial calibration curve be verified every twelve
continuous hours of analysis by a mid level calibration standard. The response must be less
than 20% difference from the initial response.
16.4.7 The surrogate standard recovery must not deviate from 100% by more than
20% (see Section 14.5.4).
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Method IP-7 _ _____ _ PAHs
16.5 High Performance Liquid Chromatography Detection
16.5.1 Section 15.4.4 requires the preparation of calibration standards at a minimum
of five concentration levels to establish correlation coefficient of at least 0.999 for a linear
least-squares fit of the data.
16.5.2 Section 15.4.5 requires that the retention time for each analyte should agree
within ±2%. • ••,<=
16.53 A daily calibration check involving an intermediate standard of the initial rive
point calibration curve should be within +.15% from day to day.
16.5.4 Section 15.5.6 requires the calculation of percent difference of surrogate standard
recovery hi order to establish control limits:
Upper Control Limit (UCL) = (%R) + 3 (SD)
Lower Control Limit (LCL) = (%R) - 3 (SD)
The surrogate recovery must fall within the control limits.
17. Calculations
17.1 Sample Volume
17.1.1 Retrieve the data logger and download to a computer using the procedure
outlined in Section 11.2.20. . ,,_.,.
Note: All volumetric flows have been corrected to STP as illustrated in Section 11.2.1b.
17.1 2 The total sample volume (VJ is calculated from the periodic flow readings using
the following equation.
Vs = [(Qj + Q2 -. + Qn)/N] x [T]
where:
Vs = total sample volume at STP conditions, m
QI, Q2, ...Qn =flow rates determined at the beginning, end, and intermediate points during
sampling, L/minute, see Section 11.2.2.6 and Section 11.2.2.7,
N = number of data points
T = elapsed sampling time, minutes
17 3 Sample Concentration
17.2.1 Gas Chromatography with Flame lonization Detection
17.2.1.1 The concentration of each analyte in the sample may be determined from
the external standard technique by calculating from the peak response, the amount of
standard injected using the calibration curve or the calibration factor determined in Section
13.4.1.6.
17 2.12 The concentration of a specific analyte is calculated as follows:
Concentration, ng/m3 = [(Ax)(Vt)(D)]/[(CF)(V ,)(V,)]
Revised 9/30/89 Pa8e 51
-------
Method IP-7 PAHs
where:
CF = calibration factor for chromatographic system, peak height or area response per mass
injected, Section 13.4.1.6
Ax = response for the analyte in the sample, area counts or peak height
Vt = volume of total sample, pL
D = dilution factor, if dilution was made on the sample prior to analysis. If no dilution
was made, D=l, dimensionless
V, = volume of sample injected, (iL
Vs = total sample volume at standard temperature and pressure (25°C and 760 mm Hg),
m3, see Section 112.16 and Section 17.1.2.
17 22 Gas Chromatography-Mass Spectroscopy Detection
1122.1 When an analyte has been identified, the quantification of that analyte will
be based on the integrated abundance from the monitoring of the primary characteristic ion.
Quantification will take place using the internal standard technique. The internal standard
used shall be the one nearest the retention time of that of a given analyte (see Section
14.3.2.1).
17222 Calculate the concentration of each identified analyte in the sample as
follows:
Concentration, ng/m3 = [(Ax)(Is)(Vt)(D)]/[(A1s)(RF)(V1)(Vs)]
where:
Ax = area of characteristic ion(s) for analyte being measured, counts
Is = amount of internal standard injected, ng
Vt = volume of total sample, iiL
D = dilution factor, if dilution was made on the sample prior to analysis. If no dilution
was made, D = 1, dimensionless
A1s = area of characteristic ion(s) for internal standard, counts
RF = response factor for analyte being measured, see Section 14.3.2.5
V, = volume of analyte injected, pL
Vs = total sample volume at standard temperature and pressure (25°C and
760 mm Hg), m3, see Section 17.1
1723 High Performance Liquid Chromatography Detection
17.2.3.1 The concentration of each analyte in the sample may be determined from
the external standard technique by calculating response factor and peak response using the
calibration curve.
17232 The concentration of a specific analyte is calculated as follows:
Concentration, ng/m3 = [(RFc)(Ax)(Vt)(D)]/[(V1)(Vs)]
where:
RFC = response factor calculated in Section 15.4.7, ng/area counts
Ax = response for the analyte in the sample, area counts or peak height
Revised 9/30/89 Page 52
-------
Method IP-7 PAHs
Vt = volume of total sample, /iL
D = dilution factor, if dilution was made on the sample prior to analysis. If no dilution
was made, D = 1, dimensionless
Vt = volume of sample injected, /iL
Vs = total sample volume at standard temperature and pressure (25°C and 760 mm Hg),
m3, see Section 17.13
173 Sample Concentration Conversion From ng/m3 to ppbv
173.1 The concentrations calculated in Section 172 can be converted to ppbv for general
reference.
1732 The analyte concentration can be converted to ppbv using the following equation:
CA (ppbv) = CA (ng/m3) x 24.4/MWA
where:
CA = concentration of analyte calculated according to Section 17.2.1 through Section
17.2.3, ng/m3
MWA = molecular weight of analyte, g/g-mole
24.4 = molar volume occupied by ideal gas at standard temperature and pressure (25°C
and 760 mm Hg), L/mole
18. Acknowledgements
The determination of PAHs in ambient air is a complex task, primarily because of the wide
variety of compounds of interest and the lack of standardized sampling and analysis
procedures. Compendium Method IP-7 is an effort to address these difficulties.
While there are numerous procedures for sampling and analyzing PAHs in ambient air, this
method draws upon the best aspects of each one and combine them into a standardized
methodology. To that end, the following individuals contributed to the research,
documentation and peer review of this manuscript.
Topic Contact Address/Telephone
Analytical System
GC-MS Dr. Jane C. Chuang Battelle Laboratory
Columbus Division
505 King Avenue
Columbus, OH 43201-2693
(614) 424-5222
GC-FDD Mr. Ron Buckson Engineering-Science
57 Executive Park South, NE
Suite 590
Atlanta, GA 30329
(404) 325-0770
Revised 9/30/89 Page 53
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Method IP-7
PAHs
HPLC Ms. Susan Rasor
Mr. Rob Martz
Sampling System
Portable Tripod Mr. Jody Hudson
Tripod
Low Flow Rate Dr. Bob Coutant
Sampler
Acoustic
Enclosed
Sampler
Dr. Mike Kuhlman
Dr. Jane C. Chuang
Storage
Dr. Jane C. Chuang
Acurex Corporation
4915 Prospectus Drive
Durham, NC
(919) 541-2147
U.S. EPA
Environmental Services Division
Region VH
25 Funston Road
Kansas City, KS 66115
(913) 236-3884
Battelle Laboratory
Columbus Division
505 King Avenue
Columbus, OH 43201-2693
(614) 424-5247
Battelle Laboratory
Columbus Division
505 King Avenue
Columbus, OH 43201-2693
(614) 424-5393
Battelle Laboratory
Columbus Division
505 King Avenue
Columbus, OH 43201-2693
(614) 424-5222
Battelle Laboratory
Columbus Division
505 King Avenue
Columbus, OH 43201-2693
(614) 424-5222
Revised 9/30/89
Page 54
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Method IP-7
PAHs
Dr. Nancy Wilson
Dr. Bob Lewis
Mr. Harilal L. Patel
Dr. Steve Swarin
Methodology
U.S. EPA
Atmospheric Research and Exposure
Assessment Laboratory (AREAL)
MD-44
Research Triangle Park, NC 27711
(919) 5414723
Allegheny Co. Health Dept.
Bureau of Air Pollution Control
301-39th Street
Pittsburgh, PA 15201
(412) 578-8113
General Motors Research Lab.
Analytical Chemistry Department
3-201-RAV
Warren, MI 48090-9055
(313) 986-0806
19. References
1. Dubois, L., Zdrojgwski, A., Baker, C, and Monknao J. L., "Some Improvement in the
Determination of Benzo[a]Pyrene in Air Samples," Air Pollution Control Association J.,
17:818-821, 1967.
2. Intersociety Committee 'Tentative Method of Analysis for Polynuclear Aromatic
Hydrocarbon of Atmospheric Particulate Matter," Health Laboratory Science, 7(1):31-40,
1970.
3. Cautreels, W., and Van Cauwenberghe, K., "Experiments on the Distribution of Organic
Pollutants Between Airborne Particulate Matter and Corresponding Gas Phase," Atmos.
Environ., 12:1133-1141, 1978.
4. 'Tentative Method of Microanalysis for Benzo[a]Pyrene in Airborne Particules and
Source Effluents," American Public Health Association, Health Laboratory Science, 7(1):56-
59, 1970.
5. 'Tentative Method of Chromatographic Analysis for Benzo[a]Pyrene and
Benzo[k]Fluoranthene in Atmospheric Particulate Matter," American Public Health
Association, Health Laboratory Science, 7(l):60-67, 1970.
6. 'Tentative Method of Spectrophotometric Analysis for Benzo[a]Pyrene in Atmospheric
Particulate Matter," American Public Health Association, Health Laboratory Science, 7(1):68-
71, 1970.
Revised 9/30/89
Page 55
-------
Method IP-7 PAHs
7. Jones, P. W., Wilkinson, J. E., and Strup, P. E., Measurement of Polycyclic Organic
Materials and Other Hazardous Organic Compounds in Stack Gases: State-of-art, U.S. EPA-
600/2-77-202, 1977.
8. Walling, J. F., Standard Operating Procedure for Ultrasonic Extraction and Analysis of
Residual BenzofaJPyrene from Hi-Vol Filters via Thin-Layer Chromatography, U.S.
Environmental Protection Agency, Environmental Monitoring Systems Laboratory, Methods
Development and Analysis Division, Research Triangle Park, NC, EMSL/RTP-SOP-
MDAD-015, December, 1986.
9. Rasor, S., Standard Operating Procedure for Pofynuclear Aromatic Hydrocarbon Analysis
by High Performance Liquid Chromatography Methods, Acurex Corporation, Research
Triangle Park, NC, 1978.
10. Rapport, S. W., Wang, Y. Y., Wei, E. T., Sawyer, R., Watkins, B. E., and Rapport, H.,
"Isolation and Identification of a Direct-Acting Mutagen in Diesel Exhaust Particulates,"
Envir. Sci TechnoL, 14:1505-1509, 1980.
11. Konlg, J., Balfanz, E., Funcke, W., and Romanowski, T., "Determination of Oxygenated
Polycyclic Aromatic Hydrocarbons in Airborne Paniculate Matter by Capillary Gas
Chromatography and Gas Chromatography/Mass Spectrometry,"j4/uz£ Chem., 55:599-603,
1983.
12. Chuang, J. G, Bresler, W. E., and Hannan, S. W., Evaluation of Pofyurethane Foam
Cartridges for Measurement of Pofynuclear Aromatic Hydrocarbons in Air, U.S. Environmental
Protection Agency, Environmental Monitoring Systems Laboratory, Methods Development
and Analysis Division, Research Triangle Park, NC, EPA-600/4-85-055, September, 1985.
13. Chuang, J. G, Hannan, S. W., and Koetz, J. R., Stability of Pofynuclear Aromatic
Compounds Collected from Air on Quartz Fiber Filters andXAD-2 Resin, U.S. Environmental
Protection Agency, Environmental Monitoring Systems Laboratory, Methods Development
and Analysis Division, Research Triangle Park, NC, EPA-600/4-86-029, September, 1986.
14. Feng, Y., and Bidleman, T. F., "Influence of Volatility on the Collection of Polynuclear
Aromatic Hydrocarbon Vapors with Polyurethane Foam," Envir. Set TechnoL, 18:330-333,
1984.
15. Yamasaki, H., Kuwata, K., and Miyamoto, H., "Effects of Ambient Temperature on
Aspects of Airborne Polycyclic Aromatic Hydrocarbons," Envir. ScL TechnoL, 16:89-194,
1982.
16. Chuang, J. G, Hannan, S. W., and Koetz, J. R., Comparison of Polyurethane Foam and
XAD-2 Resin as Collection Media for Pofynuclear Aromatic Hydrocarbons in Air, U.S.
Environmental Protection Agency, Environmental Monitoring Systems Laboratory, Methods
Development and Analysis Division, Research Triangle Park, NC, EPA-600/4-86-034,
December, 1986.
Revised 9/30/89 Page 56
-------
Method IP-7 PAHs
17. Chuang, J. G, Mack, G. A., Mondron, P. J., and Peterson, B. A., Evaluation of
Sampling and Analytical Methodology for Pofynuclear Aromatic Compounds in Indoor Air,
U.S. Environmental Protection Agency, Environmental Monitoring Systems Laboratory,
Methods Development and Analysis Division, Research Triangle Park, NC, EPA-600/4-
85-065, January, 1986.
18. Winberry, W. T., and Murphy, N.T., Supplement to Compendium of Methods for the
Determination of Toxic Organic Compounds in Ambient Air, U.S. Environmental Protection
Agency, Environmental Monitoring Systems Laboratory, Quality Assurance Division,
Research Triangle Park, NC, EPA-600/4-87-006, September, 1986.
19. Winberry, W. T., and Murphy, N. T., Second Supplement to Compendium of Methods
for the Determination of Toxic Organic Compounds in Ambient Air, U.S. Environmental
Protection Agency, Environmental Monitoring Systems Laboratory, Quality Assurance
Division, Research Triangle Park, NC, EPA 600/4-89-018, June, 1988.
20. Methods for Organic Chemical Analysis of Municipal and Industrial Wastewater, U.S.
Environmental Protection Agency, Environmental Monitoring and Support Laboratory,
Cincinnati, OH, EPA-600/4-82-057, July 1982.
21. ASTM Annual Book of Standards, Part 31, D 3694, "Standard Practice for Preparation
of Sample Containers and for Preservation," American Society for Testing and Materials,
Philadelphia, PA, p. 679, 1980.
22. Burke, J. A., "Gas Chromatography for Pesticide Residue Analysis; Some Practical
Aspects," Journal of the Association of Official Analytical Chemists, 48:1037, 1965.
23. Cole, T., Riggin, R., and Glaser, J., Evaluation of Method Detection Limits an Analytical
Curve for EPA Method 610 - PNAs, 5th International Symposium on Polynuclear Aromatic
Hydrocarbons, Battelle Columbus Laboratory, Columbus, OH, 1980.
24. Handbook of Analytical Quality Control in Water and Wastewater Laboratories, U.S.
Environmental Protection Agency, Environmental Monitoring and Support Laboratory,
Cincinnati, OH 45268, EPA-600/4-79-019, March, 1979.
25. ASTM Annual Book of Standards, Part 31, D 3370, "Standard Practice for Sampling
Water," American Society for Testing and Materials, Philadelphia PA, p. 76, 1980.
26. Protocol for the Collection and Analysis of Volatile POHC's (Principal Organic Hazardous
Constituents) using VOST (Volatile Organic Sampling Train), PB84-170042, EPA-600/8-84-
007, March, 1984.
27. Sampling and Analysis Methods for Hazardous Waste Combustion - Methods 3500, 3540,
3610, 3630, 8100, 8270, and 8310; Test Methods For Evaluating Solid Waste (SW-846), U.S.
Environmental Protection Agency, Office of Solid Waste, Washington, DC.
28. Riggin, R. M., Compendium of Methods for the Determination of Toxic Organic
Compounds in Ambient Air, U.S. Environmental Protection Agency, Environmental
Revised 9/30/89 Page 57
0 J
-------
Method IP-7 PAHs
Monitoring Systems Laboratory, Quality Assurance Division, Research Triangle Park, NC,
EPA-600/4-84-041, April, 1984.
29. Chuang, C. C, and Peterson, B. A., Review of Sampling and Analysis Methodology for
Pofynuclear Aromatic Compounds in Air from Mobile Sources, Final Report, EPA-600/S4-
85-045, August, 1985.
30. Measurement of Potycyclic Organic Matter for Environmental Assessment, U.S.
Environmental Protection Agency, Industrial Environmental Research Laboratory, Research
Triangle Park, NC, EPA-600/7-79-191, August, 1979.
31. Hudson, J. L., Standard Operating Procedure No. FA 113C: Monitoring For Particulate
and Vapor Phase Pollutants Using the Portable Particulate/Vapor Air Sampler, U.S.
Environmental Protection Agency, Region VII, Environmental Monitoring and Compliance
Branch, Environmental Services Division, Kansas City, KS, March, 1987.
32. Technical Assistance Document for Sampling and Analysis of Toxic Organic Compounds
in Ambient Air, U.S. Environmental Protection Agency, Environmental Monitoring Systems
Laboratory, Quality Assurance Division, Research Triangle Park, NC, EPA-600/4-83-027,
June, 1983.
33. Arey, J., Zielinska, B., Atkinson, R., and Winer, A. M.Atmos. Environ., 21:1437-1444,
1987.
34. Chuang, J. C, Mack, G. A., Koetz, J. R., and Petersen, B. A., EPA/600/4-86/036;
Environmental Monitoring Systems Laboratory, U.S. Environmental Protection Agency,
Research Triangle Park, NC, 1987.
35. Gamer, R. C, Stanton, C. A., Martin, C. N., Chow, F. L., Thomas, W., Hubner, D., and
Herrmann, R., Environ. Mutagen., 8:109-117, 1986.
36. Pyysalo, H., Tuominen, T., Mattila, T., and Pohjola, V.,Atmos. Environ., 21:1167-1180,
1987.
37. Siak, J., Chan, T. L., Gibson, T. L., and Wolff, G. T.,Atmos. Environ., 19:369-376,1985.
38. Tokiwa, H., Kitamofi, S., Nakagwa, R., Horikawa, K., and Matamala, L., Mutation
Research, 121:107-116, 1983.
39. Miller, M., Alfheim, I., Larssen, S., and Mikalsen, A., Environ. ScL TechnoL, 16:221-
225, 1982.
40. Lewtas, J., Goto, S., Williams, K., Chuang, J. C, Peterson, B. A., and Wilson, N. K.,
Atmos. Environ., 21:443-449, 1987.
41. Chuang, J. C, Mack, G. A., Peterson, B. A., and Wilson, N. K., Pofynuclear Aromatic
Hydrocarbons: Chemistry, Characterization, and Carcinogenesis, Cooke, M., and Dennis,
A, J., Eds., Battelle Press, Columbus, OH, pp. 155-171, 1986.
Revised 9/30/89 Page 58
-------
Method IP-7 PAHs
42. Kuhlman, M. R., and Chuang, J. C, Design and Preliminary Evaluation of a Low Flow
Rate Indoor Air Sampler, U.S. Environmental Protection Agency, Environmental Monitoring
Systems Laboratory, Methods Development and Analysis Division, Research Triangle Par,
NC, Contract 68-02-4127, WA-54, September, 1989.
43. Wilson, N. K., Kuhlman, M. R., Chuang, J. C, Mack, G. A., and Howes, J. E.,A Quiet
Sampler for the Collection of Semi-Volatile Organic Pollutants in Indoor Air, U.S.
Environmental Protection Agency, Atmospheric Exposure and Assessment Research
Laboratory, Methods Research Branch, Research Triangle Park, NC, May, 1988.
44. ASTM Annual Book of Standards, Part 31, D 3694, "Standard Practice for Preparation
of Sample Containers and for Preservation," American Society for Testing and Materials,
Philadelphia, PA, p. 679, 1980.
45. HPLC Troubleshooting Guide - How to Identify, Isolate, and Correct Many HPLC
Problems, Supelco Inc., Supelco Park, Bellefonte, PA, 16823-0048, Guide 826, 1986.
46. Carcinogens - Working with Carcinogens, Department of Health, Education, and Welfare,
Public Health Service, Center for Disease Control, National Institute for Occupational
Safety and Health, Publication No. 77-206, August, 1977.
47. OSHA Safety and Health Standards, General Industry, (29CFR1910), Occupational
Safety and Health Administration, OSHA 2206, Revised, January, 1976.
48. "Safety in Academic Chemistry Laboratories," American Chemical Society Publication,
Committee on Chemical Safety, 3rd Edition, 1979.
Revised 9/30/89 Page 59
'"
-------
Method IP-7
PAHs
Table 1. Formulas and Physical Properties of Selective PAHs
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
Benzo(b)fluoranthene
Benzo(e)pyrene
Benzo(g,h,i)perlene
Benzo(k)fluoranthene
Chrysene
Dibenzo(a,h)anthracene
Fluoranthene
Fluorene
Indeno(l,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
*Many of these compounds sublime.
Formula
C12H10
C12H8
C14H10
C18H12
C20H12
C20H12
C20H12
C22H12
C18H12
C22H14
C16H10
C13H10
C22H12
C10H8
C14H10
C1RH,n
Molecular
Weight
154.21
152.20
178.22
228.29
252.32
252.32
252.32
276.34
252.32
228.29
278.35
202.26
166.22
276.34
128.16
178.22
202.26
Melting
Point TO*
96.2
92-93
218
158-159
177
168
178-179
273
217
255-256
261
110
116-117
161.5-163
80.2
100
156
Boiling
Point(°O
279
265-275
342
-
310-312
-
-
-
480
-
-
-
293-295
-
217.9
340
399
Case#
83-32-9
208-96-8
120-12-7
56-55-3
50-32-8
205-99-2
192-92-2
191-24-2
207-08-9
218-01-9
53-70-3
206-44-0
86-73-7
193-39-5
91-20-3
85-01-8
129-00-0
Revised 9/30/89
Page 60
-------
Method IP-7 PAHs
Table 2. Retention Times for Selective PAHs for Packed
and Capillary Columns Using Flame
lonization Detector
Compound Packed1 Capillary2
Acenaphthene 10.8 8.60
Acenaphthylene 10.4 11.38
Anthracene 15.9 11.65
Benzo(a)anthracene 20.6 12.60
Benzo(a)pyrene 29.4 14.82
Benzo(b)fluoranthene 28.0 15.00
Benzo(ghi)perylene 38.6 19.05
Benzo(k)fluoranthene 28.0 20.05
Chrysene 24.7 26.90
Dibenzo(a,h)anthracene 36.2 27.20
Fluoranthene 19.8 34.00
Fluorene 12.6 34.20
Indeno(l,2,3-cd)pyrene 36.2 35.98
Naphthalene 4.5 42.80
Phenanthrene 15.9 43.00
Pyrene 20.6 44.18
1 GC conditions: Chromosorb W-AW-DMCS (100/120 mesh) coated with 3% OV-
17,packed in a 1.8-m long x 2 mm ID glass column, with nitrogen carrier gas at a flow
rate of 40 mL/min. Column temperature was held at 100°C for 4 min. then
programmed at 8°/minute to a final hold at 280°C.
2 Capillary GC conditions: 30 meter x 0.25 mm ID fused silica, DB-5 capillary column;
on column injection; oven temperature held at 40°C for 1 minute; program at 15°C/min
to 200°C; program at 3°C/min to 300°C (see Figure 17 for representative chromatogram
under these conditions).
Revised 9/30/89 Page 61
(D(\
-------
Method IP-7 PAHs
Table 3. DFTPP Key Ions and Ion Abundance Criteria
Mass Ion Abundance Criteria
51 30-60% of mass 198
68 Less than 2% of mass 69
70 Less than 2% of mass 69
127 40-60% of mass 198
197 Less than 1% of mass 198
198 Base peak, 100% relative abundance
199 5-9% of mass 198
275 10-30% of mass 198
365 Greater than 1% of mass 198
441 Present but less than mass 443
442 Greater than 40% of mass 198
443 17-23% of mass 442
Revised 9/30/89 Page 62
-------
Method IP-7
PAHs
Table 4. GC and MS Operating Conditions
Chromatography
Column
Carrier Gas
Injection Volume
Injection Mode
Temperature Program
Initial Column Temp.
Initial Hold Time
Program
Final Hold Time
Mass Spectrometer
Detection Mode
J & W Scientific, DB-5 crosslinked 5% phenylmethyl
silicone (30 m x 0.25 mm, 0.25 /on film thickness) or
equivalent
Helium velocity 20 cm3/sec at 250°C
1/iL
On-column injection
60°C
1 min
60°C to 200°C at 15°C/min; 200°C to 310°C at 3°C/min
15 min until benzo(ghi)perylene eludes
Multiple ion detection, SIM mode
Revised 9/30/89
Page 63
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Method IP-7
PAHs
Table 5. Approximate Retention Time and Characteristic Ions
From GC-MS Detection for Selected PAHs
Approximate1
Retention Characteristic Ions Double
Compound Time (min') Primary Secondary Charge Ions
152 77
153 76
176 89
226 114
125 126
125 126
277 138
125 226
229 114 .
279 139
203 101
167 83
227 138
127 64
176 89
203 101
1 Capillary GC conditions: 30 m x 0.25 mm DB-5 fused silica capillary column; on-
column injection; oven temperature held at 60°C for 1 minute; program at 15°C/min to
200°C; program at 3°C/min to 310°C (see Figure 19 for representative chromatogram
under these conditions).
Acenaphthene 10.57
Acenaphthylene 10.24
Anthracene 14.04
Benzo(a)anthracene 26.42
Benzo(a)pyrene 35.53
Benzo(b)fluoranthene 33.55
Benzo(ghi)perylene 43.70
Benzo(k)fluoranthene 33.72
Chrysene 26.66
Dibenzo(a,h)anthracene 42.62
Fluoranthene 18.36
Fluorene 11.56
Indeno(l,2,3-cd)pyrene 42.34
Naphthalene 7.10
Phenanthrene 13.84
Pyrene 19.37
154
152
178
228
252
252
276
252
228
278
202
166
276
128
178
202
153
151
179
229
253
253
138
253
226
139
101
165
138
129
179
200
Revised 9/30/89
Page 64
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Method IP-7 PAHs
Table 6. Characteristic Ions From GC-MS Detection
for Deuterated Internal Standards and Selected PAHs
Compound M/Z
D8-naphthalene 136
D10-phenanthrene 188
Phenanthrene 178
Anthracene 178
Fluoranthene 202
D10-pyrene 212
Pyrene 202
Cyclopenta[c,d]pyrene 226
Benzo[a]anthracene 228
D12-chrysene 240
Benzo[e]pyrene 252
D12-benzo[a]pyrene 264
Benzo[a]pyrene 252
Revised 9/30/89 Page 65
*****«"?
-------
Method IP-7
PAHs
Table 7. Commercially Available Columns for PAH
Analysis Using HPLC
Company
The Separation Group
P.O. Box 867
Hesperia, California 92345
Column Identification
201-TP
Rainin Instrument Company Ultrasphere - ODS
Mack Road
Wasurn, MA 01801-4626
Supelco, Inc. LC-PAH
Supelco Park
Bellefonte, PA 16823-0048
DuPont Company ODS
Biotechnology Systems
Barley Mill Plaza, P24
Wilmington, DE 19898
Perkin-Elmer Corp. HC-ODS
Corporate Office
Main Avenue
Norwalk, CT 06856
Waters Associates /j-Bondapak
34-T Maple St.
Milford, MA 01757
Column Name
VYDAC
ALEX
Supelcosil
Zorbax
Sil-X
/j-Bondapak NH2
Revised 9/30/89
Page 66
6*3
-------
Method IP-7 PAHs
Table 8. Typical Retention Time for Selective PAHs
by HPLC Separation* and UV Detection
Retention Times
Compound (minutes)
Acenaphthene 18.0
Acenaphthylene 15.8
Anthracene 21.0
Benzo(a)anthracene 26.3
Benzo(a)pyrene 31.1
Benzo(b)fluoranthene 293
Benzo(ghi)perylene 33.9
Benzo(k)fluoranthene 30.2
Chrysene 26.7
Dibenzo(a,h)anthracene 32.7
Fluoranthene 22.5
Fluorene 18.5
Indeno(l,2,3-cd)pyrene 34.6
Naphthalene 14.0
Phenanthrene 19.9
Pyrene 23.4
* HPLC parameters: VYDAC 201 guard column, reverse phase VYDAC 201 TP 5415
analytical column. Isocratic elution for 10 minutes using acetonitrile/water (4:6)(v/v),
then linear gradient elution to 100% acetonitrile withhi 15 minutes, then 100%
acetonitrile for 10 minutes, then linear gradient to acetonitrile/water (4:6)(v/v) within 10
minutes. UV detector operating at 254 nm.
Revised 9/30/89 Page 67
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Method IP-7 PAHs
Table 9. Typical Retention Time for Selective PAHs
by HPLC Separation and UV Detection
Compound Method 831Q1 Fluorescence2 Ultraviolet2
Acenaphthene 20.5 - 18.0
Acenaphthylene 18.5 - 15.8
Anthracene 23.4 21.0 21.0
Benzo(a)anthracene 28.5 26:3 26.3
Benzo(a)pyrene 33.9 31.1 31.1
Benzo(b)fluoranthene 31.6 29.3 29.3
Benzo(ghi)perylene 36.3 33.9 33.9
Benzo(k)fluoranthene 32.9 30.2 30.2
Chrysene 29.3 26.7 26.7
Dibenzo(a,h)anthracene 35.7 32.7 32.7
Fluoranthene 24.5 22.5 22.5
Fluorene 21.2 18.5 18.5
Indeno(l,2,3-cd)pyrene 37.4 34.6 34.6
Naphthalene 16.6 - 14.0
Phenanthrene 22.1 19.9 19.9
Pyrene 25.4 23.4 23.4
1 Condition A HPLC Parameters: Reverse phase HC-ODS Si -X, 5 micron particle
size, in a 250 mm x 2.6 mm ID stainless steel column. Isocratic elution for 5 min using
acetonitrile/ water (4:6)(v/v), then linear gradient elution to 100% acetonitrile over 25
min at 0.5 mL/min flow rate.
Note: If columns having other internal diameters are used, the flow rate should be
adjusted to maintain a linear velocity of 2 mm/sec. UV detector operating at 254 nm.
2 Condition B HPLC Parameters: VYDAC 201 guard column, reverse phase VYDAC
201 TP 5415 analytical column. Isocratic elution for 10 minutes using acetonitrile/water
(4:6)(v/v), then linear gradient elution to 100% acetonitrile within 15 minutes, then
100% acetonitrile for 10 minutes, then linear gradient to acetonitrile/water (4:6)(v/v)
within 10 minutes. UV detector operating at 254 nm.
Revised 9/30/89 Page 68
-------
Method IP-7
PAHs
Table 10. Retention Times (RTs) and Minimum Detection Limits (MDLs)
for Selected PAHs by HPLC Analysis' Using UV and Fluorescence Detection
Ultraviolet Detector
Retention Time Detection Limit
Fluorescence Detector
Retention Time Detection Limit
PAH
Naphthalene 14.0 250pg//*L
Acenaphthylene 15.85 250pg//iL
Acenaphthene 18.0 250pg//iL
Huorene 18.5 50pg//iL 18.5
Phenanthrene 19.9 50pg//tL 19.9
Anthracene 21.0 50pg//*L 21.0
Fluoranthene 22.5 50pg/j»L 22.5
Pyrene 23.4 50pg//iL 23.4
Benzo(a)anthracene 26.3 50pg//*L 26.3
Chrysene 26.7 50pg//*L 26.7
Benzo(b)fluoranthene 29.3 50pg//*L 29.3
Benzo(k)fluoranthene 30.2 50pg//dL 302
Benzo(a)pyrene 31.1 50pg//iL 31.1
Dibenzo(a,h)anthracene 32.7 50pg/0L 32.7
Benzo(ghi)perylene 33.9 50pg//iL 33.9
Indeno(l,2,3-cd)pyrene 34.6 50pg//iL 34.6
' HPLC Conditions:
Guard Column:
Analytical Column:
Column Temperature:
Mobile Phase:
Solvent Composition Time (Minutes')
40% Acetonitrile/60% water 0
100% Acetonitrile 25
100% Acetonitrile 35
40% Acetonitrile/60% water 45
Linear gradient elution at 1.0 mL/min
Detector: UV, operating at 254 nm
Fluorescence, programmable wavelength to set monochromators at:
5pg//*L
10pg//*L
50pg//iL
10pg//xL
10pg//iL
5pg/ML
5pg//dL
5pg//iL
5pg//*L
50pg//iL
VYDAC 201 GCCIOYT
VYDAC 201 TP5415 C-18 RP (0.46 x 25 cm)
27.0 ± 2°C
Flow Rate: 1.0 mL/minute
Injection Volume: 10 fiL
Time
0.0
19.2
21.9
23.2
24.7
28.0
34.6
Fixed Scale
0.5
Excitation (nrn)
254
270
285
330
260
295
300
Emission
300
380
450
385
400
405
500
Revised 9/30/89
Page 69
-------
Method IP-9 _ Reactive Gases/Particulate Matter
7. Apparatus
Note: The following descriptions relate to Figure 2. Most of these parts are available
commercially by University Research Glassware. However, it is important to note that
these items can be made by any qualified vendor; therefore, it is not necessary that these
specific items are obtained and utilized.
7.1 Sampling
7.1.1 Elutriator and acceleration jet assembly - Under normal sampling conditions, the
elutriator or entry tube is made of either Teflon* coated glass or aluminum. When using
glass, the accelerator jet assembly is fixed onto the elutriator and the internal surfaces of
the entire assembly are coated with Teflon*. When aluminum is used, the accelerator jet
assembly is removable. The jet is made of Teflon* or polyethylene and the jet support is
made of aluminum. Again, all internal surfaces are coated with Teflon*. Both assemblies
are available with 2, 3 and 4 mm inside diameter jets (nozzles) [University Research
Glassware, 118 E. Main St., Carrboro, NC, 27510, (919-942-2753)]. ,
7.1 2 Teflon* impactor support pin and impactor frit support tools - Made of either
Teflon* or polyethylene and are used to aid in assembling, removing, coating and cleaning
the impactor frit [University Research Glassware, 118 E. Main St., Carrboro, NC, 27510,
(919-942-2753)]. * . . „ , A-
7.13 Impactor frit and coupler assembly - The impactor frit is 10 mm x 3 mm and is
available with a porosity range of 10-20 Mm. The frits should be made of porous ceramic
material or fritted stainless steel. Before use the impactor frit surface is coated with a Dow
Corning 660 oil and toluene solution for use, and sits in a Teflon* seat support fixed within
the coupler. The coupler is made of thermoplastic and has Teflon* clad sealing "0"-nngs
which are located on both sides of the seat support inside the coupler. The couplers are
composed of two free moving female threads which house the support tools when
assembling and removing the impactor frit, and couple the denuders when sampling. There
are arrows printed on the metal band which holds the female threads together. These
arrows should be pointing in the direction of air flow (see Figure 1) when the ADS is
assembled. .
Note: In situations when there are substantial high concentrations of coarse particles
(>2.5 pm), it is recommended that a Teflon* -coated aluminum cyclone be used in place
of the acceleration jet and impactor assembly, as illustrated in Figure 3. The cyclone is
made of Teflon* -coated stainless steel. Figure 4 illustrates the location of the cyclone with
respect to the denuder, heated enclosure and meter box assembly ready for sampling
[University Research Glassware, 118 E. Main St., Carrboro, NC, 27510, (919-942-2753)].
7.1.4 Annular denuder - The denuder consists of two concentric glass tubes. The tubes
create a 1 mm orifice which allows the air sample to pass through. The inner tube is inset
25 mm from one end of the outer tube; this end is called the flow straightener end. The
other end of the inner tube is flush with the end of the outer tube. Both ends of the inner
tube are sealed. In this configuration, the glass surfaces facing the orifice are etched to
provide greater surface area for the coating. There are three types of denuders available.
One is the older version which accommodates the impactor support pin assembly, and can
Revised 9/30/89 ~ ~
-------
Method IP-7
PAHs
Annular
Denuder
Inlet
Size
Select
Inlet
Optional
Sorbent (or
Vapor Phase
Compounds
/ Particle
Collector
Seml-Rlgld
Fiberglass
Board
Sample
Air
Outlet
Plywood
Laminate
Outlet
Motor
Cooling
Air Inlet
Flow Rate
Controller
Cover
Locking
Latches
Vacuum
Inlet
Industrial
Vacuum
Motor
Motor
Cooling
Air Outlet
Figure 2. Acoustically Enclosed Medium Volume Sampler
Revised 9/30/89
Page 71
-------
Method IP-7
PAHs
Sorbent for
Vapor Phase
Compounds
To Vacuum
Motor and
Flow Controller
Example Support Package
Containing Flow Controllers,
Pumps and Recorder
Figure 3. Tripod Sampler with Portable Meter Box Assembly
Revised 9/30/89
Page 72
/,,,
-------
Method IP-7
PAHs
Particle
Collection
Seven Day
Programmable
Timer
orbent tor
Vapor'Phase
'Compounds
To Vacuum>
Motor and
Flow Controller
Electronic
Package
For Flow
Transducer
Acoustic
Insulation
Vibration
isolation
Figure 4. Battelle-Columbus Laboratory Medium Volume
Air Sampler with Tripod Sampling Head
Revised 9/30/89
Page 73
-------
Method IP-7
PAHs
co 90
o
CO
O
cc
o
o
CM
111
CC
CO
_l
HI
ffi
o
01
a
01
HI
UJ
cc
3
CO
CO
01
cc
Q.
o
CO
o
m
01
80
70
60
50
40
30
20
8 io
NC-70
NC-20
63 250 1000 4000 8000
OCTIVE-BAND CENTER FREQUENCIES IN HERTZ
Figure 5. Noise Criterion for Indoor Air Sampler
Revised 9/30/89
Page 74
-------
Method IP-7
PAHs
Water In
Soxhlet
Extraction.
Tube and
Thimble
5J£—*- Water Out IA07-77
_ Allihn
Condenser
Flask
(a) Soxhlet Extraction Apparatus
with Allihn Condenser
3 Ball Macro
Synder Column
500 mL
Evaporator
Bask
10 mL
Concentrator
Tube
(b) Kudema-Danlsh (K-D) Evaporator
with Macro Synder Column
Disposable 6 Inch
Pasteur Pipette
-1 Gram Sodium Sulfate
10 Gram Silica
~Ge! Slurry
Glass Woo! Plug
(c) Silica Gel Clean-up Column
Figure 6. Apparatus Used in Sampling Analysis
Revised 9/30/89
Page 75
-------
Method IP-7
PAHs
Injection
Port
Flow
Controller
,-\ GC Column -,% £
\i; '(Capillary 1 Vjj^
,; \orPacked) <*-
" %^
Carrier
Gas
Bottle
Flame
lonlzatlon
(Fl)
Detector
Mass
Spectroscopy
(MS)
in
SCAN Mode
Figure 7. GC Separation with Subsequent Flame lonization (FI)
or Mass Spectroscopy (MS) Detection
Revised 9/30/89
Page 76
-------
Method IP-7
PAHs
. Helium
Guard Analytical
Column Column
Water Reservoir HlghPressre
Solvent
Waste
Binary
Proportioning
Valve
ffl
nnn
n
o n
___
"v
J --
Variable
Wavelength
UV/Fluorescence
Detector
Figure 8. Important Components of an HPLC System
Data System
and Recorder
Revised 9/30/89
Page 77
-------
Method IP-7
PAHs
Protective
Cap
4" Diameter
Pallllex Filter
and Support
'articulate
Filter
Support
'Absorbent
Cartridge and
Support
Protective Cap
Filler
Retaining
Ring
Slllcone
Gasket
4" Diameter
Pallllex Filter
TX40H120WW
Filler
Support
Screen
Filter Support
Base
Silicon*
Gasket
Glass Cartridge
Adsorbent
(XAD-2 or PUF)
Retaining Screen
Slllcone
Gasket
Adsorbent
Support
Figure 9. General Metal Works Sampling Head with Protective Cap
Revised 9/30/89
Page 78
-------
Method IP-7
PAHs
AIR INLET
GASKETS
STAINLESS SCREENS
QUARTZ WOOL
ALUMINUM
PYREX
STAINLESS SCREENS
GASKET
TO VACUUM
Figure 10. Alternative Design for Medium Volume
Indoor Air Sampler with Open Face Filter Assembly
Revised 9/30/89
Page 79
-------
Method IP-7
PAHs
(A) Leveling Bubble
Manometer
Protective
Cap
(B)Water Level Gage
Sorbent for
Vapor Phase
Compounds
Flow Control
Needle Valve
Flow Sensor
Vacuum Pump
Exhaust
Exhaust
Figure 11. Calibration Assembly for Medium Volume Sampling System
Revised 9/30/89
Page 80
-------
Method IP-7 PAHs
Flow Sensor Calibration Data Sheet
Name
Date
Wet test meter fluid temperature (Tm) *C *K
Mass flow meter #
Mass flow meter range setting
Barometric pressure (Pb) mm Hg WTM C.F.
Transducer I WTM I
Water vapor pressure (p ) mm Hg
Flow Transducer Wet Test Meter Flow Rate
% Full Scale Volts Vm Va Ap Tm Vs 9 Vs Qs
80
60
40
20
10
u = V x C F L
*a *m A ^"' '» L
Pm= Pb (mm Hg) - Ap (mm Hg), mm Hg
Tm= °V + 273.16, °K
pv = vapor pressure of wet test meter water, mm Hg
6 = time, minutes
Qs = standard volumetric flow rate, L/min
Figure 12. Flow Sensor Calibration Data Sheet
Revised 9/30/89 Page 81
-------
Method IP-7
PAHs
Sampler Site
Sampler Location.
Date
Before
After
Barometric Pressure .
Ambient Temperature.
en. Daio ... Performed Bv :
Sampler
S/N
Sampling
Location
1.0.
Height
Ground
Identification
No.
Rlter
XAD-2
or PUF
Sampling Period
Start
Stop
Totaling
Sampling
Time, mln.
Pump Timer
Hr. Mln.
Sampler Bow
Vs
QS
Within
± 10%
Checked By.
Date
Figure 13. Field Test Data Sheet
Revised 9/30/89
Page 82
-------
Method IP-7
PAHs
READY
DEFINE •
MENU TREE
-SENSOR-*-CHANL-
-DAYS-
SELECT,
-TYPE-*-CAL-
ENTER-
-PT1-PT2
NXTCh
HNL«
HRS-*-MIN-*-SEC-
REC.TIME
CUP RATE-»-BAUD-*-flEADY
- DAYS-»-HRS-*-MIN-*-SEC
-READY
-DISP VALUE*
DISPLAY-*-AN INPUT-*- CHNL-*- DISP VALUE •
TIME-*-DISP VALUE •
BATTERY-*- DISP VALUE •
CAPACITY-*- DISP VALUE •
RECORD-*-START— DISP . CHNL
DISP NEXT CHNL
•-C
EVENT
•I RECD.END-*- READY
RE-START-*- DISP CHNL
Jl DISPLAY
ERASE-*-READY
PLAYBACK-*-SEND DATA-*- READY
• Press SELECT and ENTER together to return to Ready
• Press SELECT and ENTER together to stop recording
A Returns to DISPLAY in main menu
ATTENTION ALL RED FUNCTIONS MUST BE DONE
DEFAULT CONDITIONS:
Record time: 1 hour
Output rate: 9600 baud
Time Elasped: 00:00:00:00
Figure 14. Data Logger Menu Tree
Revised 9/30/89
Page 83
-------
Method IP-7
PAHs
1 Adsorbent
PUForXAD-2)
Surrogate Standard
Addition for GOF1D
and GC/MS Analysis
(Section 12.2.1)
Soxhlet Extraction In Methytena Chloride
18 Hours/3 Cycles/Hr) or
Ether/Hexane Solvent
(Section 112.1)
4_
Surrogate Standard
Addition (or
HPLC Analysis
(Section 12.2.1}
Drying with Anhydrous Sodium SuKate
(Section 12i2)
Kuderna-Danlsh (K-D) Evaporator
Attached with Macro Synder Column
(Section 123J)
Solvent Exchange to Cyclohexane by
K-D Apparatus with Macro Snyder Column
(Section 113.2)
-*
Add 5 mL of
Cyclohexane
(No Extract Clean-up Required)
|ulred)
Concentrate
toLOmL
1
(Extract Clean-Up
' Required)
Silica Gel Column Topped with
Sodium SuKate
(Section 12.4.1}
or Lobar Column
(Section (12.4.2)
-4
I—
-
Add 0.5 mL
Cyclohexane
Pentane
Elution
Methylene
Chloride/Pentane
Elution
Methanol
Elution
Methylene Chloride/Pentane Fraction
Concentrated by K-D Apparatus to 1 mL
(Section 12.4.1.3)
Analysis by
GC or HPLC
Gas Chromatography
Analysis
(Section 13.0)
Solvent Exchange to Acetonftrile
by K-D Apparatus
(Section 15.2)
HPLC Analysis
(Section 15.4)
Ultraviolet
(UV) Detection
Fluorescence
(FL) Detection
Figure 15. Sample Clean-Up, Concentration, Separation and Analysis Sequence
Revised 9/30/89
Page 84
-------
Method IP-7
PAHs
Establish Gas Chromatograph
Operating Parameters:
(Section 13.3)
Prepare Calibration Standards
(Section 13.4)
Select Internal Standards
Having Similar Behavior to
Compounds of Interest
(Section 13.4.2)
I
Internal Standard
•4-
Calibration Technique
(Section 13.4)
External Standard
-*•
Prepare Calibration Standards
for EachAnalyta
of Interest
(Section 13.4.1)
Prepare Calibration/
Internal Standards
(Section 13.4.2.1)
Inject Calibration Standard:
Prepare Calibration Curve
or Calibration Factor (CF)
(Section 13.4.1.5)
Inject Calibration Standards:
Calculate Response Factor (RF)
(Section 13.4.2.2)
Verify Working Calibration
Curve Each Day
(Section 13.4.1.7)
Verify Working Calibration
Curve or RF Each Day
(Section 13.4.2.6)
Calculate Retention
Time Windows
(Section 13.5)
4-
Introduce Extract Into
Gas Chromatograph by
Direct Injection
(Section 13.6.1)
Does Response Exceed
Linear Range
of System?
(Section 13.6.3.1)
Yes
Dilute Extract
and Reanalyze
(Section 13.6.3.1)
Determine Identity and
Quantity of Each Analyte,
Using Appropriate Formulas
and Curves
(Section 13.6.3 and 17.2.1)
Figure 16. GC Calibration and Retention Time Window Determination
Revised 9/30/89
Page 85
-------
Method IP-7
PAHs
Injection: 1.0 /zL on-column
Column: 30m x 0.25 mm DB-5 capillary with 0.25 fm film thickness
Program: 40"C (1 min), 15*C/min to 200'C, 3*C/min to 300°C
Detector: Flame ionization
1. Naphthalene
2. Acenaphthylene
3. Acenaphthene
4. Fluorene
5. Phenanthrene
6. Anthracene
7. Fluoranthene
8. Pyrene
9. Benzo(a)anthracene
10. Chrysene
11. Benzo(b)fluoranthene
12. Benzo(k)fluoranthane
13. Benzo(a)pyrene
14. Indeno(l,2,3-cd)pyrene
15. D1benzo(a,h)anthracene
16. 6enzo(ghijperylene
Figure 17. Typical Chromatogram of Selected PAHs by GC
Equipped with FI Detector
Revised 9/30/89
Page 86
-------
Method IP-7
PAHs
Establish Gas ChromatograpW
Mass Speetroscopy Operating Parameters:
Prepare Calibration Standards
(Section 14.2}
Select Internal Standards
Having Similar Behavior to
Compounds of Interest
Normally Deuterated PAHs
(Section 14.3.2 and 14.3.2.1)
Tune GC/MSwtth DFTPP
(Section 14.2}
Internal Standard
4-
Prepare Calibration
Standards
(Section 14.3.2.4.1)
Add Internal
Standards
(Section 14.3.1.10)
Inject Calibration Standards:
Calculate Response Factor
(Section 14.3.2.5)
Verify Working Calibration
Curve or RF Each Day
(Section 14.3.2.6)
Calibratlon Technique
(Section 14.3)
External Standard
->
Introduce Extract Into
GC/MS by Direct Injection
(Section 14.4)
Does Response Exceed
Linear Range of System?
(Section 14.4.3)
Prepare Calibration Standards
for Each Analysis
of Interest
(Section 14.3.1)
Yes
Inject Calibration Standard:
Prepare Calibration Curve
or Calibration Factor (CF)
(Section 14.3.1.12)
Verify Working Calibration
Curve Each Day
(Section 14.3.1.13)
Dilute Extract and
Reanalyze
(Section 14.4.3)
Calculate Concentration of
Each Anatyte, Using
Appropriate Formulas
(Section 14.4.4 and 17.22}
Daily GC/MS Tuning
With DFTPP
(Section 14.5.1)
&-
GC/MS Performance Test
(Section 143)
-^
12-Hr Calibration Verification
(Section 14.5.3)
Daily 1-Polnt
Calibration Verification
(Section 14.5.2}
Figure 18. GC-MS Calibration and Analysis
Revised 9/30/89
Page 87
-------
Method IP-7
PAHs
HJOC-i
11025-
2TTS0-
13E75-
CJ
!3
10
11
12
13
14
16
20
I
25
15-
Injection:1.0 pi on-column
Column: 30m x 0.25 mm DB-5 capillary with 0.25 fim film thickness
Program: 60'C (1 min), 15°C/min to 200'C, 3*C/min to 310°C
Detector: Mass selective detector
1. Naphthalene + dg-naphthalene
2. Acenaphthylene
3. Acenaphthene
4. Fluorene
5. Phenanthrene + djg phenanthrene
6. Anthracene
7. Fluoranthene
8. Pyrene
S. Benzo(a)anthracene +
10. Chrysene
11. Benzo(b)fluoranthene
12. Benzo(k)fluoranthene
13. Benzo(a)pyrene
chrysene 14. Indeno(l,2.3-cd)pyrene
15. Dibenzo(ah)anthracene
16. Benzo(gh1)perylene
Figure 19. Typical Chromatogram of Selected PAHs by GC-MS
Revised 9/30/89
Page 88
-------
Method IP-7
PAHs
t
5
o>
12
16 20 24 28 32
Retention Time, minutes
40
Figure 20. Typical Chromatogram of Selected PAHs Associated
with HPLC Analysis Involving Ultraviolet Detection
Revised 9/30/89
Page 89
-------
Chapter IP-8
DETERMINATION OF ORGANOCHLORINE PESTICIDES IN INDOOR AIR
1. Scope
This document describes a method for sampling and analysis of a variety of organochlorine
pesticides in indoor air. The procedure is based on the adsorption of chemicals from
indoor air on polyurethane foam (PUF) using a low volume sampler. The low volume PUF
sampling procedure is applicable to multicomponent atmospheres containing organochlorine
pesticide concentrations from 0.01 to 50 0g/m3 over 4- to 24-hour sampling periods. The
detection limit will depend on the nature of the analyte and the length of the sampling
period. The analysis methodology described hi this document is currently employed by
laboratories using EPA Method 608. The sampling methodology has been formulated to
meet the needs of pesticide sampling in indoor air. The sampling methodology involves a
low volume (1 to 5 L/minute) sampler to collect vapors on a sorbent cartridge containing
PUF. Airborne particles may also be collected, but the sampling efficiency is not known.
Pesticides are extracted from the sorbent cartridge with 5% diethyl ether in hexane and
determined by gas-liquid chromatography coupled with an electron capture detector (BCD).
For some organochlorine pesticides, high performance liquid chromatography (HPLC)
coupled with an ultraviolet (UV) detector or electrochemical detector may be preferable.
This method describes the use of an electron capture detector.
2. Significance
2.1 Pesticide usage and environmental distribution are common to rural and urban areas
of the United States. The application of pesticides can cause adverse health effects to
humans by contaminating soil, water, air, plants, and animal life.
22 Many pesticides exhibit bioaccumulative, chronic health effects; therefore, monitoring
the presence of these compounds in ambient air is of great importance.
2.3 Use of portable, low volume PUF sampling system allows the user flexibility in locating
the apparatus. The user can place the apparatus in a stationary or mobile location. The
portable sampling apparatus may be positioned in a vertical or horizontal stationary location
(if necessary, accompanied with supporting structure). Mobile positioning of the system can
be accomplished by attaching the apparatus to a person to test air in the individual's
breathing zone. Moreover, the PUF cartridge used in this method provides for successful
collection of most pesticides.
Revised 9/30/89 Page i
-------
Method IP-8
DETERMINATION OF ORGANOCHLORINE PESTICIDES IN INDOOR AIR
1. Scope
2. Applicable Documents
3. Summary of Method
4. Significance
5. Definitions
6. Interferences
7. Apparatus
7.1 Sample Collection
7.2 Sample Analysis
8. Reagents and Materials
9. Assembly and Calibration of Sampling System
9.1 Description of Sampling Apparatus
9.2 Calibration of Sampling System
10. Preparation of Sampling (PUF) Cartridges
11. Sample Collection
12. Sample Preparation, Cleanup, and Analysis
12.1 Sample Preparation
12.2 Sample Cleanup
12.3 Sample Analysis
13. GC Calibration
14. Calculations
15. Sampling and Retention Efficiencies
16. Method Variation
17. Performance Criteria and Quality Assurance
17.1 Standard Operation Procedures (SOPs)
17.2 Process, Field, and Solvent Blanks
17.3 Sampling Efficiency and Spike Recovery
17.4 Method Sensitivity
17.5 Method Precision and Bias
17.6 Method Safety
18. References
Revised 9/30/89 Pflge
-------
Method IP-8
DETERMINATION OF ORGANOCHLORINE PESTICIDES IN INDOOR AIR
1. Scope
1.1 This document describes a method for sampling and analysis of a variety of
organpchlorine pesticides in indoor air. The procedure is based on the adsorption of
chemicals from indoor air on polyurethane foam (PUF) using a low volume sampler.
12 The low volume PUF sampling procedure is applicable to multicomponent atmospheres
containing organochlorine pesticide concentrations from 0.01 to 50 pg/m3 over 4 to 24 hour
sampling periods. The detection limit will depend on the nature of the analyte and the
length of the sampling period.
1.3 Specific compounds for which the method has been employed are listed in Table 1.
The analysis methodology described in this document is currently employed by laboratories
using EPA Method 608. The sampling methodology has been formulated to meet the needs
of pesticide sampling in indoor air.
2. Applicable Documents
2.1 ASTM Standards
D1356 Definitions of Terms Related to Atmospheric Sampling and Analysis
D1605-60 Standard Recommended Practices for Sampling Atmospheres for Analysis of
Gases and Vapors
D4861-88 Standard Practice for Sampling and Analysis of Pesticides and Polychlorinated
Biphenyls in Indoor Atmospheres
E260 Recommended Practice for General Gas Chromatography Procedures
E355 Practice for Gas Chromatography Terms and Relationships
22 Other Documents
U.S. EPA Technical Assistance Documents (1)
Indoor/Ambient Air Studies (2-9)
Existing Procedures (10-11)
3. Summary of Method
3.1 A low volume (1 to 5 L/min) sampler is used to collect vapors on a sorbent cartridge
containing PUF. Airborne particles may also be collected, but the sampling efficiency is
not known.
32 Pesticides are extracted from the sorbent cartridge with 5% diethyl ether in hexane and
determined by gas-liquid Chromatography coupled with an electron capture detector (BCD).
Nojg: For some organochlorine pesticides, high performance liquid Chromatography
(HPLC) coupled with an ultraviolet (UV) detector or electrochemical detector may be
preferable. This method describes the use of an electron capture detector.
3.3 Interferences resulting from analytes having similar retention times during gas-liquid
Chromatography are resolved by improving the resolution or separation, such as by changing
Revised 9/30/89 ~
-------
Method IP-8 Pesticides
the chromatographic column or operating parameters, or by fractionating the sample by
column chromatography.
3.4 The sampling procedure is also applicable to other pesticides which may be determined
by gas-liquid chromatography coupled with a nitrogen-phosphorus detector (NPD), flame
photometric detector (FPD), Hall electrolytic conductivity detector (HECD), or a mass
spectrometer (MS).
4. Significance
4.1 This procedure is intended to be used primarily for non-occupational exposure
monitoring in domiciles, public access buildings and offices.
42 A broad spectrum of pesticides are commonly used in and around the house and for
insect control in public and commercial buildings. Other semi-volatile organic chemicals,
such as PCBs, are also often present in indoor air, particularly in large office buildings.
This procedure will promote needed accuracy and precision in the determination of many
airborne chemicals which may prove to present unacceptable long-term health risks or
contribute to short-term episodes, such as "sick building syndrome."
4.3 Use of a portable, low volume PUF sampling system allows the user flexibility in
locating the apparatus. The user can place the apparatus in a stationary or mobile location.
The portable sampling apparatus may be positioned in a vertical or horizontal stationary
location (if necessary, accompanied with supporting structure). Mobile positioning of the
system can be accomplished by attaching the apparatus to a person to test air in the
individual's breathing zone. Moreover, the PUF cartridge used in this method provides for
successful collection of most pesticides. Figure l(a) illustrates PUF sampling system in a
fixed location and Figure l(b) shows the sampling system attached to an individual.
5. Definitions
Definitions used in this document and in user-prepared Standard Operating Procedures
(SOPs) should be consistent with ASTM D1356, D1605-60, and E355. All abbreviations
and symbols are defined within this document at point of use. Additional definitions and
abbreviations are provided in Appendices A-l and B-2 of this Compendium.
5.1 Sampling efficiency (SE) - ability of the sampling medium to trap vapors of interest.
%SE is the percentage of the analyte of interest collected and retained by the sampling
medium when it is introduced as a vapor in air or nitrogen into the air sampler and the
sampler is operated under normal conditions for a period of time equal to or greater than
that required for the intended use.
52 Retention efficiency (RE) - ability of sampling medium to retain a compound added
(spiked) to it in liquid solution.
52.1 Static retention efficiency - ability of the sampling medium to retain the solution
spike when the sampling cartridge is stored under clean, quiescent conditions for the
duration of the test period.
Revised 9/30/89 Page 4
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Method IP-8 Pesticides
522 Dynamic retention efficiency - ability of the sampling medium to retain the solu-
tion spike when air or nitrogen is drawn through the sampling cartridge under normal
operating conditions for the duration of the test period. The dynamic RE is normally equal
to or less than the SE.
5.3 Retention time (RT) - time to elute a specific chemical from a chromatographic
column. For a specific carrier gas flow rate, RT is measured from the time the chemical
is injected into the gas stream until it appears at the detector.
5.4 Relative retention time (RRT) - a ratio of RTs for two chemicals for the same
chromatographic column and carrier gas flow rate, where the denominator represents a
reference chemical.
6. Interferences
6.1 Any gas or liquid chromatographic separation of complex mixtures of organic chemicals
is subject to serious interference problems due to coelution of two or more compounds.
The use of capillary or narrow bore columns with superior resolution and/or two or more
columns of different polarity will frequently eliminate these problems.
62 The electron capture detector responds to a wide variety of organic compounds. It is
likely that such compounds will be encountered as interferences during GC-ECD analysis.
The NPD, FPD, and HECD detectors are element specific, but are still subject to
interferences. UV detectors for HPLC are nearly universal, and the electrochemical
detector may also respond to a variety of chemicals. Mass spectrometric analyses will
generally provide positive identification of specific compounds.
6.3 Certain organochlorine pesticides (e.g., chlordane) are complex mixtures of individual
compounds that can make difficult accurate quantification of a particular formulation in a
multiple component mixture. Polychlorinated biphenyls (PCBs) may interfere with the
determination of pesticides.
6.4 Contamination of glassware and sampling apparatus with traces of pesticides can be a
major source of error, particularly at lower analyte concentrations. Careful attention to
cleaning and handling procedures is required during all steps of sampling and analysis to
minimize this source of error.
6.5 The general approaches listed below should be followed to minimize interferences.
6.5.1 Polar compounds, including certain pesticides (e.g., organophosphorus and
carbamate classes), can be removed by column chromatography on alumina. This sample
clean-up will permit analysis of most organochlorine pesticides.
6.52 PCBs may be separated from other organochlorine pesticides by column chroma-
tography on silicic acid.
6.53 Many pesticides can be fractionated into groups by column chromatography on
Florisil (Floridin Corp.).
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Method IP-8 Pesticides
7. Apparatus
7.1 Sample Collection
7.1.1 Sampling pump - (DuPont Alpha-1 Air Sampler, E.I. DuPont de Nemours & Co.,
Inc., Wilmington, DE, 19898, or equivalent). The pump should be quiet and unobtrusive and
provide a constant flow (< ±5%).
7.1.2 Sampling cartridge shown in Figure 2 - constructed from a 20 mm (i.d.) x 10 cm
borosilicate glass tube drawn down to a 7 mm (o.d.) open connection for attachment to the
pump via vinyl tubing. The cartridge can be fabricated inexpensively from glass by Kontes
(P.O. Box 729, Vineland, NJ, 08360), or equivalent.
7.13 Sorbent, polyurethane foam (PUF) - cut into a cylinder, 22 mm in diameter and
7.6 cm long, fitted under slight compression inside the cartridge. The PUF should be of the
polyether type, density of 0.022 g/cm3. This type of foam is used for furniture upholstery,
pillows, and mattresses; it may be obtained from Olympic Products Co. (Greensboro, NC),
or equivalent source. The PUF cylinders (plugs) should be slightly larger in diameter than
the internal diameter of the cartridge. They may be cut by one of the following means:
• High-speed cutting tool, such as a motorized cork borer. Distilled water should be
used to lubricate the cutting tool.
• Hot wire cutter. Care should be exercised to prevent thermal degradation of the
foam.
• Scissors, while plugs are compressed between the 22 mm circular templates.
Alternatively, pre-extracted PUF plugs and glass cartridges may be obtained commercially
(Supelco, Inc., Supelco Park, Bellefonte, PA, 16823, No. 2-0557, or equivalent).
12 Sample Analysis
7.2.1 Gas chromatograph (GC) with an electron capture detector (BCD) and either an
isothermally controlled or temperature programmed heating oven. The analytical system
should be complete with all required accessories including syringes, analytical columns,
gases, detector, and strip chart recorder. A data system is recommended for measuring
peak heights. Consult EPA Method 608 for additional specifications.
722 Gas Chromatographic Columns
7.2.2.1 The following 4 or 2 mm (i.d.) x 183 cm borosilicate glass GC columns may
be used packed with
• 1.5% SP-2250 (Supelco, Inc.)/1.95% SP-2401 (Supelco, Inc.) on 100/120 mesh
Supelcoport (Supelco, Inc.)
• 4% SE-30 (General Electric, 50 Fordham Rd., Wilmington, MA, 01887, or
equivalent)/6% OV-210 (Ohio Valley Specialty Chemical, 115 Industry Rd., Marietta,
OH, 45750, or equivalent) on 100/200 mesh Gas Chrom Q (Alltec Assoc., Applied
Science Labs, 2051 Waukegan Rd, Deerfield, IL, 60015, or equivalent)
• 3% OV-101 (Ohio Valley Specialty Chemical) on UltraBond (Ultra Scientific, 1 Main
St., Hope, RI, 02831, or equivalent)
• 3% OV-1 (Ohio Valley Specialty Chemical) on 80/100 mesh Chromosorb WHP
(Manville, Filtration, and Materials, P.O. Box 5108, Denver, CO, 80271, or equivalent)
Revised 9/30/89 " Page 6
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Method IP-8 _ _ Pesticides
12 22 Capillary GC columns, such as 0.25 mm (i.d.) x 30 m DB-5 (J&W Scientific,
3871 Security Park Dr., Rancho Cordova, CA, 95670, or equivalent) with 0.25 /«n film
thickness may be used.
122 3 HPLC columns, such as 4.6 mm x 25 cm Zorbax SEL (DuPont Co., Concord
Plaza, Wilmington, DE, 19898, or equivalent) or p-Bondapak C-18 (Millipore Corp., 80
Ashby Rd., Bedford, MA, 01730, or equivalent) can be used.
12 2A Other columns may also give acceptable results.
12 .3. Microsyringes - 5 /iL volume or other appropriate sizes.
8. Reagents and Materials
Note: For a detailed listing of various other items required for extract preparation, cleanup,
and analysis, consult U.S. EPA Method 608 which is provided in Appendix A of Method
TO-4 hi the Compendium.
8.1 Round bottom flasks - 500 mL, best source.
8 2 Soxhlet extractors - 300 mL, with reflux condensers, best source.
83 Kuderna-Danish concentrator apparatus - 500 mL, with Snyder columns, best source.
8.4 Graduated concentrator tubes - 10 mL, Kontes, P.O. Box 729, Vineland, NJ, 08360,
Cat. No. K-570050, size 1025, or equivalent.
8.5 Graduated concentrator tubes - 1 mL, Kontes, Vineland, NJ, Cat. No. K-570050, size
0124, or equivalent.
8.6 TFE fluorocarbon tape - 1/2 in, best source.
8.7 Filter tubes - size 40 mm (i.d.) x 80 mm, Corning Glass Works, Science Products,
Houghton Park, AB-1, Corning, NY, 14831, Cat. No. 9480, or equivalent.
8.8 Serum vials - 1 mL and 5 mL, fitted with caps lined with TFE fluorocarbon, best
source.
8.9 Pasteur pipettes - 9 in, best source.
8.10 Glass wool - fired at 500°C, best source.
8.11 Boiling chips - fired at 500°C, best source.
8.12 Forceps - stainless steel, 12 in, best source.
8.13 Gloves - latex or polyvinyl acetate, best source.
8.14 Steam bath, best source.
8.15 Heating mantle, - 500 mL, best source.
8.16 Analytical evaporator, nitrogen blow-down (N-Evap*, Organomation Assoc., P.O. Box
159, South Berlin, MA, 01549, or equivalent).
Revised 9/30/89 Pa8e 7
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Method IP-8 Pesticides
8.17 Acetone - pesticide quality, best source.
8.18 n-Hexane - pesticide quality, best source.
8.19 Diethyl ether preserved with 2% ethanol - Mallinckrodt, Inc., Science Products
Division, P.O. Box 5840, St. Louis, MO, 63134, Cat. No. 0850, or equivalent.
8.20 Sodium sulfate - anhydrous, analytical grade, best source.
8.21 Alumina - activity grade IV, 100/200 mesh, best source.
8.22 Glass chromatographic column - 2 mm Ld. x 15 cm long, best source.
823 Soxhlet extraction system, including Soxhlet extractors (500 and 300 mL), variable
voltage transformers, and cooling water source, best source.
8.24 Vacuum oven connected to water aspirator, best source.
825 Die - use to cut PUF adsorbent, best source.
$26 Ice chest, best source.
827 Silicic acid - pesticide quality, best source.
828 Octachloronaphthalene (OCN) - research grade, Ultra Scientific, Inc., 1 Main St.,
Hope, RI, 02831, or equivalent.
9. Assembly and Calibration of Sampling System
9.1 Description of Sampling Apparatus
9.1.1 The entire sampling system is diagrammed in Figure 1. This apparatus was
developed to operate at a rate of 1-5 L/minute and is used by U.S. EPA for low volume
sampling of indoor air. The method writeup presents the use of this device.
9.12 The sampling module in Figure 2 consists of a glass sampling cartridge in which
the PUF plug is retained.
92 Calibration of Sampling System
92.1 Air flow through the sampling system is calibrated by the assembly shown in
Figure 3. The air sampler must be calibrated in the laboratory before and after each
sample collection period, using the procedure described below.
922 For accurate calibration, attach the sampling cartridge in-line during calibration.
Vinyl bubble tubing (Fisher Scientific, 711 Forbes Ave., Pittsburgh, PA, 15219, Cat. No. 14-
170-132, or equivalent) or other means (e.g., rubber stopper or glass joint) may be used to
connect the large end of the cartridge to the calibration system. Refer to ASTM Standard
Practice D3686, Annex A2 or Standard Practice D4185, Annex Al for procedures to
calibrate small volume air pumps.
Revised 9/30/89 Page 8
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Method IP-8 Pesticides
10. Preparation of Sampling (PUT) Cartridges
10.1 The PUF adsorbent is white and yellows upon exposure to light. For initial cleanup
and quality assurance purposes, the PUF plug is placed in a Soxhlet extractor and extracted
with acetone for 14 to 24 hours at 4 to 6 cycles per hour. (If commercially pre-extracted
PUF plugs are used, extraction with acetone is not required.) This procedure is followed
by a 16 hour Soxhlet extraction with 5% diethyl ether in n-hexane. When cartridges are
reused, 5% ether in n-hexane can be used as the cleanup solvent.
10.2 The extracted PUF is placed in a vacuum oven connected to a water aspirator and
dried at room temperature for 2 to 4 hours (until no solvent odor is detected). The clean
PUF is placed in labeled glass sampling cartridges using gloves and forceps. The cartridges
are wrapped with hexane-rinsed aluminum foil and placed in glass jars fitted with TFE
fluorocarbon-lined caps. The foil wrapping may also be marked for identification using a
blunt probe.
103 At least one assembled cartridge from each batch should be analyzed as a laboratory
blank before any samples from that batch are considered acceptable for use. A blank level
of <10 ng/plug for single component compounds is considered to be acceptable. For
multiple component mixtures, the blank level should be < 100 ng/plug.
11. Sample Collection
11.1 After the sampling system has been assembled and calibrated as per Section 9, it can
be used to collect air samples as described below.
The prepared sample cartridges should be used within 30 days of loading and should
be handled only with clean latex or polyvinyl acetate gloves.
113 The clean sample cartridge is carefully removed from the aluminum foil wrapping (the
foil is returned to jars for later use) and attached to the pump with flexible tubing. The
sampling assembly is positioned with the intake downward or in a horizontal position. The
sampler is located in an unobstructed area at least 30 cm from any obstacle to air flow.
The PUF cartridge intake is positioned 1 to 2 m above the floor level. Air temperature(s)
and barometric pressure(s) are recorded periodically on the Sampling Data Form shown
in Figure 4.
11.4 After the PUF cartridge is correctly inserted and positioned, the power switch is
turned on and the sampling begins. The elapsed time meter is activated and the start time
is recorded. The pumps are checked during the sampling process and any abnormal condi-
tions discovered are recorded on the data sheet.
11.5 At the end of the desired sampling period, the power is turned off and the PUF
cartridges are wrapped with the original aluminum foil and placed in sealed, labeled
containers for transport back to the laboratory. At least one field blank is returned to the
laboratory with each group of samples. A field blank is treated exactly like a sample except
Revised 9/30/89 Page 9
63?'
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Method IP-8 Pesticides
that no air is drawn through the cartridge. Samples are stored at -10°C or below until
analyzed.
12. Sample Preparation, Cleanup, and Analysis
Note: Sample preparation should be performed under a properly ventilated hood.
12.1 Sample Preparation
12.1.1 All samples should be extracted within 1 week after collection.
12.1.2 All glassware is washed with a suitable detergent; rinsed with deionized water,
acetone, and hexane; rinsed again with deionized water; and fired in an oven (500°C).
12.13 Sample extraction efficiency is determined by spiking the samples with a known
solution. Octachloronaphthalene (OCN) is an appropriate standard to use for pesticide
analysis using GC-ECD techniques. The spiking solution is prepared by dissolving 10 mg
of OCN in 10 mL of 10% acetone in n-hexane, followed by serial dilution with n-hexane
to achieve a final concentration of 1 pg/mL.
12.1.4 The extracting solution (5% ether/hexane) is prepared by mixing 1900 mL of
freshly opened hexane and 100 mL of freshly opened ethyl ether (preserved with ethanol)
to a flask.
12.1.5 All clean glassware, forceps, and other equipment to be used are placed on
rinsed (5% ether/hexane) aluminum foil until use. The forceps are also rinsed with 5%
ether/hexane. The condensing towers are rinsed with 5% ether/hexane and 300 mL are
added to a 500 mL round bottom boiling flask (with no more than three boiling chips).
12.1.6 Using clean gloves, the PUF cartridges are removed from the sealed container
and the PUF is placed into a 300 mL Soxhlet extractor using prerinsed forceps.
12.1.7 Before extraction begins, 100 pL of the OCN solution are added dropwise to the
top of the PUF plug. Addition of the standard demonstrates extraction efficiency of the
Soxhlet procedure.
Note: Incorporating a known concentration of the solution onto the sample provides a
quality assurance check to determine recovery efficiency of the extraction and analytical
processes.
12.1.8 The Soxhlet extractor is then connected to the 500 mL boiling flask and
condenser. The glass joints of the assembly are wet with 5% ether/hexane to ensure a tight
seal between the fittings. If necessary, the PUF plug can be adjusted using forceps to
wedge it midway along the length of the siphon. The above procedure should be followed
for all samples, with the inclusion of a blank control sample.
12.1.9 The water flow to the condenser towers of the Soxhlet extraction assembly is
checked and the heating unit is turned on. As the samples boil, the Soxhlet extractors are
inspected to ensure that they are filling and siphoning properly (4 to 6 cycles/hour).
Samples should cycle for a minimum of 16 hours.
12.1.10 At the end of the extracting process, the heating units are turned off and the
samples are cooled to room temperature.
12.1.11 The extracts are concentrated to a 5 mL solution using a Kuderna-Danish
(K-D) apparatus. The K-D is set up and assembled with concentrator tubes. This assembly
Revised 9/30/89 Page 10
fc3'
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Method IP-8 Pesticides
is rinsed and one boiling chip is added to each concentrator tube. The lower end of the
filter tube is packed with glass wool and filled with anhydrous sodium sulfate to a depth of
40 mm. The filter tube is placed in the neck of the K-D. The Soxhlet extractors and
boiling flasks are carefully removed from the condenser towers and the remaining solvent
is drained into each boiling flask. Sample extract is carefully poured through the filter tube
into the K-D. Each boiling flask is rinsed three times by swirling hexane along the sides.
Once the sample has drained, the filter tube is rinsed down with hexane. Each Synder
column is attached to the K-D and rinsed to wet the joint for a tight seal. The complete K-
D apparatus is placed on a steam bath and the sample is evaporated to approximately 5
mL. Do not let sample go to dryness. The sample is removed from the steam bath and
allowed to cool. Each Synder column is rinsed with a minimum of hexane and sample is
allowed to cool. Sample volume is adjusted to 10 mL in a concentrator tube, which is then
closed with a glass stopper and sealed with TFE fluorocarbon tape. Alternately, the sample
may be quantitatively transferred (with concentrator tube rinsing) to prescored vials and
brought up to final volume. Concentrated extracts are stored at -10°C until analyzed.
Analysis should occur no later than two weeks after sample extraction.
122 Sample Cleanup
122.1 If only organochlorine pesticides are sought, an alumina cleanup procedure is
appropriate. Before cleanup, the sample extract is carefully reduced to 1 mL using a gentle
stream of clean nitrogen.
1222 A glass chromatographic column (2 mm i.d. x 15 cm long) is packed with
alumina, activity grade IV, and rinsed with approximately 20 mL of n-hexane. The
concentrated sample extract is placed on the column and eluted with 10 mL of n-hexane
at a rate of 0.5 mL/minute. The eluate volume is adjusted to exactly 10 mL and analyzed
as per Section 12.3.
122.3 If other pesticides are sought, alternate cleanup procedures may be required
(e.g., Florisil). EPA Method 608 identifies appropriate cleanup procedures.
123 Sample Analysis
12 J.I Organochlorine pesticides and many nonchlorinated pesticides are responsive to
electron capture detection (Table 1). Most of these compounds can be determined at
concentrations of 1 to 50 ng/mL by GC-ECD.
1232 An appropriate GC column is selected for analysis of the extract. (For example,
4 mm i.d. x 183 cm glass, packed with 1.5% SP-2250/1.95% SP-2401 on 100/120 mesh
Supelcoport, 200°C isothermal, with 5% methane/95% argon carrier gas at 65 to 85
mL/min). A chromatogram showing a mixture containing single component pesticides
determined by GC-ECD using a packed column is shown in Figure 5. Corresponding
chromatographic characteristics are shown in Table 2.
12 33 A standard solution is prepared from reference materials of known purity.
Standards of organochlorine pesticides may be obtained from the National Bureau of
Standards and from the U.S. EPA.
Revised 9/30/89 Page 11
(o-
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, ,„ „ Pesticides
Method IP-8 _ _ __ _ ___ - -
12.3.4 Stock standard solutions (1.00 / For
improved resolution, a capillary column is used such as 0.25 mm (i.d.) x 30 m DB-5 with
0.25 fim film thickness.
Revised 9/30/89
Page 12
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_ _ 4, , ro 0 Pesticides
Method IP-8 .
12.3.12 A chromatogram of a mixture containing single component pesticides
determined by GC-ECD using a capillary column is shown in Figure 6. A table ol the
corresponding chromatographic characteristics follows in Table 3. ^rnm»
123.13 Class separation and improved specificity can be achieved by column chroma-
tographic separation on Florisil as per EPA Method 608. For improved specificity a Hall
electrolytic conductivity detector operated in the reductive mode may be substituted for the
electron capture detector. Limits of detection will be reduced by at least an order of
magnitude.
13. GC Calibration
Appropriate calibration procedures are identified in EPA Method 608, Section 7 (11).
131 Establish gas chromatographic operating parameters. The gas chromatographic system
may be calibrated using the external standard technique (Section 13.2) or the internal
standard technique (Section 13.3).
13.2 External Standard Calibration Procedure
1321 Prepare calibration standards at a minimum of three concentration levels for
each parameter of interest by adding volumes of one or more stock standards to a
volumetric flask and diluting to volume with isooctane. One of the external standards
should be at a concentration near, but above, the method detection limit and the other
concentrations should correspond to the expected range of concentrations found in real
samples or should define the working range of the detector.
1322 Using injections of 2 to 5 /iL of each calibration standard, tabulate peak height
or area responses against the mass injected. The results can be used to prepare a
calibration curve for each compound. Alternatively, if the ratio of response to amount
injected (calibration factor) is a constant over the working range (<10% relative standard
deviation, RSD), linearity through the origin can be assumed and the average ratio or
calibration factor can be used in place of a calibration curve.
1323 The working calibration curve or calibration factor must be verified on each
working day by the measurement of one or more calibration standards. If the response for
any parameter varies from the predicted response by more than ±10%, the test must be
repeated using a fresh calibration standard. Alternatively, a new calibration curve or
calibration factor must be prepared for that compound.
133 Internal Standard Calibration Procedure
13.2 1 To use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior to the compounds of interest. The analyst must further
demonstrate that the measurement of the internal standard is not affected by method or
matrix interferences. Because of these limitations, no internal standard can be suggested
that is applicable to all samples.
1332 Prepare calibration standards at a minimum of three concentration levels for
each parameter of interest by adding volumes of one or more stock standards to a
Revised 9/30/89 " " PaSe 13
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»» *u j T» e Pesticides
Method IP-8
volumetric flask. To each calibration standard, add a known constant amount of one or
more internal standards, and dilute to volume with isooctane. One of the standards shou d
be at a concentration near, but above, the MDL and the other concentrations should
correspond to the expected range of concentrations found in real samples or should deiine
the working range of the detector. .
1333 Using injections of 2 to 5 ML of each calibration standard, tabulate peak height
or area responses against concentration for each compound and internal standard, and
calculate response factors (RF) for each compound using
RF = (ASC1S)/(A1SCS)
where:
AS = response for the parameter to be measured
Ais = response for the internal standard
Ci* = concentration of the internal standard, fig/L
Cs = concentration of the parameter to be measured, fig/L
If'the RF value over the working range is a constant (< 10% RSD), the RF can be assumed
to be invariant and the average RF can be used for calculations. Alternatively, the results
can be used to plot a calibration curve of response ratios, A?/A1s, vs. RF.
13 J 4 The working calibration curve or RF must be verified on each working day by
the measurement of one or more calibration standards. If the response for any parameter
varies from the predicted response by more than ±10%, the test must be repeated using
a fresh calibration standard. Alternatively, a new calibration curve must be prepared for
that compound.
14. Calculations
141 The concentration of the analyte in the extract solution is taken from a standard curve
where peak height or area is plotted linearly against concentration in nanograms per milli-
liter (ng/mL). If the detector response is known to be linear, a single point is used as a
calculation constant.
142 From the standard curve, determine the ng of analyte standard equivalent to the peak
height or area for a particular compound.
14.3 Determine if the field blank is contaminated. Blank levels should not exceed 10
ng/sample for organochlorine pesticides or 100 ng/sample for other pesticides. If the blank
has been contaminated, the sampling series must be held suspect.
14.4 Quantity of the compound in the sample (A) is calculated using the following
equation:
A = 1000 • [(As x VJ/VJ
where:
A = total amount of analyte in the sample, ng
Revised 9/30/89 PaSe 14
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Method 1P-8 _ __ _ Pesticides
As = calculated amount of material injected onto the chromatograph based on calibration
curve for injected standards, ng
Ve = final volume of extract, mL
V, = volume of extract injected, juL
1000 = factor for converting microliters to milliliters
14.5 The extraction efficiency (EE) is determined from the recovery of
octachloronaphthalene (OCN) spike as follows:
EE(%) = (S/Sa) x 100
where:
S = amount of spike recovered, ng
Sa = amount of spike added to plug, ng
14.6 The total amount of nanograms found in the sample is corrected for extraction
efficiency and laboratory blank as follows:
A, = (A -
where:
A,. = corrected amount of analyte in sample, ng
A0 = amount of analyte in blank, ng
14.7 The total volume of air sampled under ambient conditions is determined using the
following equation:
Va = [ 2 CT, x F,)]/1000
i=l
where:
Va = total volume of air sampled, m
T, = length of sampling segment between flow checks, min
F,- = average flow during sampling segment, L/min
1000 = factor for converting liters to cubic meters
14.8 The air volume is corrected to 25°C and 760 mm Hg (STP) as follows:
Vs = Va • [(Pb - PJ/760 mm Hg] • [298/(237 + TA)]
where:
Vs = volume of air at standard conditions, m
Va = total volume of air sampled, m3
Pb = average ambient barometric pressure, mm Hg
Pw = vapor pressure of water at calibration temperature, mm Hg
TA = average ambient temperature, °C
14.9 If the proper criteria for a sample have been met, concentration of the compound in
a cubic meter of air is calculated as follows:
Revised 9/30/89 ae 1S
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»* *v j TO o Pesticides
Method IP-8 _—.
ng/m3 = AC/VS • 100/SE(%)
SE = sampling efficiency as determined by the procedure outlined in Section 15
If it is desired to convert the air concentration value to parts per trillion (wt/wt) in dry air
at STP, the following conversion is used:
ppt = 0.844 (ng/m3)
The air concentration is converted to parts per trillion (v/v) in air at STP as follows:
pptv = 24.45 (ng/m3)/MW
where:
MW = molecular weight of the compound of interest
15. Sampling and Retention Efficiencies
151 Before using this procedure, the user should determine the sampling efficiency for the
compound of interest. The sampling efficiencies shown in Tables 4 and 5 were determined
for approximately 1 m3 of air at about 25°C, sampled at 3.8 L/min. Sampling efficiencies
for the pesticides shown in Table 6 are for 24 hours at 3.8 L/min and 25 C. Sampling
efficiencies for carbonates, ureas, triazines, and pyrethrine are provided in Table 7. for
compounds not listed, longer sampling times, different flow rates, or other air temperatures,
the following procedure may be used to determine sampling efficiencies.
152 SE is determined by a modified impinger assembly attached to the sampler pump (see
Figure 7) Clean PUF is placed in the pre-filter location and the inlet is attached to a
nitrogen line. PUF plugs (22 mm x 7.6 cm) are placed in the primary and secondary traps
and are attached to the pump. .
Note- Nitrogen should be used instead of air to prevent oxidation of the compounds under
test. The oxidation would not necessarily reflect what may be encountered dunng actual
sampling and may give misleading sampling efficiencies.
15 J A standard solution of the compound of interest is prepared in a volatile solvent (e.g.,
hexane pentane, or benzene). A small, accurately measured volume (e.g., 1 mL) of the
standard solution is placed into the modified midget impinger. The sampler pump is set
at the rate to be used in sampling application and then activated. Nitrogen is drawn
through the assembly for a period of time equal to or exceeding that intended for sampling
application. After the desired sampling test period, the PUF plugs are removed and
analyzed separately as per Section 123.
15.4 The impinger is rinsed with hexane or another suitable solvent and quantitatively
transferred to a volumetric flask or concentrator tube for analysis.
15.5 The sampling efficiency (SE) is determined using the following equation:
% SE = W1/(W0 - Wr) • 100
Revised 9/30/89 ~~~ PaSe 16
-------
Method IP-8 Pesticides
where:
W, = amount of compound extracted from the primary trap, ng
W = original amount of compound added to the impinger, ng
W° = residue left in the impinger at the end of the test, ng
15.6 If material is found in the secondary trap, it is an indication that breakthrough has oc-
curred The addition of the amount found in the secondary trap, W2, to Wj, will provide
an indication of the overall sampling efficiency of a tandem-trap sampling system. The sum
of \v\, W2 (if any), and Wr must equal (approximately ± 10%).W0 or the test is invalid.
157 If the compound of interest is not sufficiently volatile to vaporize at room
temperature the impinger may be heated in a water bath or other suitable heater to a
maximum of 50°C to aid volatilization. If the compound of interest cannot be vaporized
at 50°C without thermal degradation, dynamic retention efficiency (REd) may be used to
estimate sampling efficiency. Dynamic retention efficiency is determined in the manner
described in 15.8. Table 6 lists those organochlorine pesticides for which dynamic retention
efficiencies have been determined.
15 8 A pair of PUF plugs is spiked by slow, dropwise addition of the standard solution to
one end of each plug. No more than 0.5 to 1 mL of solution should be used. Amounts
added to each plug should be as nearly the same as possible. The plugs are allowed to dry
for 2 hours in a clean, protected place (e.g., desiccator). One spiked plug is placed in the
primary trap so that the spiked end is at the intake and one clean unspiked plug is placed
in the secondary trap. The other spiked plug is wrapped in hexane-rinsed aluminum foil
and stored in a clean place for the duration of the test (this is the static control plug,
Section 15 9) Prefiltered nitrogen or ambient air is drawn through the assembly as per
Section 153. Each PUF plug (spiked and static control) is analyzed separately as per
Section 123.
Note: Impinger may be discarded.
15.9 Retention Efficiency (RE) is calculated as follows:
% RE = (W,/W0) • 100
where:
Wj = amount of compound recovered from primary plug, ng
W0 = amount of compound added to primary plug, ng
If a residue, W2, is found on the secondary plug, breakthrough has occurred. The sum of
W, + W, must equal W0 within 25% or the test is invalid. For most compounds tested by
this procedure, % RE values are generally less than % SE values determined per Section
15.1. The purpose of the static RE determination is to establish any loss or gam of analyte
unrelated to the flow of nitrogen or air through the PUF plug (see Table 8).
Revised 9/30/89 Pa&e 17
-------
., ., , T0 0 Pesticides
Method IP-8 -
16. Method Variation
This section provides analytical procedures for a variety of pesticides other than
organochlorine. Samples for the pesticides mentioned below are collected as described in
Section 7.1.
16.1 Organophosphorus pesticides are responsive to flame photometric and nitrogen-
phosphorus (alkali flame ionization) detection. Most of these compounds can be analyzed
at concentrations of 50 to 500 ng/mL using either of these detectors. Procedures given in
12.3.2 through 12.3.9 and 12.3.11 through 123.3 apply, except for the selection of internal
standards. Use parathion as an internal standard.
162 Carbamate and triazine pesticides are most commonly analyzed by HPLC because of
poor thermal stability or high polarity. Detection limits will be in the 1 to 5 /tg/mL range.
Many carbamates and triazine pesticides may also be analyzed intact by GC on a2 mm
(i.d.) x 183 cm glass column of 3% OV-101 on Ultra-Bond and determined by HECD.
Detection limits will be about 1 /ig/mL.
163 Carbaryl*, atrazine*, propoxur*, bendiocarb« and captan* have been successfully
analyzed by capillary column chromatography as discussed in Section 12.3.11.
16,4 Many urea pesticides, pyrethrins, phenols, and other polar pesticides may be analyzed
by HPLC with fixed or variable wavelength UV detection. Either reversed-phase or normal
phase chromatography may be used. Detection limits are 0.2 to 10 Mg/mL of extract. An
acceptable procedure follows: Select HPLC column (for example, Zorbax-SIL, 4.6 mm i.d.
x 25 cm, or u-Bondapak CIS, 3.9 mm x 30 cm, or equivalent). Select solvent system (for
example, mixtures of methanol or acetonitrile with water or mixtures of heptane or hexane
with isopropanol). Follow analytical procedures given in 123.2 through 12.3.y. 11
interferences are present, adjust the HPLC solvent system composition or use column
chromatographic clean-up with silica gel, alumina or Florisil. An electrochemical detector
may be used to improve sensitivity for some ureas, carbamates and phenohcs. Much more
care is required in using this detector, particularly in removing dissolved oxygen from the
mobile phase and sample extracts. Chlorophenols have been successfully analyzed intact
by GC on a 4 mm (i.d.) x 60 cm glass column packed with double support-bonded
diethylene glycol succinate (DEGS).
16.5 Mass spectrometric analyses may be used for more unambiguous confirmation of
pesticides. Essentially all pesticides may be determined by GC-MS or HPLC-MS.
16.5.1 Many of the pesticides shown in Table 1 have been successfully analyzed by
GC-MS by the following procedure:
16 5.1.1 GC column carrier gas and flow rate as described in 12.3.2.
16.5.12 Temperature program, 40°C (2 min) to 295°C (10°C ^ min).
16.5.13 Splitless injection, 2 juL maximum volume (injection time 30 to 40 sec);
injector temperature, 205°C.
16.5.1.4 Interface temperature, 240°C.
Revised 9/30/89 PaSe 18
-------
Method IP-8 _ ; _ Pesticides
16.5.1.5 Mass spectrometer, quadrupole, electron ionization, multiple ion detection
mode.
16.5.1.6 Internal standards, D10-phenanthrene and D12chrysene.
16.6 See ASTM Standard Practice D3687 for solvent-flush injection technique,
determination of relative retention times, and other procedures pertinent to GC and HPLC
analyses.
16.7 If concentrations are too low to detect by the analytical procedure of choice, the
extract may be concentrated to 1 mL or 0.5 mL by carefully controlled evaporation under
an inert atmosphere. The following procedure is appropriate:
16.7.1 Place K-D concentrator tube in a water bath and analytical evaporator (nitrogen
blow-down) apparatus. The water bath temperature should be 25°C to 50°C.
16.72 Adjust nitrogen flow through hypodermic needle to provide a gentle stream.
16.73 Carefully lower hypodermic needle into the concentrator tube to a distance of
about 1 cm above the liquid level.
16.7.4 Continue to adjust needle placement as liquid level decreases.
16.7.5 Reduce volume to slightly below desired level.
16.7.6 Adjust to final volume by carefully rinsing needle tip and concentrator tube well
with solvent (usually n-hexane).
17. Performance Criteria and Quality Assurance
This section summarizes required quality assurance (QA) measures and provides guidance
concerning performance criteria that should be achieved within each laboratory.
17.1 Standard Operating Procedures (SOPs)
17.1.1 Users should generate SOPs describing the following activities accomplished in
their laboratory: . .
• assembly, calibration, and operation of the sampling system, with make and model 01
equipment used
• preparation, purification, storage, and handling of sampling cartridges
• assembly, calibration, and operation of the GC-ECD system, with make and model
of equipment used
• all aspects of data recording and processing, including lists of computer hardware and
software used ,.
17.12 SOPs should provide specific stepwise instructions and should be readily
available to, and understood by, the laboratory personnel conducting the work.
172 Process, Field, and Solvent Blanks
172.1 One PUF cartridge from each batch of approximately twenty should be anal-
yzed, without shipment to the field, for the compounds of interest to serve as a process
1722 During each sampling episode, at least one PUF cartridge should be shipped to
the field and returned, without drawing air through the sampler, to serve as a field blank.
Revised 9/30/89 ae 19
-------
Method 1P-8 Pesticides
172 3 Before each sampling episode, one PUF plug from each batch of approximately
twenty should be spiked with a known amount of the standard solution. The spiked plug
will remain in a sealed container and will not be used during the sampling period. The
spiked plug is extracted and analyzed with the other samples. This field spike acts as a
quality assurance check to determine matrix spike recoveries and to indicate sample
^nl^During the analysis of each batch of samples, at least one solvent process blank
(all steps conducted but no PUF cartridge included) should be earned through the
procedure and analyzed. . nn
172.5 Blank levels should not exceed 10 ng/sample for single components or 100
ng/sample for multiple component mixtures (e.g., for organochlonne pesticides).
173 Sampling Efficiency and Spike Recoveiy
173.1 Before using the method for sample analysis, each laboratory must determine
its sampling efficiency for the component of interest as per Section 15.
1732 The PUF in the sampler is replaced with a hexane-extracted PUK ihe vur
is spiked with a microgram level of compounds of interest by dropwise addition of hexane
solutions of the compounds. The solvent is allowed to evaporate.
1733 The sampling system is activated and set at the desired sampling flow rate, me
sample flow is monitored for 24 hours. .
173.4 The PUF cartridge is then removed and analyzed as per Section 12.3.
173.5 A second sample, unspiked, is collected over the same time period to account
for any background levels of components in the ambient air matrix.
173.6 In general, analytical recoveries and collection efficiencies of 75% are considered
to be acceptable method performance.
173.7 Replicate (at least triplicate) determinations of collection efficiency should be
made. Relative standard deviations for these replicate determinations of ±15% or less are
considered acceptable performance. t
173.8 Blind spiked samples should be included with sample sets periodically as a check
on analytical performance.
17.4 Method Sensitivity
Several different parameters involved in both the sampling and analysis steps of this method
collectively determine the sensitivity with which each compound is detected. As the volume
of air sampled is increased, the sensitivity of detection increases proportionately within
limits set by the retention efficiency for each specific component trapped on the
polyurethane foam plug and the background interference associated with the analysis ot
each specific component at a given site sampled. The sensitivity of detection of samples
recovered by extraction depends on the inherent response of the particular GC detector
used in the determinative step and the extent to which the sample is concentrated for
analysis. It is the responsibility of the analyst(s) performing the sampling and analysis steps
to adjust parameters so that the required detection limits can be obtained.
Revised 9/30/89 Pa8e 20
v
-------
Method IP-8 Pesticides
17.5 Method Precision and Bias
17.5.1 Precision and bias in this type of analytical procedure are dependent upon the
precision and bias of the analytical procedure for each compound of concern, and the
precision and bias of the sampling process.
17.52 The reproducibility of this method has been determined to range from 5 to 30%
(measured as the relative standard deviation) when replicate sampling cartridges are used
(N>5). Sample recoveries for individual compounds generally fall within the range of 90
to 110%, but recoveries ranging from 65 to 125% are considered acceptable. PUF alone
may give lower recoveries for more volatile compounds (e.g., those with saturation vapor
pressures > 10"3 mm Hg). In those cases, another sorbent or a combination of PUF and
Tenax GC should be employed.
17.6 Method Safety
This procedure may involve hazardous materials, operations, and equipment. This method
does not purport to address all of the safety problems associated with its use. It is the
user's responsibility to consult and establish appropriate safety and health practices and
determine the applicability of regulatory limitations prior to the implementation of this
procedure. This should be part of the user's SOP manual.
18. References
1. Riggin, R. M., Technical Assistance Document for Sampling and Analysis of Toxic Organic
Compounds in Ambient Air, EPA-600/4-83-027, U.S. Environmental Protection Agency,
Research Triangle Park, NC, 1983.
2. Lewis, R., and MacLeod, K., "Portable Sampler for Pesticides and Semivolatile Industrial
Organic Chemicals in Air," Analytical Chemistry, 54:310-315, 1982.
3. Lewis, R., Brown A., and Jackson, M., "Evaluation of Polyurethane Foam for Sampling
of Pesticides, Polychlorinated Biphenyls and Polychlorinated Naphthalenes in Ambient Air,"
Analytical Chemistry, 49:1668-1672, 1977.
4. Armour, J., and Burke, J., "Method for Separating Polychlorinated Biphenyls from DDT
and Its Analogs," Journal of the Association of Official Analytical Chemists, 53(4):761-768,
1970.
5. Manual of Analytical Methods for the Analysis of Pesticides in Human and Environmental
Samples, U.S. Environmental Protection Agency Report No. EPA-600/8/80/038, Research
Triangle Park, NC, June, 1980 (NTIS No. PB82-208752).
6. Hall, R., and Harris, D., "Direct Gas Chromatographic Determination of Carbamate
Pesticides Using Carbowax-20M Modified Supports and the Electrolytic Conductivity
Detector," Journal of Chromatography, 169:245-259, 1979.
7. Johnson, D. E., Schattenberg, H. J., Brewer, J. H., Wheeler, H. G., and Hsu, J. P.,
"Evaluation of Sampling and Analytical Methods for Determination of Human Exposure
to Selected Pesticides and PCBs by Inhalation, Ingestion and Dermal Contact," Southwest
Revised 9/30/89 Pa8e 21
-------
™ *i. A m a Pesticides
Method IP-8 _____ —
Research Institute, San Antonio, Texas. Final Report under U.S. Environmental Protection
Agency, Contract No. 68-02-3745.
8 Edgerton, T., and Moseman, R., "Gas Chromatography of Underivatized Chlorinated
Phenols on Support Bonded Polyester Column Packings," Journal of Chromatographic
Science, 18:25-29, 1980.
9 Riggin R. M., Compendium of Methods for the Determination of Toxic Organic
Compounds in Ambient Air, EPA-600/4-84-041, U.S. Environmental Protection Agency,
Research Triangle Park, NC, April, 1984.
10 Manual of Analytical Methods for Determination of Pesticides in Humans and
Environmental Standards, EPA-600/8-80-038, U.S. Environmental Protection Agency,
Research Triangle Park, NC, July, 1982.
11. "Test Method 608, Organochlorine Pesticides and PCBs," in EPA-600/4-82-057, U. S.
Environmental Protection Agency, Cincinnati, OH, July, 1982.
Revised 9/30/89 Page 22
-------
Method IP-8
Pesticides
Table 1. Pesticides Determined by Gas
Chromatography/Electron Capture Detector (GC-ECD)
Aldrin
BHC (a-and 0-Hexa-
chlorocyclohexanes)
Captan
Chlordane, technical
Chlorothalonil
Chlorpyrifos
2,4,-D esters
fi,fi,-DDT
fi,fi,-DDE
Dieldrin
Dichlorvos (DDVP)
Dicofol
2,4,5-Trichlorophenol
Folpet
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Lindane (r-BHC)
Methoxychlor
Mexacarbate
Mi rex
trans-Nonachlor
Oxychlordane
Pentachlorobenzene
Pentachlorophenol
Ronnel
Revised 9/30/89
Page 23
-------
Method IP-8 Pesticides
Table 2. Chromatographic Characteristics of the Single Component Pesticide
Mixture (5 /tl) Determined by GC-ECD Using a Packed Column
Retention Compound Concentration in pg Area/
Time Name on Column Height
2.77 gamma-BHC (Lindane) 500 8.2
3.37 Heptachlor 500 10.4
4.03 Aldrin 500 12.0
8.90 Dieldrin 500 24.7
14.63 p,p'-DDT 500 39.0
24.87 Dibutylchlorendate* 2500 61.4
26.82 Methoxychlor 2500 57.5
* Internal standard used for earlier pesticide detection.
Revised 9/30/89 Pa8e 24
-------
Method IP-8 Pesticides
Table 3. Chromatographic Characteristics of the Single Component Pesticide
Mixture (2 01) Determined by GC-ECD Using a Capillary Column
Retention Compound Concentration in pg Area/
Time Name on Column Height
14.28 gamma-BHC (Lindane) 200 5.2
17.41 Heptachlor 200 5.3
18.96 Aldrin 200 5.4
23.63 Dieldrin 200 5.8
27.24 p,p'-DDT 200 5.6
29.92 Methoxychlor 1000 5.5
31.49 Dibutylchlorendate* 1000 5.4
* Internal standard used for earlier pesticide detection.
Revised 9/30/89 Page 25
-------
Method IP-8
Pesticides
Table 4. Sampling Efficiencies for Some
Organochlorine Pesticides
Compound
cr-Hexachlorocyclo-
hexane (ot-BHC)
0-Hexachlorocyclo-
hexane (Lindane)
Hexachlorobenzene**
Chlordane, technical
p.,p/-DDT
ft,a'-DDE
Mi rex
Pentachlorobenzene**
Pentachlorophenol**
2,4,5-Tri chlorophenol **
2,4-D Esters:
isopropyl
butyl
isobutyl
isooctyl
Quantity
Introduced, us
0.005
0.5
0.5
0.5
0.5
Air
Volume, Sampling Efficiency, /.
m3 mean RSD n
0.9
115
0.05-1.0
0.5, 1.0
0.2
0.6, 1.2
0.2, 0.4
0.6, 1.2
1.0
1.0
1.0
0.9
0.9
0.9
0.9
0.9
0.9
0.9
0.9
0.9
91.5
94.5
84.0
97.5
102
85.9
94
107
108
8
8
11
21
11
22
12
16
3
5
5
8
12
12
7
5
5
5
3.6
3.6
3.6
3.6
92.0
82.0
79.0
>80*
5
10
20
--
12
11
12
- -
**
* Not vaporized. Value based on %RE = 81.0 (RSD = 10%, n = 6).
•- Semivolatile organochlorine pesticides.
Revised 9/30/89
Page 26
-------
Method IP-8 Pesticides
Table 5. Sampling Efficiencies for Organophosphorus Pesticides
Sampling
Quantity Efficiency, %
Compound
Dichlorvos (DDVP)
Ronnel
Chlorpyrifos
Diazinon8
Methyl parathion*
Ethyl parathion3
Malathion9
a Analyzed by gas chromatography with nitrogen phosphorus detector or flame
photometric detector.
b Air volume = 0.9 m3.
c Decomposed in generator; value based on %RE = 101 (RDS =7, n = 4).
Introduced. b uq
0.2
0.2
0.2
1.0
0.6
0.3
0.3
mean
72.0
106
108
84.0
80.0
75.9
100°
RSD
13
9
18
19
15
_.
n
2
12
18
18
--
Revised 9/30/89 Page 27
IffU
-------
Method IP-8
Pesticides
Table 6.
Extraction and 24-hour Sampling Efficiencies for Various
Pesticides and Related Compounds
Extraction
Efficiency, %*
Compound mean RSD
Chlorpyrifos
Pentachloro-
phenol
Chlordane
Lindane
DDVP
2,4-0 methyl
ester
Heptachlor
Aldrin
Dieldrin
Ronnel
Diazinon
trans -Nonachl or
Oxychl ordane
a-BHC
Chlorothalonil
Heptachlor
epoxide
* Mean values
** Mean values
83.3
84.0
95.0
96.0
88.3
--
99.0
97.7
95.0
80.3
72.0
97.7
100.0
98.0
90.3
100.0
11.5
22.6
7.1
6.9
20.2
--
1.7
4.0
7.0
19.5
21.8
4.0
0.0
3.5
8.4
0.0
Sampling Efficiency**, %, at:
10 nq/m3 100 nq/m3 1000 na/m3
mean
83.7
66.7
96.0
91.7
51.0
75.3
97.3
90.7
82.7
74.7
63.7
96.7
95.3
86.7
76.7
95.3
RSD
18.0
42.2
1.4
11.6
53.7
6.8
13.6
5.5
7.6
12.1
18.9
4.2
9.5
13.7
6.1
5.5
for one spike at 550 ng/plug and
for three determinations.
mean
92.7
52.3
74.0
93.0
106.0
58.0
103.0
94.0
85.0
60.7
41.3
101.7
94.3
97.0
70.3
97.7
RSD
15.1
36.2
8.5
2.6
1.4
23.6
17.3
2.6
11.5
15.5
26.6
15.3
1.2
18.2
6.5
14.2
two spikes at
mean
83.7
66.7
96.0
91.7
51.0
75.3
97.3
90.7
82.7
74.7
63.7
96.7
95.3
86.7
76.7
95.3
RSD
18.0
42.2
1.4
11.6
53.7
6.8
13.6
5.5
7.6
12.2
19.9
4.2
9.5
13.7
6.1
5.5
5500 ng/plug.
Revised 9/30/89
Page 28
-------
Method IP-8
Pesticides
Table 7. Sampling Efficiencies for Carbamates, Ureas,
Triazines, and Pyrethrins
Spike
Level,3
Static
Recovery,%
Retention
Efficiency,%
Sampling
Efficiency,^
Compound
Carbamates:
Propoxur
Carbofuran
Bendicarb
Mexacarbate
Carbaryl
Ureas:
Monuron
Diuron
Linuron
Terbuthiuron
Fluometuron
Chlortoluron
Triazines:
Simazine
Atrazine
Propazine
Pyrethrins:
PyrethrinI
Pyrethrinll
Allethrin
d-trans-Allethrin
Dicrotophos
Resmethrin
Fenvalerate
Ltg/pluq mean RSD n mean RSD n mean RSD n
19
20
20
18
20
20
10
10
10
25
25
25
25
25
61.4
55.3
57.3
62.8
56.6
87.0
84.1
86.7
85.0
91.4
86.2
103
104
105
90.5
88.6
69.2
76.8
72.0
76.5
87.9
10
12
11
19
14
8
8
8
10
11
6
7
11
10
11
9
9
22
14
3
6
6
6
6
6
6
6
6
6
6
6
5
5
5
6
6
5
6
6
6
6
77.6
64.2
69.8
62.7
63.6
91.2
90.0
92.5
88.8
101
92.0
101
98.9
99.9
95.6
69.9
58.3
74.4
71.7
66.7
57.2
37
46
43
41
53
6
2
4
8
3
7
9
7
14
22
29
12
9
8
14
20
6
6
6
6
6
5
5
5
5
5
5
6
6
6
5
5
6
5
5
6
3
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
aAir volume = 0.9 m3.
bDecomposed in generator.
cNot vaporized.
Estimated on the basis of 20 pg Pyrethrin with a composition of 48.4% and
30.3% by weight of Pyrethrins I and II, respectively.
Revised 9/30/89
Page 29
-------
Method IP-8
Pesticides
Table 8. Extraction and 24-Hour Sampling Efficiencies
for Various Pesticides and Related Compounds
Extraction
Retention Efficiency**, %, at:
:tTicie
mean
57.0
73.0
65.5
86.7
sncy~, TO
RSD
8.5
12.7
4.9
11.7
in ng/m3 100 na/m3
mean RSD mean RSD
38.0 25.9 65.0 8.7
56.0 -- 45.5 64.3
..
78.0 --
1000
mean
69.0
84.3
78.5
93.0
na/m3
RSD
--
16.3
2.1
--
Compound
Dicofol
Captan
Methoxlychlor
Folpet
* Mean values for one spike at 550 ng/plug and two spikes at 5500 ng/plug.
** Mean values for generally three determinations.
Revised 9/30/89
Page 30
-------
Method IP-8
Pesticides
115V Adapter/
Charger Plug
(a) Fixed Site Monitoring (b) Personal Monitoring
Figure 1. Sampling for Pesticides
Revised 9/30/89
Page 31
-------
Method IP-8
Pesticides
Figure 2. Polyurethane Foam (PUF) Sampling Cartridge
Revised 9/30/89
Page 32
-------
Method IP-8
Pesticides
FLOW RATE
METER (0-1 in H20)
/O ' */
fv_
(
FLOW RATE
VALVE
)
/• 500 mL
4 BUBBLE
TUBE
AIR IN
DISH WITH
BUBBLE SOLUTION
PRESSURE DROP
METER (0-50 in H20)
V
PRESSURE DROP
VALVE
Figure 3. Calibration Assembly for Air Sampler Pump
Revised 9/30/89
Page 33
-------
Method IP-8
Pesticides
Site Date Performed by
Sampler
S/N
Sampling
Location
I.D
Height
Above
Ground
PUF Cart.
No.
Samplinc
Start
Period
StOD
Sampling
Time min.
Pump Timer
hr. min.
Low flow
Indication
Yes
Np
Comments
Checked by_
Date
Figure 4. Low Volume Pesticide Sampling Data Form
Revised 9/30/89
Page 34
£73
-------
Method IP-8
Pesticides
OPERATING CONDITIONS
Column Type:
Temperature:
Detector:
Carrier Gas:
Flow Rate:
1.5% SP 2250/1.95% SP 2401,
1/4" glass.
200 °C isothermal.
Electron Capture.
5% Methane/95% Argon.
65 to 85 mUmin.
Lindane
Heptachlor
Aldrin
Dibutylchlorendate
Methoxychlor
Dieldrin
TIME
Figure 5. Chromatograph Showing a Mixture of Single Component
Pesticides Determined by GC/ECD Using a Packed Column
Revised 9/30/89
Page 35
-------
Method IP-8
Pesticides
OPERATING CONDITIONS
Column Type:
DB-5 0.32 capillary,
0.25 um film thickness
Column Temperature Program: 90°C (4 min)/16°C per min to
154°C/4°C per min to 270°C.
Detector: Electron Capture
Carrier Gas: Helium at 1 mL/min.
Make Up Gas: 5% Methane/95% Argon at 60 mL/min.
TIME
Dibutylchlorendate
Methoxychlor
Heptachlor
Lindane
JL
L. *. I
y
Udrin Endrir
Dieldrin
i
p,p' DDT
Figure 6. Chromatograph Showing a Mixture of Single Component
Pesticides Determined by GC/ECD Using a Capillary Column
Revised 9/30/89
Page 36
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Method IP-8
Pesticides
AIR INLET
PRE-FILTER
'O' RING SEAL
COLLECTION
MEDIUM
AIR TO PUMPING
SYSTEM
COLLECTION
MEDIUM
BACK-UP
Figure 7. Apparatus for Determining Sampling Efficiencies
Revised 9/30/89
Page 37
-------
Chapter IP-9
DETERMINATION OF REACTIVE ACIDIC AND BASIC
GASES AND PARTICULATE MATTER IN INDOOR AIR
(ANNULAR DENUDER TECHNIQUE)
1. Scope
This document describes a sampling and analytical protocol for the annular denuder system
(ADS) This system was developed to measure reactive acidic and basic gases and
paniculate matter which are contained in indoor ambient air. The chemical species which
can be measured by the ADS are gaseous SO2, HNO2, HNO3 and NH3 and particulate
SO/ NO," NH4+ and FT. Other similar chemical species can be successfully collected by
the system with just a few simple modifications (i.e., changing the denuder coating solutions,
the denuder sequence and the liner or filter types and sequence). Once collected, the
pollutant concentrations are quantified by ion chromatography (1C) analysis and/or
Technicon colorimeter autoanalysis. The 1C protocols for sample preparation, analysis and
quantification are detailed within the ADS method. The Technicon autoanalyzer protocols
are utilized to quantify ammonia (NH3), nitrate (NO3'), and sulfate (SO4~) in ambient air
samples.
2. Applicability
2.1 Recently, these and other acid gases and aerosols, and particulate matter have been
of growing concern to indoor air quality groups. Much emphasis has been directed to
understanding the many chemical forms in which these pollutants can exist and the
conditions which cause chemical changes to occur. Industrial and commercial facilities, as
well as hazardous waste storage and treatment facilities, contribute significantly to indoor
air contamination through various source-specific emissions. Although several of the
previously mentioned pollutants can be instrumentally measured to quantify their
concentration in the ambient air, many of the established methods are not adequate (or
sensitive enough) to measure these pollutants at the levels typically found in non-urban
locations. As a result, monitoring and research efforts have been designed to assess what
sources are responsible for targeted pollutant emissions, what health and ecological impacts
are incurred, and what the maximum allowable ambient concentrations should be.
2.2 The ADS has been utilized in such research efforts. The system's configuration has
made it a very appealing asset to monitoring crews. Its ability to collect the chemical
species of interest with little or no interference from sampling artifacts has separated it
from other air monitoring techniques. Each sampling network can assemble the treated
denuders and filters in such a manner that specific pollutants, which can cause ambient
concentrations to be falsely assessed, are withdrawn from the air stream before interfering
chemical reactions can occur. Subsequently, it is very important to investigate all possible
chemical reactions between the species of interest before setting up the ADS.
2.3 As with all monitoring methods, the ADS has its limitations. Operation below 20%
relative humidity may result in less than quantitative collection of SO2. Also, the annular
denuders are fragile and require great care when handled. Studies are being conducted to
Revised 9/30/89
r.
k
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Chapter IP-9 Reactive Gases/Particulate Matter
determine how well Teflon® coated aluminum denuders collect acid aerosols. Other studies
include identifying interferents which can cause under- or over-estimations of pollutant
concentrations to be made and accounting for interferant reactions in the calculations.
Revised 9/30/89 Page "
-------
Method IP-9
DETERMINATION OF REACTIVE ACIDIC AND BASIC
GASES AND PARTICULATE MATTER IN INDOOR AIR
(ANNULAR DENUDER TECHNIQUE)
1. Scope
2. Applicable Documents
3. Summary of Method
4. Significance
5. Definitions
6. Interferences
7. Apparatus
7.1 Sampling
7.2 Analysis
8. Reagents and Materials
9. Preparation of Coating and Extraction Reagents
1C)! Elutriator and Acceleration Jet (Inlet) Assembly
11. Impactor Frit Preparation and Installation
12. Filter Pack Preparation and Assembly
13. Annular Denuder System Preparation
13.1 Annular Denuder Coating Procedure
13.2 Annular Denuder Drying Procedure
13.3 Annular Denuder System (ADS) Assembly
13.4 Laboratory Leak-check of ADS
14. Sampling
14.1 Start-up
14.2 Sample Shutdown
14.3 Corrective Action for Leak Test Failure
15. ADS Disassembly
16. Extraction Procedures
16.1 Impactor Frit Coating Extraction
16.2 Denuder Extraction
16.3 Filter Extraction
17. Ion Chromatography Analysis
17.1 Standards Preparation
17.2 Reagent Preparation
17.3 Sample Preparation
17.4 Basic System Operations - Start-Up and Shut-Down
17.4.1 Start-up Procedure for Ion Chromatograph
17.4.2 Data Acquisition Start-up
17.4.3 Calibration of 1C
17.4.4 System Shut-down
17.5 Basic Troubleshooting
Revised 9/30/89
Page 1
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Method IP-9 Reactive Gases/Particulate Matter
18. Ammonia Analysis by Technicon Autoahalysis
18.1 Standard and Stock Solutions Preparation
18.2 Reagent Preparation
19. pH Analysis
19.1 Standard and Reagent Preparation
19.2 Calibration of pH Meter
19.3 Pre-Analysis Calibrations
19.4 pH Test 0.01 N Perchloric Acid Solution
19.5 Analysis of Working Standards
19.6 Analysis of Filter Extracts
20. Atmospheric Species Concentration Calculations
20.1 Assumptions of Annular Denuder System
20.2 Calculations Using Results from 1C Analysis
20.3 Estimates of Errors in Concentrations Deduced from
Denuder Data
20.4 Calculations Using Results from pH Analysis
21. Variations of Annular Denuder System Usage
22. Method Safety
23. Performance Criteria and Quality Assurance
24. References
Appendix - Spectra-Physics Integrator Program for 1C Analysis
Revised 9/30/89 Page 2
-------
Method IP-9
DETERMINATION OF REACTIVE ACIDIC AND BASIC
GASES AND PARTICULATE MATTER IN INDOOR AIR
(ANNULAR DENUDER TECHNIQUE)
1. Scope
11 This document describes the protocol for the quantitative measurement of reactive
acidic and basic gases and paniculate matter which are contained in indoor atmospheres.
12 The chemical species which can be determined by this method are gaseous SO2, HNO2,
HNO,, and NH3 and paniculate SO4=, N(V, NH4+, and IT, as well as the mass of fine
paniculate matter (d50 < 2.5 0m). Detection and quantitation limits are given in Table 1.
13 The methodology detailed in this document is a composite of methodologies developed
by U.S. Environmental Protection Agency (USEPA), Harvard University and the CNR
Laboratories. It is currently employed in a number of air pollution studies in Italy, U.b.A
Canada, Mexico, Germany, Austria, and Spain, and in such institutions as public health
services, epidemiology and environmental research centers.
14 The equipment described herein is utilized to measure acidic and basic gases anc
paniculate matter contained in both indoor and outdoor atmospheres. The outdoor methoc
was originally developed for monitoring regional-scale acidic and basic gases and paniculate
matter in support of U.S. EPA field programs involving the Integrated Air Cancer Research
Program and the Acid Deposition Network. Similarly, the methodology has been used to
characterize the urban haze in Denver, Houston and Los Angeles.
2. Applicable Documents
2.1 ASTM Standards
D1356 Definitions of Terms Related to Atmospheric Sampling and Analysis
2.2 Other Documents
Ambient Air Studies (1-9)
U.S. EPA Technical Assistance Document (10)
3. Summary of Method
3.1 Indoor air is drawn through an elutriator-accelerator jet assembly, an impactor frit and
coupler assembly, and past glass denuder walls which have been etched and coated with
chemicals that absorb the gaseous species of interest. The remaining air stream is then
filtered through Teflon* and Nylasorb* membrane filters. Teflon* and nylon membrane
filters are used to capture ammonium and nitrate aerosol and sulfate paniculate matter.
Nitric acid and sulfur dioxide will also be collected by the nylon filter but these
measurements are treated as interference. Figure 1 illustrates the annular denuder system
(ADS) assembled ready for testing. Figure 2 shows the field sampling box with the ADb
and pump-timer (11).
Revised 9/30/89 Page 3
£&(
6? 6*6
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Method IP-9 Reactive Gases/Particulate Matter
3.2 After sampling, the annular denuders are extracted with 5 mL of deionized water The
extracted solutions are subsequently analyzed for ions corresponding to the collected
gaseous species (see Figure 1). The filters are placed into filter bottles where five or ten
mL of the 1C eluent are pipetted into each filter bottle with the filters face downward and
completely covered by the eluent. The filter bottle is capped and put in an ultrasonic bath
for 30 minutes. The bottles are stored in a clean refrigerator at 5°C until analysis.
3 3 The analysis of anion and cation concentrations collected by the denuders and filter
pack is typically performed by ion chromatographic and Technicon* colorimeter
autoanalytic procedures. The H+ concentration of extracts from the Teflon* filter
downstream of the denuders is performed by use of pH measurements using commercially
available pH meters calibrated with standards (11).
4. Significance
41 Reactive acidic (SO2, HNO2 and HNO3) and basic (NH3) gases and particles are found
in the atmosphere as a result of emission from a variety of fossil fuel combustion sources
including industrial and commercial facilities, hazardous waste storage and treatment
facilities etc. Measurements of these chemical species are currently being used in a broad
range of environmental studies such as in 1) epidemiological programs to assess the impact
of acid aerosols on respiratory impairment, 2) receptor modeling to determine the origin
of particles that impact EPA's PM-10 air paniculate standard, 3) assessment of the impact
of paniculate nitrate and sulfate on visibility, and 4) the quantification of the impact of
acidic and basic air pollutants on issues related to acid ram.
42 The unique features of the annular denuder which separates it from other established
monitoring methods are elimination of sampling artifacts due to interaction between the
collected gases and particles, and the preservation of the samples for subsequent analysis
which is accomplished by removing NH3 in the gas stream by the citric acid coated denuder
and reducing the probability of the paniculate sulfate (SO4=) captured by the filter pack
being neutralized to ammonium sulfate [(NH4)2SO4]. If NH3 is not extracted from the gas
stream prior to filtration, correction of paniculate sulfate and gaseous sulfur dioxide would
be required for accurate measurements to be obtained.
5. Definitions
Definitions used in this document and any user prepared Standard Operating Procedures
(SOPs) should be consistent with ASTM D1356. All abbreviations and symbols are defined
within this document at the point of use.
5 1 Paniculate mass - a generic classification in which no distinction is made on the basis
of origin, physical state, and range of particle size. (The term "paniculate" is an adjective,
but it is commonly used incorrectly as a noun.)
5.2 Primary particles (or primary aerosols) - dispersion aerosols formed from particles that
are emitted directly into the air and that do not change form in the atmosphere. Examples
include windblown dust and ocean salt spray.
Revised 9/30/89 " " Pa8e 4
-------
Method IP-9 Reactive Gases/Particulate Matter
53 Secondary particles (or secondary aerosols) - dispersion aerosols that form in the
atmosphere as a result of chemical reactions, often involving gases. A typical example is
sulfate ions produced by photochemical oxidation of SO2.
5 4 Particle - any object having definite physical boundaries in all directions, without any
limit with respect to size. In practice, the particle size range of interest is used to define
"particle" In atmospheric sciences, "particle" usually means a solid or liquid subdivision of
matter that has dimensions greater than molecular radii (-10 nm); there is also not a firm
upper limit, but in practice it rarely exceeds 1 mm.
5.5 Aerosol - a disperse system with a gas-phase medium and a solid or liquid disperse
phase Often, however, individual workers modify the definition of "aerosol by arbitrarily
requiring limits on individual particle motion or surface-to-volume ratio Aerosols are
formed by 1) the suspension of particles due to grinding or atomization, or 2) condensation
of supersaturated vapors.
5.6 Coarse and fine particles - these two fractions are usually defined in terms of the
separation diameter of a sampler. Coarse particles are those with diameters greater than
25 /im but less than 10 nm and that are collected by the sampler; the fine particles are
those with diameters less than 2.5 /tin and that are collected by the sampler.
Note: Separation diameters other than 2.5 fan. have been used.
5.7 Annular - of, rotating to, or forming a ring. In the annular denuder sampler, the
annular refers to the cylinder to which coating is applied to the interior parallel planes to
remove gaseous pollutants by diffusion chemistry.
5.8 Denuder - the denuder refers to the process gaseous pollutants from the gas stream.
6. Interferences
6.1 Operation below 20% relative humidity (RH) may result in less than quantitative
collection of SO2. Atmospheric water vapor in concentrations above 30% RH has been
shown not to be an interferant for SO2 collection.
62 Studies are being conducted to identify interferents and calculations are being
developed to correct the measurements obtained by the annular denuder system for
identifiable interferents. For example, the presence of ozone (O3) is known to oxidize
nitrous acid (HNO2) to nitric acid (HNO3); therefore, measurements of HNO2 are often
underestimates. Calculations have been developed to adjust for this oxidation process and
provide more accurate estimations of HNO2 concentrations in the atmosphere.
6.3 Other studies include the possible chemical reactions (organic and inorganic) which
may occur with selected coating solutions which interfere with the accurate measurement
of the chemical species of interest.
6.4 The efficiency of impactor collection decreases when the impactor surface is loaded.
The average operational time before such loading occurs has not been determined.
Revised 9/30/89 Page 5
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Method IP-9 _ Reactive Gases/Particulate Matter
7. Apparatus
Note: The following descriptions relate to Figure 2. Most of these parts are available
commercially by University Research Glassware. However, it is important to note that
these items can be made by any qualified vendor; therefore, it is not necessary that these
specific items are obtained and utilized.
7.1 Sampling
7.1.1 Elutriator and acceleration jet assembly - Under normal sampling conditions, the
elutriator or entry tube is made of either Teflon* coated glass or aluminum. When using
glass, the accelerator jet assembly is fixed onto the elutriator and the internal surfaces of
the entire assembly are coated with Teflon*. When aluminum is used, the accelerator jet
assembly is removable. The jet is made of Teflon* or polyethylene and the jet support is
made of aluminum. Again, all internal surfaces are coated with Teflon*. Both assemblies
are available with 2, 3 and 4 mm inside diameter jets (nozzles) [University Research
Glassware, 118 E. Main St., Carrboro, NC, 27510, (919-942-2753)]. ,
7.1 2 Teflon* impactor support pin and impactor frit support tools - Made of either
Teflon* or polyethylene and are used to aid in assembling, removing, coating and cleaning
the impactor frit [University Research Glassware, 118 E. Main St., Carrboro, NC, 27510,
(919-942-2753)]. * . . „ , A-
7.13 Impactor frit and coupler assembly - The impactor frit is 10 mm x 3 mm and is
available with a porosity range of 10-20 Mm. The frits should be made of porous ceramic
material or fritted stainless steel. Before use the impactor frit surface is coated with a Dow
Corning 660 oil and toluene solution for use, and sits in a Teflon* seat support fixed within
the coupler. The coupler is made of thermoplastic and has Teflon* clad sealing "0"-nngs
which are located on both sides of the seat support inside the coupler. The couplers are
composed of two free moving female threads which house the support tools when
assembling and removing the impactor frit, and couple the denuders when sampling. There
are arrows printed on the metal band which holds the female threads together. These
arrows should be pointing in the direction of air flow (see Figure 1) when the ADS is
assembled. .
Note: In situations when there are substantial high concentrations of coarse particles
(>2.5 pm), it is recommended that a Teflon* -coated aluminum cyclone be used in place
of the acceleration jet and impactor assembly, as illustrated in Figure 3. The cyclone is
made of Teflon* -coated stainless steel. Figure 4 illustrates the location of the cyclone with
respect to the denuder, heated enclosure and meter box assembly ready for sampling
[University Research Glassware, 118 E. Main St., Carrboro, NC, 27510, (919-942-2753)].
7.1.4 Annular denuder - The denuder consists of two concentric glass tubes. The tubes
create a 1 mm orifice which allows the air sample to pass through. The inner tube is inset
25 mm from one end of the outer tube; this end is called the flow straightener end. The
other end of the inner tube is flush with the end of the outer tube. Both ends of the inner
tube are sealed. In this configuration, the glass surfaces facing the orifice are etched to
provide greater surface area for the coating. There are three types of denuders available.
One is the older version which accommodates the impactor support pin assembly, and can
Revised 9/30/89 ~ ~
-------
Method IP-9 Reactive Gases/Particulate Matter
only be the first denuder in sequence. It is available in glass with the impactor support
holder made of glass and the impactor support pin assembly made of Teflon*. The
denuder is 265 mm long with size #30 threads for coupling. It is available with flow
straighteners at both ends; however, most denuders in use today only have one flow
straightener end. The second most recent denuder version, which can be used as any
denuder in sequence, is available in glass with only one flow straightener end. It is 242 mm
long and has size #30 threads. Finally, the third denuder design involves two inner
concentric glass tubes (1 mm separation) positioned around a solid center glass rod as
illustrated in Figure 5. Once again, the glass surfaces are etched to provide greater surface
area for the coating. The inner glass tubes and coater rod are inset 25 mm from one end
of the outer Teflon*-coated stainless steel tube to serve as the flow straightener end. All
denuder types should be equipped with thermoplastic or polyethylene caps when purchased
[University Research Glassware, 118 E. Main St., Carrboro, NC, 27510, (919-942-2753)].
7.1.5 Caps for annular denuder - Caps are made of either polyethylene or thermoplastic
and are used in the coating and drying processes, for storage and for shipment. The
thermo-plastic caps include a removable Teflon* seal plate when purchased. Repeated
reuse of these types of caps have caused some contamination due to the improper cleaning
of the cap and Teflon* seal plate, i.e., fluid tends to be trapped under the seal plate. The
polyethylene caps are not equipped with seal plates. Observation has concluded that
polyethylene caps tend to dry faster and seal better than the thermoplastic caps. Less
sample contamination has been reported, also [University Research Glassware, 118 E. Main
St., Carrboro, NC, 27510, (919-942-2753)].
7.1.6 Annular denuder couplers - The couplers should be made of thermoplastic and
equipped with Teflon* MO"-rings which sandwich a silicone rubber ring on three sides. This
provides elasticity for better sealing under extremely cold temperature conditions in which
Teflon* does not give. There are two types of couplers available. In the older version,
the couplers have removable seal rings. Problems with denuder breakage and leakage due
to improper threading of the couplers with the denuders led to the development of a second
type of coupler. The new couplers are equipped with permanent seal rings which provide
more even threading and a better seal when coupled. Some couplers have built-in
flow-straighteners. The couplers are used to couple the annular denuders together and for
coupling the last denuder with the filter pack [University Research Glassware, 118 E. Main
St., Carrboro, NC, 27510, (919-942-2753)].
7.1.7 Drying manifold assembly - The manifold is made of pyrex and is available to
accommodate as many as 4 drying denuders. The denuders are attached to the manifold
with back-to-back Bakalite bored caps. The bored caps are connected with a Teflon®
connector ring. Air is pushed through an air dryer/ cleaner bottle made of 2 1/2 inch
heavy wall pyrex which contains silica gel, calcium sulfate and activated charcoal (not
available with assembly). The tubing which connects the dryer/cleaner bottle to the drying
manifold should be secured at each cap with either Teflon* washers or Teflon® washers
coupled with Teflon* hose barbs [University Research Glassware, 118 E. Main St.,
Carrboro, NC, 27510, (919-942-2753)].
Revised 9/30/89 Pa§e 7
I
i.
-------
Method IP-9 Reactive Gases/Particulate Matter
7.1.8 Filter pack assembly - The filters are supported by stainless steel porous screens
and are housed in a polyethylene filter ring housing. The Teflon* filter ring housing
directly follows the Teflon* filter housing inlet component. The "nylon" filter ring housing
follows the Teflon* filter ring housing and sits on a Teflon* "O"-ring which seals the filter
ring housing components to the filter housing outlet component. (There can be up to
4-filters in series depending on the species of interest.) The filter housing outlet component
is aluminum and accommodates a polyethylene screw sleeve which seals the filter pack
assembly. The sleeve is available in different lengths to accommodate up to 4 filter ring
housing units. A stainless steel "Quick-Release" plug screws into the aluminum outlet
component for connecting the pump-timer to the filter pack assembly. It is equipped with
an orange "dust cover" (male plug) upon purchase [University Research Glassware, 118 E.
Main St., Carrboro, NC, 27510, (919-942-2753)].
7.1.9 Vacuum tubing - Low density polyethylene tubing, 3/8 inch diameter for distances
of less than 50 ft., 1/2 inch diameter for distances greater than 50 ft. Since this tubing is
used downstream from the sampler, similar sized tubing or pipe of any material may be
substituted. The tubing must have sufficient strength to avoid collapsing under vacuum
[Fisher-Scientific, 711 Forbes Ave., Pittsburgh, PA, 15219, (412-787-6322)].
7.1.10 Tube fitting - Compression fittings (Swagelok*, Gyrolok* or equivalent) to
connect vacuum tubing (above) to an NPT female connector or filter holder and connect
vacuum tubing to fitting on differential flow controller. The fittings may be constructed of
any material since they are downstream of the sampler [Fisher-Scientific, 711 Forbes Ave.,
Pittsburgh, PA, 15219, (412-787-6322)].
7.1.11 Annular denuder system (ADS) sampling box - The housing box is made of a
"high-impact" plastic and is insulated with polyurethane. It is 4 feet long by 6 inches wide
and 6 inches deep. There are two heater units, a fan blower and an air outlet located in
the lid of the housing. Also, located on the lid are the automatic and manual control
switches and a 12-V power supply outlet for the heater and fan. The bottom of the box
houses the ADS. The elutriator end of the ADS protrudes through one end of the box,
while the denuders are supported in the box by chrome plated spring clips. If the Teflon*-
coated aluminum cyclone is used to remove coarse particles, it is also housed in the heated
sampling box, with the elutriator end protruding through the sampling box, as illustrated
in Figure 4. There is a vacuum plug known as a "quick-release" coupler that is linked to
the filter pack of the ADS. This connects the ADS to 1 1/4 in. Teflon* rubber "clad"
shrink tubing which exhausts the air stream to the ambient air. The box is sledge hammer
proof [University Research Glassware, 118 E. Main St., Carrboro, NC, 27510, (919-942-
2753)].
7.1.12 Annular denuder field-to-lab case - The field-to-lab case is made of rigid plastic
and insulated with polyurethane. It is made to be hand carried, not shipped, and is used
to transport 4 total annular denuder systems each consisting of either 3 annular denuder
sections or 2 annular denuder sections and 1 denuder-impactor assembly. The systems are
packed already assembled and capped, and either ready for sampling or ready for sample
analysis. The case has a carrying handle, a lock and 3 latches and is equipped with 2 keys
Revised 9/30/89 Page 8
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Method IP-9 Reactive Gases/Particulate Matter
[University Research Glassware, 118 E. Main St., Carrboro, NC, 27510, (919-942-
2753^1
7.1.13 Annular denuder shipping case - The shipping case is made of formica, backed
with plywood and insulated with polyurethane. The corners are reinforced with metal. It
is made to withstand shipping by truck, UPS and Federal Express Each case is stackable
and lockable and has a carrying handle. Seven total annular denuder systems can be
packed in the case, provided each system contains 4 denuders each. The systems can
consist of either 3 denuders (242 mm long) and 1 denuder-impactor assembly (265 mm
long) or 4 denuders (242 mm long). Each component of the system is packed in its own
storage compartment. The personal sampler assemblies can also be &™^*W£*f
this case [University Research Glassware, 118 E. Main St., Carrboro, NC, 27510, (919-942-
7.1.14 Differential flow controller (pump) - This unit pumps air through the sampler at
a fixed rate of between 5 and 20 standard L/min (typically 10 L/min) wrth a precision of
±5% over the range of 25 to 250 mm Hg vacuum [University Research Glassware, 118 b.
Main St., Carrboro, NC, 27510, (919-942-2753)].
7115 Dry eas meter (DGM) - The DGM should pull 10 L of gas per revolution
[Nutech, Corp.f 2806 Cheek Rd., Durham, NC, 27704, (919-682-0402)].
12 Analysis
7.2.1 Ion chromatograph - A chromatograph equipped with the appropriate anion and
cation exchange resin filled separator and suppressor columns and conductivity detector for
measuring acidic (SO2, HNO2 and HNO3) and basic (NH3) ions in solution^(i.e
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Method IP-9 Reactive Gases/Partlculate Matter
72.10 Forceps - Recommended dressing forceps made of stainless steel or chrome-plated
steel and without serrations. Used for handling filters (Millipore).
72.11 Stopwatch - Used for measuring flow rate of gas stream through DGM, best
source.
72.12 Ultrasonic cleaner - Used for filter extractions and parts cleaning. Most are
temperature controlled. It is recommended to control the temperature during extraction
at 65°C [Cole-Palmer Instrument Co., 7425 N. Oak Park Ave., Chicago, IL, 60648, (800-
323-4340)].
72.13 Clean air hood - Closed air hood with ammonia free air circulation. Used for
Teflon* filter extraction for pH analysis, best source.
8. Reagents and Materials
8.1 Teflon® filters - Zefluor* (PTFE) membrane filters 47 mm diameter with a 2 Mm pore
size. Only one side is Teflon* coated; this side should face the air stream [Gelman
Sciences, 600 S. Wagner Rd., Ann Arbor, MI, 48106, (800-521-1520)].
82 Nylasorb* filters - Membrane filters 47 mm diameter with a 1 /on pore size. These
filters are specially prepared and batch analyzed for low SO4=, NO2", and NO3' background
levels. If other brands of nylon membrane filters are used, they should be batch analyzed
to ensure low and replicable levels of SO4=, NO2", and NO3" [Gelman Sciences, 600 S.
Wagner Rd., Ann Arbor, MI, 48106, (800-521-1520)].
8.3 Denuder extract storage vials - 30 mL (1 oz) screw-cap polyethylene sampling vials
(Nalgene or equivalent). Allow eight (8) per sample for each sampling period, best source.
8.4 Filter extract storage vials -100 mL polyethylene vials (Nalgene or equivalent). Allow
two (2) vials for each sampling period, best source.
8.5 1C analysis vials and caps - The vials are available in 5 mL and 0.5 mL and are made
of polypropylene. The filter caps are made of plastic and contain a Teflon* filter through
which the sample is extracted for analysis. Both the vials .and filter caps should be
disposable, best source.
8.6 Labels - Adhesive, for sample vials, best source.
8.7 Parafilm - Used for covering flasks and pH cups during pH analysis, best source.
8.8 Kimwipes® and Kay-dry towels - Used for cleaning sampling apparatus and analysis
equipment, best source.
8.9 Stoppers - Cork or polyethylene, best source.
8.10 Sodium carbonate (Na2CO3) - ACS reagent grade, best source.
8.11 Sodium chloride (NaCl) - ACS reagent grade, best source.
8.12 Methanol (methyl alcohol - CH3OH) - ACS reagent grade, best source.
8.13 Toluene - ACS reagent grade, best source.
Revised 9/30/89 Page 10
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Method IP-9 Reactive Gases/Particulate Matter
8.14 Glycerol (glycerin - CH2OHCHOHCH2OH) - ACS reagent grade, best source.
8.15 Citric acid (monohydrate - HOC (CH2CO) OH)2COOH : H2O) - ACS reagent grade,
best source.
8.16 Hydrogen peroxide (H2O2) - ACS reagent grade, best source.
8.17 Ethanol (C2H5OH) - ACS reagent grade, best source.
8.18 Sulfuric acid (H2SO4) - ACS reagent grade, best source.
8.19 Potassium chloride (KC1) - ACS reagent grade, best source.
820 Perchloric acid (HC1O4) - ACS reagent grade (60-62°C), best source.
821 Distilled deionized water (DDW) - ASTM Type I water.
822 pH buffers - Standard buffers 4.00 and 7.00 for internal calibration of pH meter, best
source.
823 Silica gel - ACS reagent grade (indicating type), best source.
824 Sodium bromide (NaBr) - ACS reagent grade, best source.
825 Activated charcoal - ACS reagent grade, best source.
826 Balance - Electronic analytical with internal calibration weights and enclosed weighing
chamber. Precision of 0.1 mg [Fisher-Scientific, 711 Forbes Ave., Pittsburgh, PA, 15219,
(412-787-6322)].
827 Gloves - Polyethylene disposable. Used for impactor frit assembly and filter pack
assembly, best source.
8.28 Dow Corning high temperature vacuum oil - Dow Corning 660 oil used for impactor
frit coating solution, best source.
829 Zero air - A supply of compressed clean air, free from particles, oil, NO, NO2, SO2,
HNO3, and HONO. The supply may be either from a commercial cylinder or generated
on site, best source.
8.30 1C eluent solution - For extracting filters. This should be the same eluent as used
for the ion chromatographic analysis of the filters. If the filter analysis is not to be
performed by ion chromatography, then a slightly basic solution (e.g., 0.003 N NaOH or
sodium carbonate/bicarbonate) should be used to extract the Nylasorb® filter, while the
Teflon* filter should be extracted with DDW.
9. Preparation of Coating and Extraction Reagents
9.1 Impactor frit coating solution preparation - Weigh 1 g of silicone oil (Dow Corning
high temperature 660 oil) and place in a 100 mL polyethylene storage bottle. Add 100 mL
of toluene. Mix thoroughly, close container, and store at room temperature.
(WARNING - FLAMMABLE LIQUID).
Revised 9/30/89 " Pa8e n
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Method IP-9 Reactive Gases/Particulate Matter
92 Impactor frit extraction solution preparation - Add 100 mL of 1C eluent to a clean
polyethylene storage container. Pipette 5 mL of methanol into container. Mix thoroughly.
Store, covered at room temperature.
93 Annular Denuder Coating Solutions Preparation
Note: Different coatings may be used depending on the chemical species of interest.
9.3.1 NaCl coating solution - Clean a 100 mL polyethylene storage vial and let dry at
room temperature. Weigh 0.1 g of reagent grade NaCl and add to vial. Add 90 mL of
deionized water and 10 mL of methanol. Mix thoroughly; store, covered at room
temperature.
932 Na2CO3 coating solution - Clean a 100 mL polyethylene storage vial and let dry
at room temperature. Measure 50 mL of methanol (WARNING - TOXIC, FLAMMABLE
LIQUID) with a graduated cylinder and pour into vial. Measure 50 mL of DDW with a
graduated cylinder and add to vial. Weigh 1 g of glycerol and add to DDW. Weigh 1 g of
a2CO3 and add to vial. Mix thoroughly, solution may fizz; wait for fizzing to stop before
sealing vial. Store at room temperature.
933 Citric acid coating solution - Clean a 100 mL polyethylene storage vial and let dry
at room temperature. Measure 50 mL of methanol (WARNING - TOXIC, FLAMMABLE
LIQUID) with a graduated cylinder and pour into vial. Weigh 0.5 g of citric acid and add
to vial. Mix thoroughly; store, covered at room temperature.
10. Elutriator and Acceleration Jet (Inlet) Assembly
Note: Figure 6A shows the all glass configuration.
10.1 The internal walls of the elutriator and jet assembly are coated with Teflon® to
prevent losses of reactive species (SO2, HNO3, NH3) during sampling. The elutriator
prevents water and large particles from entering the inlet and thus extends the life of the
impaction surface located immediately downstream of this assembly.
10.2 Figure 6B shows an aluminum version of this inlet. All inner surfaces of the
aluminum unit are Teflon® coated. The main difference between the all glass and the
aluminum inlet is the jet component of the aluminum inlet is replaceable as shown in
Figure 3B. The jet component is made of either Teflon® or polyethylene and is available
in various diameters as needed to accommodate selected sample flow rates. The jet may
be replaced using the tool shown in Figure 6B. The jet diameter for a sample flow rate of
10 L/min is 3.33 mm. At this flow rate the inlet has a D50 cutpoint of 2.5 /xm. If a
different flow rate is to be used, the jet diameter must be changed to retain a D50 cutpoint
to 2.5 fan. Figure 7A shows the relationship between jet diameter and flow rate to retain
a D50 at 2.5 /mi. Table 2 contains the jet diameters and Reynolds number to maintain a
D50 of 2.5 /im cutpoint at different flow rates between 1 and 20 L/min.
Note: If the sampling area has substantial concentrations of coarse particles ( > 2.5 /an), the
user may select to replace the acceleration jet and impactor assembly with the Teflon®-
coated aluminum cyclone. The D50 cutpoint at a flow rate of 10 L/min is 2.5 /«n, as
illustrated in Figure 7B.
Revised 9/30/89 ~~~~~ Page 12
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Method IP-9 Reactive Gases/Particulate Matter
11. Impactor Frit Preparation and Installation
11.1 Impactor Frit Installation
11.1.1 Impactor-coupler - The impactor-coupler assembly shown in Figure 8 is comprised
of two parts: the replaceable impactor frit and the coupler-impactor housing seat The
impactor surface is a porous ceramic or porous stainless steel frit, 10 mm x 3 mm. This frit
is inserted into the coupler-impactor housing using the tools shown in Figure 9. It is
imperative that the in-tool is completely screwed in behind the impactor seat before the
frit is pressed into place. The impactor frit is pressed gently but firmly into the seat of the
impactor housing with your clean gloved finger. The impactor should fit into the housing
so that it does not protrude above the seat. The impactor frit has a slight bevel. Ihe
narrow surface should be inserted into the impactor seat.
11.1.2 Impactor-denuder - The impactor-denuder assembly shown in Figure y is
comprised of three parts: the replaceable impactor frit, the impactor seat support pm and
the annular denuder impactor-pin support. The impactor frit is the same as descnbed in
Section 11.1.1 and is inserted, as previously described, into the impactor seat support pin.
The impactor support pin can either be hand-held while inserting the frit or it can be
placed upright into the aluminum frit holder #3 (see Figure 10). Press the support pin
into the denuder pin support. The pin is grooved and has a viton "O"-ring to keep the pin
snug in the denuder support during cold weather use (Teflon* tends to shrink at low
temperatures). The support pin is removed by using the removal tool shown in Figure 9.
11.2 Impactor Frit Preparation
With the impactor frit in the impactor seat of either the coupler (see Figure 8) or the
Teflon* impactor seat support pin which fits into the first denuder (see Figure 9), pipette
50 ML of the toluene-660 oil coating solution onto the impactor frit surface and allow to dry
at room temperature. Cap both sides of the coupler impactor or denuder-impactor until
use.
12. Filter Pack Preparation and Assembly
Note: Any number of filters can be used depending on the target species of interest. The
configuration referred to in this section does not collect NH4+.
12.1 With clean gloves, disassemble the filter pack (see Figure 11) by unscrewing the large
outer Teflon* collar (sleeve) from the aluminum filter housing outlet component.
Note: It is necessary to remove the polyethylene cap first. Lay the pieces out on clean
Kimwipes*. Insert black viton "O"-rings (see Figure 11).
122 Lay a clean Teflon* filter ring housing, with its large opening face-up, on a clean
Kimwipe*. Place a clean stainless steel screen in the filter ring housing.
12.3 Using clean filter forceps, place a Nylasorb* nylon filter on the screen. Insert a
second filter ring housing on top of the nylon filter with its large opening face-up. This
forms a "sandwich" with the nylon filter held between the two filter ring housings.
Revised 9/30/89 Pa8e 13
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Method IP-9 _ Reactive Gases/Particulate Matter
12.4 Place another clean screen on the second filter ring housing. Using clean filter
forceps, place a Teflon® filter on the screen. . ,
Note- If a Teflasorb* Teflon* filter is used, be sure to place the Teflon* coated side not
thTwebbed side, toward the air stream. If the webbed side is facing the air stream, SO«
extraction from the filters may be inefficient.
12 5 Place the Teflon* filter housing inlet component (see Figure 11) on top of the
Teflon* filter This forms another "sandwich" with the Teflon* filter held between the
second filter ring housing and the housing inlet component. The housing inlet component
connects the filter pack assembly to the last annular denuder through a thermoplastic
coupler. Be careful not to twist the filterpack components, or damage will occur to the
filters.
12 6 Lay the aluminum filter housing outlet component, with its large opening face-up, on
a clean Kimwipe*. Insert a black viton "O"-ring in the aluminum filter base.
12.7 Insert the filter ring sandwiches (prepared in Sections 12.1-12.5) with the filter housing
inlet component extending upward, on the viton "O"-ring in the aluminum filter base. Place
COMPONENTS!
12.8 Install the "Quick-Release" plug into the filter outlet component. DO NOT
OVERTIGHTEN!
12.9 Install the polyethylene cap onto the filter inlet component and the orange dust cover
onto the Quick-Release plug until ready to attach denuders.
13. Annular Denuder System Preparation
All new annular denuder parts obtained from suppliers should be cleaned by placing them
in a dilute soap solution in an ultrasonic cleaner for about 10 minutes. The parts should
then be thoroughly rinsed in DDW and allowed to dry at room temperature.
13.1 Annular Denuder Coating Procedure
Note: If the first denuder holds the impactor, a blank Teflon* impactor support pin should
be installed in the pin support holder before the coating procedure.
13 1 1 Cap the end of the denuder which has the inner tube flush to the outer tube and
set denuder upright on the capped end. For the denuders with flow-straighteners at both
ends either end can be capped. Measure 10 mL of the appropriate coating solution into
a graduated cylinder. Pipette the 10 mL into the flow-straightener end of the upnght
capped annular denuder.
13.1.2 Cap the open end of the denuder and holding horizontally, rotate the denuder
to distribute the coating solution evenly (see Figure 12).
Revised 9/30/89 Page 14
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Method IP-9 Reactive Gases/Particulate Matter
13 13 Remove cap from flow-straightener end of denuder and decant excess coating
solution into a clean denuder extract storage bottle labeled "denuder blank." Bottle label
should include denuder number, coating solution and date.
13.1.4 Repeat this procedure with each denuder; label the denuders and bottles
appropriately.
132 Annular Denuder Drying Procedure
Note: As denuders dry, they change from translucent to a frosted appearance. Denuders
are dry when they become uniformly frosted.
13.2.1 Drying train and manifold clean air flow should be adjusted to 2 to 3 L/min.
Close toggle valve controlling clean air flow through manifold before attaching denuders.
1322 Attach flow-straightener end to drying manifold port at the back-to-back bored
caps (see Figure 13). , .. ,
13.2.3 Open toggle valve and allow clean air to flow through the tube for several
minutes. .- .,
132.4 Close toggle valve, and reverse ends of tubes attached to mamlold.
13.2.5 When an even frosted appearance is achieved, remove tubes from manifold, cap
both ends with clean caps and store until ready for use. Turn off air to drying manifold.
133 Annular Denuder System (ADS) Assembly
Note- Described herein is an annular denuder system consisting of 4 denuders in series.
Any number of denuders can be used as per the operators discretion. It is recommended
to assemble the denuders in such a way that the flow-straightener end always follows the
flush end of the previous denuder, except, in the event that denuders with flow-
straighteners at both ends are used. This type of assembly allows laminar flow conditions
to be restored.
133.1 Lay the ADS pieces on a clean surface (i.e., Kimwipes*).
1332 Remove the end caps from the first denuder, Denuder I is coated with NaCl
and may or may not hold the impactor frit pin support. If the first denuder is equipped
with the impactor frit pin-support, remove the blank impactor support pin. Gently insert
the impactor support pin and coated frit assembly into the denuder-pm support. If the tirst
denuder does not hold the impactor pin-support, attach the impactor frit seat equipped
coupler assembly to the flow-straightener end of the first denuder.
Note: DO NOT TIGHTEN! Do not tighten during the following procedure until Section
13.4.12 is reached.
133.3 Attach a thermoplastic coupler to the opposite denuder end. Flace a leiion
clad "O"-ring inside the coupler, if needed.
133.4 Remove the end caps of the second denuder (Na2CO3 coated). Attach the end
with the flow-straightener section to the first denuder-coupler assembly.
133.5 Attach a thermoplastic coupler to the opposite denuder end. Place a Teflon
clad "O"-ring inside the coupler, if needed.
Revised 9/30/89 Pa8e 1S
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Method IP-9 Reactive Gases/Particulate Matter
13.3.6 Remove the end caps of the third denuder (Na2CO3 coated). Attach the end with
the flow-straightener section to the second denuder-coupler assembly.
133.7 Attach a thermoplastic coupler to the opposite denuder end. Place a Teflon®
clad "O"-ring inside the coupler, if needed.
13.3.8 Remove the end caps from the fourth denuder (citric acid coated). Attach the
end with the flow-straightener section to the third denuder-coupler assembly.
13.3.9 Attach a thermoplastic coupler to the opposite denuder end. Place a Teflon®
clad "O"-ring inside the coupler, if needed.
133.10 Attach the filter pack inlet to the fourth denuder coupler assembly.
133.11 When using the first denuder equipped with the impactor frit-pin support, a
thermoplastic coupler with a Teflon* clad "O"-ring is used to attach the inlet assembly.
Attach but do not tighten!
13 3 12 Attach the elutriator-acceleration jet assembly to the first denuder-coupler
assembly. Tighten very gently - DO NOT OVERTIGHTEN or breakage will result. (This
applies when using either first denuder described).
133.13 Tighten the remaining couplers very gently - do not overtighten or breakage will
result (see Figure 1).
133.14 Cap elutriator with orange dust cover until use.
Note: When collecting and measuring gaseous HN02, HNO3, SO2, and NH3, and particulate
NO,', NH4+, and SO4=, it is essential to assemble the annular denuders as previously
described. It is impossible to distinguish the difference between deposited HNO2 and
HNO, if the NaCl coated denuder does not precede the Na2CO3 coated denuder. It is
impossible to quantify the amount of HNO2 collected if there are not two Na2CO3 coated
denuders in series. Also, NH3 must be taken out of the gas stream prior to the air stream
entering the filter pack. Otherwise, reaction of the unneutralized sulfate will result. If
ammonia (NH3) and/or H" measurements are not to be analyzed for, then the use of a
citric acid coated denuder is not important. However, with the removal of NH3, some
nitrate collected on the Teflon* filter will tend to evaporate and be found on the nylon
filter.
13.4 Laboratory Leak-Check of ADS
Note: CAUTION - Do not subject the system to sudden pressure changes or filters may
tear.
13.4.1 Remove the orange dust cap from the impactor opening. Attach the
"Quick-Release" to a pump module. Turn on the pump. Be certain that flow through the
ADS occurs by checking the rotameter.
13.4.2 Briefly cap the elutriator with the orange dust cap. The flow as indicated on the
rotameter should drop to zero if no leaks exist.
13.4.3 Disconnect the pump from the ADS at the "Quick-Release" plug. Cap the
"Quick-Release" plug with an orange dust cover. Turn off the pump. REMEMBER -
Never overtighten joints or breakage will result. If the joints can not be sealed with gentle
tightening, then the Teflon* "O"-rings are worn or defective and must be replaced.
Revised 9/30/89 PaSe 16
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Method IP-9 Reactive Gases/Particulate Matter
13.4.4 Place the assembled sampler in its field-to-lab carrying case for transport to the
field (see Figure 14).
Note: It is recommended that the ADS joints be loosened slightly when extreme
temperature changes are incurred during transportation. This will prevent unnecessary
breakage or distortion of the ADS components. Remember to allow the system to adjust
to the indoor air temperature before tightening the joints and checking for leaks.
14. Sampling
14.1 Start-up
14.1.1 Remove the ADS from its field-to-lab carrying case and load into the field
sampling box. The ADS field sampling box is insulated with polyurethane which is
configured to hold the ADS without allowing movement. Chromeplated spring clips hold
the denuders in place. Automatic and manual control switches allow the sampling box to
control the temperature of the ADS. The automatic switch should be used when the ADS
is not in use and when the ADS is sampling for extended periods of time without constant
supervision to prevent low temperature or sudden pressure change exposure of the ADS
(these types of exposure can cause leaks to occur, condensation, or the filters to tear).
When sampling, the ADS should be kept 1°C above the indoor temperature to prevent
condensation. The sampling box has two connections with the pump tinier: the plastic
suction hose connected with "Quick-Release" couplers and the 12-V power cord with a
"Quick-Disconnect" coupler. The power cord remains connected, and the suction hose is
disconnected from the box each time the unit is opened. Inside the box, the hose is
connected to the top of the filter pack with a "Quick-Release" coupler. During sampling
the sample box is kept securely closed (see Figure 2).
14.12 Allow the pump to warm up for 20-30 minutes prior to testing so the pump will
provide steady flow during testing.
14.1.3 To check the Heat/Cool cycles, flip one switch from "AUTO" to "MANUAL
and the other between "COOL" and "HEAT." Check to insure that the fan and heater (i.e.,
light bulb) work, respectively. .
14.1.4 With the elutriator still capped, turn on the pump with the switch on the timer.
The rotameter should indicate zero flow. If there is a flow, the assembly pieces need to be
recoupled. Run leak check for 5-10 seconds, then turn off pump and remove elutriator cap.
Record leak rate on Field Test Data Sheet (see Figure 15).
14.1.5 Attach DGM output to elutriator inlet. Turn on pump. Record start time on
Field Test Data Sheet (see Figure 15). Using a stopwatch, record the time for 20.0 L to
pass through the DGM. Record the DGM temperature and the absolute pressure of the
DGM.
14.1.6 Calculate the flow rate as follows:
QSTD = (V/T)(Pb/PSTD)(TSTO/Tm)(Fc)
where:
QSTO = flow rate corrected to standard conditions, O°C and 760 mm Hg, L/min
V = volume of gas pulled through denuder system, L
Revised 9/30/89 " Pa8e 17
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Method IP-9 Reactive Gases/Particulate Matter
T = time required to pull 20 L of gas through denuder system, minutes
Pb = barometric pressure, mm Hg
PSTD = standard barometric pressure, 760 mm Hg
TSTD = standard temperature, 273°C
Tm = temperature of dry gas meter, 273°C + T,,,
F = dry gas meter correction factor, dimensionless
° 14.1.7 If the calculated flow rate is not between 5 and 16 L/min, typical 10 L/min, then
readjust the flow rate and repeat Sections 14.1.4 and 14.1.5 until the rate is in the above
range. Preliminary studies should be conducted to obtain an estimate of the concentrations
of the species of interest.
14.1.8 Record the flow rate on Field Test Data Sheet.
14.1.9 Remove DGM connection tubing from elutriator inlet. Pump should remain
running so that sampling continues. Higher flow rates may be used for shorter sampling
periods. Concentration of the species of interest in indoor air and the configuration of the
sampling equipment, determine the appropriate flow rates. Sampling at 10 L/min, requires
a sampling time of 24 hours for the collection of pollutant concentrations between 0.02 and
0.83 jig/n?.
14.2 Sample Shutdown
142.1 Attach DGM connection tubing elutriator inlet with pump still running. Measure
flow rate as in Sections 14.1.5 and 14.1.6. Record flow time, temperature, and pressure on
Field Test Data Sheet (See Figure 15).
1422 Turn off pump. Record time and elapsed time meter reading on log sheet.
Remove DGM connection tubing from elutriator inlet. Remove ADS from the sampling
box, cap the ends, and place the ADS in field-to-lab carrying case for transport to lab. Be
careful not to stress the ADS during the transfer or breakage will result. CAUTION -
When the ADS is brought from a cold field sampling location to a warm laboratory, it is
necessary to loosen the denuder couplings to prevent thermal expansion from breaking the
denuders.
143 Corrective Action for Leak Test Failure
Note: These steps should be followed when failure occurs during testing at the laboratory
before transport to the field and in the field before testing.
14 J.I Sampler leaks - Note the problem on the Field Test Data Sheet. Check assembly
of ADS components. Replace gaskets. Check for proper seating of denuder surfaces.
Replace any defective parts.
14.32 Cracked or chipped denuders or elutriator assemblies - Note problem on meld
Test Data Sheet. Discard defective pieces. Do not try to extract cracked pieces.
WARNING - use caution when disassembling cracked glassware. Pieces may shatter and
cause severe cuts. Wear protective clothing.
14.3.3 Contaminated blank solutions - Note problem on Field Test Data Sheet. Follow
parts cleaning procedures closely. Examine the sampler preparation area for possible
sources of contamination and remove source, if found. Check DDW being used in the
Revised 9/30/89 "
y
ik.
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Method IP-9 Reactive Gases/Particulate Matter
solution preparations and extractions: Fill a clean 25 mL polyethylene extraction bottle
with the DDW used in solution preparation and extraction, send to lab for analysis. If
contaminated, correct deionization system.
14.3.4 Flow rate disagreement - Note problem on Field Test Data Sheet. Check vacuum
gauge on flow module. If a high vacuum exists then the sampler has become blocked. This
may be due to dust or smoke particles clogging the filters or to obstructions in the system
or tubing. Check flow module. Repair as needed.
14.3.5 Inadequate flow rate - Note problem on Field Test Data Sheet. Check rotameter
on flow controller. If adequate flow is shown here, then a leak exists between the controller
and the DGM. If no flow is shown on rotameter, then check vacuum gauge on controller.
If no vacuum exists, then pump needs repair. If a high vacuum is shown, then an
obstruction exists in the system. Check to see that the paper filter dividers were not
accidentally installed with the filters in the filter pack. Check tubing for kinks.
Note: Typically the pressure drop across the filters should be approximately 1 inch Hg at
10 L/min flow rate at sea level. This pressure drop can vary from 1-10 L/min depending
on elevation.
15. ADS Disassembly
15.1 Remove the ADS from the field-to-lab carrying case using both hands. To prevent
stress, hold the ADS by its ends. CAUTION - Do not stress the ADS while removing it
from the case.
15.2 Decouple the elutriator - jet assembly from the first denuder-impactor-coupler
assembly.
15.3 When using the denuder-impactor, the frit-pin must be removed from the support in
the denuder before removing the frit from the pin (see Figure 9). The frit is then extracted
from the pin using pin tool #3 and the frit extraction tool (see Figure 10). When using the
impactor-coupler assembly, the frit is removed from the coupler seat using pin tool #3 and
the "out" frit removal tool (see Figure 16). Put frit in covered dish and set aside for
chemical extraction.
15.4 Remove the denuders from the couplers and cover each end of the denuders with
clean end caps until extraction.
15.5 Label a clean 100 mL polyethylene bottle with the sampler ID number and filter type
(i.e., Teflon* or Nylasorb®, as appropriate) for each of the filters.
15.6 Disassemble the filter pack in a clean, ammonia-free air hood. Clean all hood
surfaces and utensils with methanol. Wearing clean gloves and using clean filter forceps,
remove the filters and place each in its storage (protective) bottle, with the exposed filter
surface facing downward, until extraction.
Note: Be careful to place the filters in the properly labeled bottles.
Revised 9/30/89 Page 19
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Method IP-9 Reactive Gases/Particulate Matter
16. Extraction Procedures
Special precaution: Samples should be analyzed as soon after collection as possible. It is
imperative that the solutions and extraction procedures are prepared and performed on the
day of pH analysis. Extraction must take place in a clean, ammonia-free, air hood. The
extracts must be processed in the order in which they will be analyzed, so that each sample
will have a similar time interval between extraction and analysis. Denuder extracts and
filters should be stored in the refrigerator until just prior to analysis. Samples stored longer
than 30 days tend to degrade due to bacteria growth and/or losses to the walls of the
extraction vessel.
16.1 Impactor Frit Coating Extraction
16.1.1 Place the impactor (which was removed before denuder extraction) into a small
extraction bottle.
16.12 Label the bottle appropriately. Pipet 10 niL of impactor extraction solution into
the bottle. The solution must cover the surface of the impactor frit.
16.1.3 Close the extraction bottle and place in an ultrasonic bath for 30 minutes.
162 Denuder Extraction
Note: If the denuder was the first denuder, which is equipped with the impactor frit-pin
support, insert a clean Teflon* impactor frit-pin, without frit in place. Then extract as
described below. This procedure is to be followed for each denuder.
16.2.1 Cap one end of the denuder. Add 5 mL of DDW with a pipet. Cap other end.
16.2.2 Rotate the denuder to wet all surfaces thoroughly with the water. Remove the
cap and pour the liquid into a clean 25 mL polyethylene extraction bottle.
1623 Repeat this procedure with a second 5 mL of DDW extract (total extract volume
is 10 mL which is placed into a single bottle).
162.4 Replace the extraction bottle cap and label the bottle with the sampler ID
number, denuder number and type (as appropriate).
16.3 Filter Extraction
16.3.1 Teflon* Filter Extraction (for pH analysis followed by ion chromatography (1C)
analysis)
Note: Teflon® is not wet by water; therefore, the filter will float on top of aqueous
solutions. It is imperative that the solutions and extraction procedures are prepared and
performed on the day of pH analysis. Extraction of the filters must take place in a clean,
ammonia-free, air hood. The filters must be processed in the order in which they will be
analyzed, so that each sample will have a similar time interval between extraction and
analysis.
16.3.1.1 Allow the hood to be flushed with ammonia-free air for at least 5 minutes
before filter extraction. All of the hood surfaces and extraction utensils must be cleaned
with a Kimwipe* moistened with ethanol.
Revised 9/30/89 Page 20
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Method IP-9 Reactive Gases/Particulate Matter
163.12 Pipet 3 mL of 0.0001 N perchloric acid (HC1O4) solution into the
appropriately labeled extraction vial (4 mL). , . . , , •
Note: It is necessary to use HC1O4 because it inhibits CO2 from dissolving into the solution
and keeps the organic compounds in solution from dissociating. Both these activities, it
allowed to take place, can cause the ionic strength of solution to change.
163.13 Place the Teflon* filter in the extraction vial. Cap tightly. Store at 5 C in
the dark until ready for analysis. . .
163.1.4 When ready for analysis, the filter must be prepared (within the air hood)
in the following manner: Using forceps and gloved hands, lift the filter from the extraction
vial Let the excess solution drain off into the vial. Holding the filter over the extraction
vial and using an automatic pipet, apply 100 ± 5 mL of ethanol to the filter. Add the
ethanol slowly to ensure that all portions of the membrane are wet with ethanol. Immerse
the filter in the aqueous solution once again. Tap the forceps against the inside of the vial
to remove liquid. Tightly replace cap. Put in ultrasonic bath for 15 minutes total, rotating
the rack 90° every 5 minutes. . ..„ * *
Note: Perchloric acid is used in place of potassium chloride, initially, to prevent
interference in the measurements of cations and anions by ion chromatography. Potassium
chloride must be added to the portions of the sample extract which are used for pH analysis
(the purpose of the salt, final concentration 0.04 M, is to increase the ionic strength and
thus to reduce the time for equilibrium of the pH electrode used for measurement). Note
also that it is necessary to use the same bottle (freshly opened) of ethanol for the extraction
of the Teflon* filters that is used for the preparation of sulfunc acid standards.
163.1.5 When ready for pH analysis, the extracts are prepared in the order of pH
measurement. Inside the air hood, remove the caps from 4 mL extraction vials. Wipe oil
any drops which may leak onto the outside of the cup.
163.1.6 Using gloved hands and a 1 mL automatic pipet, transfer 1 mL of the extract
to each of two correspondingly labeled 2 mL cups.
Note- The first 2 mL cup for each extract has the same I.D.# as the 4 mL cup and the
second 2 mL cup has the same I.D.# with a hyphen (-)• This is the same system used with
the working standards.
16.3.1.7 After transferring the extracts to the 2 mL cups, recap the 4 mL extract cup.
Then store the 4 mL cups at 5°C in a refrigerator pending sulfate analysis by 1C.
1632 Nylon Filter Extraction
1632.1 Pipet 10 mL of 1C eluent into the appropriately labeled filter vial or bottle
with caps. r , ..,.
Note: Be sure that the filter lies flat on the bottom of the bottle and that all of the filter
is covered by the extraction solution.
16322 Replace the bottle's cap and put in an ultrasonic bath for 30 minutes.
16323 Store the bottles in a clean (i.e., pollutant free) refrigerator at 5°C in the dark
until analysis.
Revised 9/30/89 ae 21
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Method IP-9 Reactive Gases/Particulate Matter
17. Ion Chromatography Analysis
Note: The analytical procedure described here is not the only appropriate procedure
available for quantifying the analytes of interest. It is not necessary that an automated
system be utilized. This particular analytical procedure was chosen because it is presently
being utilized by EPA. Modifications to this procedure may be required depending on the
intended use of the data, however, any modifications made must be justified in order to
obtain comparable data quality.
17.1 Standards Preparation
Special Precaution: Storage of these solutions should be no longer than one week. All of
the working standard solutions are used to calibrate the 1C and are made from reagent
grade stock. The crystals are dried overnight in covered petri dishes at 110°C in a vacuum
oven prior to preparing the standard solutions. Any yellowish discoloration of the dried
crystals indicates decomposition and crystals should be discarded.
17.1.1 Sodium Sulfate Stock Solution
17.1.1.1 In a clean, calibrated, 1 L flask, add 500 mL of DDW.
17.1.1.2 On weighing paper, weigh out enough reagent (Na2SO4) to make the solution
2000 ppm concentration. The target weight is 0.7394 g. Record the gross weight. Note: It
is best to weigh out slightly more than the target weight due to the adherence of the
residual crystals to the weighing paper (the residual left on the paper is generally between
0.1 mg and 1 g).
17.1.1.3 Add the reagent crystals to the 500 mL of DDW. Reweigh weighing paper
and subtract weight from the gross weight. The difference is the actual net weight.
17.1.1.4 Using a proportion, calculate the actual volume needed to make the solution
2000 ppm (see below).
target wt/actual net wt = 500 mL (target)/actual volume
or
actual volume = (500 mL * actual net wt)/target wt
17.1.1.5 Using the appropriate calibrated pipet, add the amount of DDW needed to
achieve the calculated actual volume. Mix well and cover with parafilm.
17.12 Sodium Nitrate Stock Solution
In a clean, calibrated, 1 L flask, add 500 mL of DDW.
On weighing paper, weigh out enough reagent (NaNO3) to make the solution
2000 ppm concentration. The target weight is 0.6854 g. Record the gross weight.
Note: It is best to weigh out slightly more than the target weight due to the adherence of
residual crystals to the weighing paper.
17.123 Follow Sections 17.1.1.3 through 17.1.1.5.
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Method IP-9 Reactive Gases/Particulate Matter
17.1.3 Sodium Nitrite Stock Solution
17.1 J.I In a clean, calibrated, 1 L flask, add 500 mL of DDW.
17.132 On weighing paper, weigh out enough reagent (NaNO2) to make the solution
1000 ppm concentration. The target weight is 0.7499 g. Record the gross weight.
Note: It is best to weigh out slightly more than the target weight due to the adherence of
residual crystals to the weighing paper.
17.1.3.3 Follow Sections 17.1.1.3 through 17.1.1.5.
17.1.4 Standard working solutions - The working solutions are made up as follows: Add
10 mL each of the three stock solutions (Na2SO4, NaNO3, and NaNO2) to a 200 mL
volumetric flask and dilute to the mark with DDW. Subsequent dilutions are carried out
using a 10 mL volumetric pipet and appropriate flasks. Standards of 20, 10, 5 and 1 ppm
Na2SO4 and NaNO3 (and one-half these concentrations of NaNO2) are prepared. These
are used to calibrate the 1C.
17.2 Reagent Preparation
Note: Storage of these reagents should be no longer than one week.
17.2.1 Anion eluent - The anion eluent is a solution of 1.8 ton Na2CO3 and 1.7 pm
NaHCO3. A concentrated solution can be prepared and diluted as needed.
Note: See Anion Storage Solution
17.2.1.1 Concentrated Na2CO3 solution (0.36 M) - Weigh out 38.156 g of Na2CO3
(MW = 105.99). Dissolve into 1 L of DDW. Store in refrigerator until ready to dilute.
17.2.1.2 Concentrated NaHCO3 solution (0.34 M) - Weigh out 28.564 g of NaHCO3
(MW = 84.01). Dissolve into 1 L of DDW. Store in refrigerator until ready to dilute.
17.2.1.3 Dilution of stock solutions - Bring both solutions to room temperature.
Accurately pipet 10 mL of each solution into a 2000 mL volumetric flask which has been
partially filled with DDW. Bring to the mark with DDW (1:200 dilution).
17.2.2 Anion regenerant - The regenerant is a 0.025 N H2SO4 solution. VERY
CAREFULLY dispense 2.8 mL of concentrated Ultrex sulfuric acid (36 N) into a graduated
cylinder. Partially fill the regenerant reservoir with DDW (3 L). Slowly add the acid to the
regenerant reservoir. Bring to the mark with DDW (4 L).
Note: Protective clothing and eye protection should be utilized.
17.2.3 Cation eluent - There are two cation eluents that are used for the analysis of
monovalent and divalent cations. The strong cation eluent is: 48 /tm HC1, 4 /im DAP.HC1,
4 ion. Histidine.HCl (DAP = Diaminoproprionic acid). The weak eluent consists of 12 pm
HC1, 0.25 urn DAP.HC1, 0.25 urn Histidine.HCl.
1723.1 Strong cation eluent - Weigh 0.560 g DAP and 0.840 g histidine into a one
liter volumetric flask. Add 48 mL of 1 M HC1 (Ultrex) to the flask. Bring the eluent to
the final volume by bringing to the mark with DDW. Mix thoroughly to dissolve.
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Method IP-9 Reactive Gases/Particulate Matter
17232 Weak cation eluent - Place 63 mL of the strong cation eluent in a 1 L flask.
Add 9 mL of 1 M HC1 to the flask. Bring the eluent to the final volume by bringing to the
mark with DDW. Mix thoroughly to dissolve.
I73A Cation regenerant - The cation regenerant consists of 100 pM Tetrabutyl-
ammoniumhydroxide (TBAOH). Place the TBAOH container into a warm water bath to
dissolve any crystals that may have formed. Measure 266.7 mL of the TBAOH (stock
reagent is supplied as 1.5 M, 40% in water) into a graduated cylinder. Add the TBAOH
to 4 L of DDW.
17.2.5 Anion storage solution - Since the anion columns contain carbonates from the
eluent, protection must be taken against microorganisms that will live on this food source
and clog up the columns. If the columns are not being used for long periods of time (>2
weeks), a storage solution of 0.1 M NaOH should be pumped into them.
17.3 Sample Preparation
17.3.1 Mark the auto sampler vials with the appropriate identification numbers. Place
the vials in an (1C) autosampler tray.
17.3.2 Using clean, calibrated 0.5 mL pipets transfer the denuder and the remainder of
the filter extracts from the extraction vials to a clean disposable 0.5 mL (1C) autosampler
(polyethylene) vial. Fill the autosampler vial up to the line on the side.
Note: If refrigerated, the contents of the 4 mL extraction vial must be vortex-mixed prior
to transfer to the autosampler vials.
17.3.3 Place black filter caps on top of the vials. Use the tool provided to push the
caps into the vials until they are flush with the top. (see the 1C manual for more detailed
instructions). .
17.3.4 Wipe away any excess fluid from the top of the vial to avoid contamination from
other samples.
173.5 After all of the trays are filled, place them into the left side of the autosampler.
The white dot on the tray indicates the first sample. Press the button labeled RUN/HOLD
to the RUN position. The trays should move until the first sample is under the sampling
head. The front panel should indicate a READY message. Press local/remove switch to
remove.
17.4 Basic System Operations - Start-up and Shut-down
17.4.1 Start-up Procedure for Ion Chromatograph
17.4.1.1 Figure 17 illustrates the major components of the Dionex 2020i Ion
Chromatography system. Turn helium and nitrogen tanks on by opening the valve on top
of each tank (pressure in either tank should not be less than 500 psi. Replace if necessary).
Open valves at the outlet end of both regulators. Pressure on the nitrogen regulator is
adjusted to 100 psi. Pressure on the helium regulator is adjusted to 14 psi.
17.4.12 Check the level of eluents and regenerating solutions. Turn the
Chromatography (CMA) values for the anion channel switch ON. Verify that the pressure
Revised 9/30/89 Pa§e 24
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Method IP-9 Reactive Gases/Particulate Matter
reading on the face of the .degassing unit is 7 psi. Adjust by turning dial next to pressure
gauge. Turn the degas switch to HIGH.
17.4.1.3 Turn the eluent reservoir switches, corresponding to the eluents to be
degassed, to the ON position. Let the eluents degas on HIGH for 3-5 minutes, then turn
degas switch to LOW.
17.4.1.4 Select the appropriate program on the gradient pump module using the
PROGRAM switch. (Programs are recalled from memory by first pressing the PROGRAM
switch, then the single digit reference number corresponding to the appropriate program).
17.4.1.5 Priming the eluent lines.
Note: All of the eluent lines used during analysis must be primed to remove any air
bubbles that may be present. The selected program identifies which lines are used. .
• Open the gradient pump drawer. Turn the pump to the START position for 10
seconds, or until a CLICK is heard, then turn the pump OFF. This step opens the
valve to the eluent line displayed on the front panel.
. Attach a 10 mL syringe to the priming block on the face of the gradient pump module.
With the priming block valve closed, pull the syringe plunger out to the end of the
SVTIUCC.
. Open the priming block valve. The syringe will quickly fill with eluent. Close the
valve on the priming block when the syringe is almost full. Remove syringe from block
and discard collected eluant.
. This priming procedure can be repeated if necessary. All of the eluent lines that are
to be used during a day of analysis should be primed at this time.
17.4.1.6 Open the door of the Advanced Chromatography Module. On the back of
the door at the bottom, is the conductivity detector. There are four labeled lines (anion,
cation, waste, and cell) located next to the cell. The plumbing must be configured
according to the type of analysis to be performed. If anions are being analyzed, the
ANION line must be attached to the CELL line, and the CATION line must be attached
to the WASTE line. If cations are being analyzed, the CATION line must be attached to
the CELL line, and the ANION line must be attached to the WASTE line. The line
coming from the pump must be attached to the correct port on the advanced
chromatography module. SYSTEM 1 on the left is for anions, SYSTEM 2 on the right is
for cations. . ,
Note: If switching from one system to the other, the pump and the lines coming from the
pump must be purged of the original eluent. This is done by disconnecting the pump line
from the chromatograph module, turning the pump on and running the new eluent into a
waste beaker for 2-3 minutes. .
17.4.1.7 Select the columns to be used (labeled pH or NO2) by pressing the blue
button located below the labels. To verify that the correct columns are being used, the
switch should be pressed at least once, and then set to the appropriate position. This is
done in case the indicator light is reflecting a "default" setting, regardless of the actual
position of the switch.
17.4.1.8 Turn the power switch on the autosampler ON (switch is located on the back
of the unit, on the right). The default settings will be displayed on the front panel. Attach
Revised 9/30/89 ae 25
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Method IP-9 Reactive Gases/Particulate Matter
the SAMPLE OUT line from the autosampter to the advanced chromatography module.
The connection should be made to the port marked SAMPLE of the appropriate system.
Turn the pump to START.
17.4.1.9 Turn the conductivity cell ON. Switch is located on the gradient pump
module. Turn the REGEN switch for the appropriate system ON. Verify that regenerant
is flowing by inspecting the regenerant waste line which empties into the sink. Open the
advanced chromatography module door and inspect for leaks at columns, fittings, etc. Shut
pump off if leaks are found.
17.4.1.10 Turn stripchart recorder ON. Baseline should stabilize in less than 20
minutes. If baseline is not stable, see troubleshooting Section 173 for assistance.
17.42 Data acquisition start-up - The following is a description of the current data
acquisition program used by the U.S. EPA. The program is available (U.S. EPA,
Atmospheric Chemistry and Physics Division, Office of Research and Development,
Research Triangle Park, NC) and is for IBM or IBM compatible computers. Other
appropriately designed programs may be used to compile the data collected for any given
sampling network. It is not necessary to use a computer programmed integrator for the
computation of data, however, for large sampling networks, it is recommended.
17.42.1 Turn on the IBM XT computer. From the C:> prompt, type: cd/cchart, then
type: cchart. This loads the Chromatochart software. Turn switch on relay box to
ENABLE, indicator light could go on.
17.422 Press F2 to enter the methods development module. Select option number
1 - "select channel # and load method file." "Select channel # <0>" type 0 or press
ENTER to select the default choice shown in the brackets (in this case 0). "Load method
file named" type the name of the appropriate method, then press ENTER. A directory of
all of the current methods in memory can be obtained by pressing the F2 function key.
17.42.3 Press F3 to enter the Data Acquisition module. At this point you will be
asked to save the method file. If there has not been any changes to the methods file, it
does not need to be saved. Select option #4 - "Collect Data." Press ENTER to deactivate
the method queue. "Load Run Queue named," type the name of the run queue if one has
been created. Type ENTER to deactivate the run queue.
17.42.4 'Total # runs for method <1>," type how many times the method is to be
repeated (total number of samples). "Autoanalyze Data" type Y. "Autosave data to disc"
type Y. "Data file name (xxxxx) change?", type data file name. Tress ENTER to begin
methods." Press ENTER only after the samples have been loaded into the autosampler and
the baseline has stabilized.
17.42.5 Figure 18 illustrates the chromatograms for each of the samples as output by
the programmed Spectra-Physics integrator. The program used to generate these outputs
can be found in the Appendix of this method. Note that actual output is by individual run
as illustrated by Figure 19. Most information provided here is optional to the operator.
17.43 Calibration of 1C - The instrument should be brought to normal conditions with
a warm-up time of at least thirty minutes.
Revised 9/30/89 Page 26
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Method IP-9 Reactive Gases/Particulate Matter
17.4 J.I With the "Reading" light on, check to ensure the flow rate is 1.5 mLs/minute,
the fluid pressure is 600 psi ± 100 psi and the conductivity is constant as measured by offset
difference.
17.4.3.2 Fill the 1C vials with the prepared standard solutions and (10, 5 and 1 ppm
Na2SO4 and NaNO3) and pure eluent. This will allow a four-point calibration curve to be
made.
Note: For low-level applications, more standards and blanks may be necessary in order to
obtain accurate reference curves. .
17.4.33 Load the four vials into the sample vial holder, and place the holder in the
automated sampler tray. „„,„„„ „
17.43.4 The tray is controlled by a Spectra-Physics SP4200 or SP4270 Computer
Integrator. Use the integrators operation manual to begin calibrating. (A typical program
in Basic for integrators which illustrates integrator capability is shown in the Appendix of
this procedure). By using the RUN command the analysis and data treatment phases of the
calibration are set in motion. Four calibration standards are run, the chromatograms and
peak areas displayed for each run, and the run results for each anion are fitted to a
quadratic curve by a least squares regression calculation. The three curves are plotted and
the correlation coefficients are calculated. The values of the coefficients are normally
greater than 0.999, where 1.000 indicates a perfect fit. Values of less than 0.99 indicate the
calibration procedure should be repeated.
Note: Recalibration should be carried out whenever standard concentrations show
consistently high or low results relative to the calibration curve is compared to the
calibration curve from the old standard;. Comparability of points should be within ± 0.1
ppm or ± 10%. For standard concentrations of greater than 1 ppm, comparability will
normally be within 5% or better. Old standards are assumed correct since they are
referenced to the entire historical series of previous standard solutions all of which are
comparable.
17.4.4 System Shut-down
17.4.4.1 Shut off the pump. Turn the REGEN switch and the conductivity cell to the
OFF position.
17.4.42 Switch the eluent degas switch to HIGH.
17.4.43 Turn the stripchart recorder OFF, cap the pen. Press the F10 function key
on the computer. Select option 3, to exit to DOS. Shut off the printer and the computer.
17.4.4.4 Shut the eluent degas system and reservoir switches and :he autosampler to
the OFF position. Close the valves on both gas cylinders. Then close the regulator valves.
17.5 Basic Troubleshooting
Before proceeding with the troubleshooting guide, make sure that the reagents used were
prepared correctly, and are not "old."
Revised 9/30/89 Page 27
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Method IP-9 Reactive Gases/Particulate Matter
17.5.1 Unstable Baselines
17.5.1.1 Wavy baseline - The most common reason for a wavy baseline is an air
bubble in the gradient pump. This is diagnosed by observing the pump head indicator lights
on the gradient pump module front panel. If the baseline is pulsing in phases with pump
pistons, it usually indicates a bubble. Other possibilities include a dirty or stuck check
valve, piston seal or "O"-ring, as well as an air bubble in the conductivity cell.
17.5.13. Drifting baseline - Steadily increasing or decreasing baselines usually indicate
that the suppressor column is not performing as it should. Parameters to change include
the regenerant and eluent concentrations and flow rates. Check temperature routinely as
changes in temperature can cause drifting. Balancing these should stabilize the baseline,
if the suppressor is functioning correctly. The Dionex manual describes clean-up procedures
if the suppressor is believed to be contaminated.
17.5.1.3 High baselines - As with drifting baselines, the parameters to change are
eluent and regenerant concentrations and flow rates. A high baseline usually indicates that
there is not enough baseline suppression, this can be controlled by increasing the regenerant
flow rate. .
17.5.1.4 Low baselines - Low baselines usually indicate that there is too much
suppression. Oversupression can be controlled by decreasing the flow of the regenerant.
17.52 Backpressure - Variations in system backpressure are common and should not
raise concern UNLESS the pressure change is greater than 200 psi.
17.52.1 High backpressure - The system is protected from pressure related damage
through the high and low pressure alarm settings on the front panel of the gradient pump
module. If the high pressure setting is correctly selected (200 psi above normal operating
range), the pump will automatically shut-off if this value is exceeded. The reason for high
backpressure is that there is some kind of blockage in the system. Possibilities include:
loading against a closed valve; a plugged line; contaminated columns; etc. Diagnosis of the
problem is done by removing one component of the system and observing how the pressure
changes.
17.5.22 Low pressure - Low pressure readings usually indicate a leak somewhere m
the system. Carefully check all fittings for leaks, tighten if necessary.
17.53 Flow
17.5.3.1 Regenerant lines - If there is no flow at the waste outlet end of the
regenerant line, check the following:
• Make sure that the correct regenerant switch is turned on
• Verify that the reservoir is not empty
• Make sure the nitrogen tank is turned on
• Check that the regulator is correctly set
17.5.3.2 Eluent lines - If there is no flow at the outlet end of the eluent lines check
the following:
Revised 9/30/89 Pa8e 28
•-,
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Method IP-9 Reactive Gases/Particulate Matter
• Check that the pump is on
. Check that the eluent lines are connected to the correct port
17.5.4 Software - refer to the ChromatoChart manual for detailed information on
software problems.
18. Ammonia Analysis By Technicon Autoanalysis
Presented in Sections 18.1 and 18.2 are the recipes for the standards and reagents required
for the analysis of the ammonium ion (NH4+ - or ammonia (NH3)) by Technicon
autoanalysis. The prelude of these Sections briefly describes the TRAACS 800 autoanalyzer
and the sample flow through the TRAACS 800 for NH4+ analysis. The Technicon TRAACS
800 autoanalyzer is illustrated in Figure 20. This instrument is capable of quantifying, from
a single sample, three different species, simultaneously. An aliquot of the sample is taken
from an automated sampler by syringe. A splitter divides the aliquot into the appropriate
volumes required for the particular analyses. Each of the volumes is then transferred to
the appropriate analytical cartridge. Sample flow diagrams which illustrate SCv,, NO3 and
NH/ analysis can be shown separately and independently of one another. Hence, for a
one-channel system, one can readily adapt the sample preparation and analysis protocols
for each individual analysis. The data computation (by computer) and quality assurance
protocols, however, can not be readily adapted to single-channel instruments. These
protocols need to be specific to the individual analytical instrument. In brief, for NH4
analysis, Figure 21 illustrates how the sample is carried through the Technicon autoanalyzer.
The samples, along with all standards, are taken from the auto-advance sampler tray by the
use of a proportioning pump and automated syringe. Air and EDTA are first added to the
samples and are mixed in the first set of coils. After mixing, phenolate is added and mixed
in the next set of coils. Nitroprusside is then added and mixed, followed by the addition
and mixing of hypochlorite. At this stage, the sample should be a bright blue color. After
the last mixing stage, the sample is sent through a heated bath, followed by another mixing
stage. Finally the sample is sent through a colorimeter where the results are recorded on
a digital printer and stored in a computer file for further manipulation.
18.1 Standards and Stock Solutions Preparation
Note: Before discarding the old solution, it should be checked against the fresh solution
by comparing calibration curves on the working solutions prepared from them. Slopes and
intercepts are calculated for each set of standards. The old slope and intercept are used
to calculate concentration values from readings for the new standards. This determines if
the old solution has deteriorated or if an error has been made in preparing the new
solution.
18.1.1 Ammonium solution standard (1000 Mg/mL) - Dry ammonium chloride in an
oven for one hour at 50 to 60°C and desiccate over silica gel for one hour. Weigh 2.9470
g ammonium chloride and dissolve in 800 mL DDW. Dilute to one liter with DDW and
mix thoroughly. This solution is stable for one year.
Revised 9/30/89 Page 29
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Method IP-9 Reactive Gases/Particulate Matter
18.12 Intermediate ammonium standards - To make a 100 /Jg/mL ammonium standard,
pipet 10 mL of ammonium stock standard into a 100 mL volumetric flask. Dilute to volume
with DDW and mix thoroughly. Keep refrigerated. This solution remains stable for one
month. To make a 10 /Jg/mL ammonium standard, pipet 1.0 mL of ammonium stock
standard into a 100 mL volumetric flask. Dilute to volume with DDW and mix thoroughly.
This solution remains stable for one week.
18.13 Working ammonium standards in DDW - Pipet aliquots of the 100 /zg/mL
ammonium intermediate standards with appropriate volumes of nitrate and sulfate
intermediate standards into 100 mL volumetric flasks according to the table below. Dilute
to volume with DDW. Prepare fresh daily.
Stock or
Intermediate
Standard Aliquot Concentration
Standard (ag/mL) (mL) Qg/mL)
A 1000 40.0 40.0
B 100 4.0 4.0
C 100 3.0 3.0
D 100 2.0 2.0
E 100 1.0 1.0
F 100 0.5 0.5
G 10 2.0 0.2
H 10 1.0 0.1
18.1.4 Sodium citrate stock solution - Dissolve 294.1 g of sodium citrate in 800 mL
DDW. Dilute to 1 liter and mix thoroughly. Store at room temperature.
18.1.5 20% citric acid/5% glycerol stock solution - Dissolve 25 g citric acid in 80 mL
DDW. Add 5 mL glycerol and dilute to 100 mL with DDW. Mix thoroughly and store at
room temperature.
18.1.6 Sodium citrate/citric acid/glycerol working solution - Put 100 mL sodium citrate
stock solution into a 1000 mL volumetric flask. Add 20 mL of the 10% citric acid/5%
glycerol stock solution and dilute to volume with DDW. Mix thoroughly and store at room
temperature. . .
Note: This solution will be used to make up ammonium working standards for citric
acid/glycerol-impregnated filter extract analyses.
18.1.7 Working ammonium standards in sodium citrate/ citric acid/glycerol working
solution - Pipet aliquots of the 100 /tg/mL volumetric flasks according to the table in
Section 18.1.1.3. Dilute to volume with sodium citrate/citric acid/glycerol working solution
and mix thoroughly. Prepare fresh daily.
18.1.8 Potassium chloride stock solution - Dissolve 74.6 g potassium chloride in 800 mL
DDW. Dilute to one liter with DDW and mix thoroughly. Store at room temperature.
18.1.9 Potassium chloride working solution - Put 100 mL of the potassium chloride stock
solution into a 1000 mL volumetric flask. Dilute to volume with DDW.
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Method IP-9 __ Reactive Gases/Particulate Matter
18.1.10 Working ammonium standards in potassium chloride working solution - Pipet
aliquots of the 100 ng/rnL ammonium stock standard or intermediate standards into 100
mL volumetric flasks according to the table below. Dilute to volume with potassium
chloride working solution and mix thoroughly. Prepare fresh daily.
Stock or
Intermediate
Standard Aliquot Concentration
Standard (ug/mLI (mL) Og/mL)
A 1000 40.0 40.0
B 100 4.0 4.0
C 100 3.0 3.0
D 100 2.0 2.0
E 100 1.0 1-0
F 100 0.5 0.5
G 10 1.0 0.1
H 10 0.5 0.05
18.2 Reagent Preparation
Note: When reagents are prepared, label the container with the contents, concentration,
date prepared, and the preparer's initials.
182.1 Alkaline phenol - To 800 mL DDW in a one liter volumetric flask, add 83.0 g
loose crystallized phenol. Keeping the flask in anice bath or under tap water, slowly add
96 0 mL 50% sodium hydroxide solution. Shake the flask while adding the sodium
hydroxide. Cool to room temperature, dilute to one liter with DDW and mix thoroughly.
Store in an amber glass container. This solution remains stable for three months, if kept
out of direct light.
18.2.2 Sodium hypochlorite solution - The amount of sodium hypochlonte solution vanes
from batch to batch of sodium hypochlorite (5% commercial grade). Therefore, for each
new batch, a base and gain experiment must be run to adjust the amount of sodium
hypochlorite required to obtain the existing base and gain values. In a 150 mL volumetric
flask, dilute 86 mL of 5% sodium hypochlorite solution to 100 mL with DDW and mix
thoroughly. Check base and gain values. Reduce or increase the amount of sodium
hypochlorite to obtain the same base and gain values as the previous sodium hypochlonte
batch. This solution remains stable for one day. .
1823 Sodium nitroprusside solution - Dissolve 1.1 g of sodium nitroprusside in about
600 mL of DDW, dilute to 1 liter with DDW and mix thoroughly. Store in an amber
container, and keep in refrigerator. This solution remains stable for one month, if kept out
of direct light. , ,.,,.-, j
182.4 Disodi&2um EDTA solution - Dissolve 1.0 mL of 50% w/w sodium hydroxide and
41.0 g of disodium EDTA mix thoroughly. Add 3.0 rnL of Brij-35 and mix. Store in plastic
container. This solution remains stable for six months.
Revised 9/30/89 Pa§e 31
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Method IP-9 Reactive Gases/Particulate Matter
19. pH Analysis
19.1 Standard and Reagent Preparation
19.1.1 Standard H2SO4 Solution
Note: Each of the standard H2SO4 stock solutions must be prepared fresh the day of pH
analysis.
19111 Label seven 25 mL polyethylene stoppered volumetric flasks. Also, label
each flik with the volume of 1 N H2SO4 solution indicated in the following table:
Volume of IN Stock Standard Concentration
(flL)
1 0 0
2 25 1
3 50 2
4 100 4
5 200 8
6 400 16
7 800 32
19.1.12 Use the 25 fiL automatic pipet to add 1 N stock H2SO4 to flasks #1-3. Use
the 100 t£L pipet to add 1 N stock H2SO4 to flasks #4-7. Dilute all flasks to the 25 mL
mark with absolute ethanol. Cap with stoppers or parafilm and mix well.
19.12 2 M Potassium Chloride (KC1) Solution
19.12.1 Weigh 149.2 ± 0.1 g of KC1. Add the KC1 to a 2 L flask.
19.122 Add about 700 mL of DDW water to the flask. Swirl the solution until the
KC1 is completely dissolved. , „ , • u n
19123 Pour this mixture into a 1 L graduated cylinder. Rinse the flask with a small
amount of water and transfer the rinse into the cylinder. Fill the cylinder to the 1 L mark.
19.12.4 Pour the solution from the cylinder into the 1 L polyethylene bottle. Cap
and shake the bottle to mix well. Mark the bottle with date of preparation.
19.1.3 0.1 N Perchloric Acid (HC1O4) Solution
19.13.1 Fill a 1 L graduated cylinder about 1/2 full with DDW. Transfer 10 ± 0.1
mL of 60-62% HC104 into the 1 L cylinder with a 10 mL pipet.
19.132 Fill the cylinder to the 1L mark. Pour the solution into the 1L polyethylene
ei9.133 Cap and shake the bottle to mix well. Mark the date of preparation on the
bottle.
19.1.4 0.01 N HC1O4 Solution
19.1.4.1 Fill a 1 L graduated cylinder about 1/2 full with DDW.
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Method IP-9 Reactive Gases/Particulate Matter
19.1.4.2 Measure 100 mL of the 0.1 N HC1O4 solution with the 100 mL graduated
cylinder. Add this to the 1 L cylinder. . .
19.1.4 J Fill a 1 L cylinder with DDW to the 1 L mark. Pour the solution into the
1 L polyethylene bottle. .
19.1.4.4 Cap and shake the bottle to mix well. Mark the date of preparation on the
bottle.
19.1.5 Extraction Solution (ES)
Note: This solution has the same composition as the solution used to fill the sample vials
for Teflon* filters. It must be prepared fresh on the day of pH analysis.
19.1.5.1 Measure 100 ± 10 mL of DDW into a 1 L graduated cylinder. Transfer to
a 2 L erlenmeyer flask.
19.1.52 Using a 5 mL calibrated automatic pipet, add 10 ± 0.1 mL of 0.01 M
perchloric acid (HC1O4), to flask of water.
19.1.53 Mix well and cover with parafilm until ready for use.
19.1.6 EA Solution
19.1.6.1 Measure 150 ± 2 mL of ES (prepared in 18.1.5) into a 250 mL graduated
cylinder. Transfer to a 250 mL erlenmeyer flask.
19.1.62 Using a 5 mL graduated cylinder, add 5 ± 0.1 mL of ethanol (this must be
from the same fresh bottle of ethanol that was used to prepare the standards in 18.1.1) to
19.1.6.3 Again using a 5 ir,.. graduated cylinder, add 3 ± 0.1 mL of 2 M potassium
chloride (KC1) solution to the flask.
19.1.6.4 Mix well and cover with parafilm until ready for use.
19.1.7 Working Standard Test Solutions
19.1.7.1 Place fourteen-4 mL polystyrene sample cups (as used with Technicon
Auto-Analyzer II system) labeled 1, 1*. 2, 2*...7, T into racks. Using the calibrated
dispensing pipet bottle, add 3 mL of ES solution to each 4 mL cup.
19.1.72 Using the displacement pipet, add 50 uL of absolute ethanol to each cup.
Pour about 3 mL of standard (H2SO4 solution) #1 into a labeled 4 mL cup.
19.1.7 J Immediately, pipet 50 uL of this standard into the 4 mL cups labeled 1 and
1* containing the ES solution and ethanol.
Note: This transfer must be done without delay to prevent the standard concentration
from increasing significantly due to evaporation of the ethanol solvent.
19.1.7.4 Repeat the procedure for each of the other 6 standards. If there is a delay
of more than 5 minutes between the preparation of these mixtures, and the next step, put
caps on the 4 mL cups. .
19.1.7.5 To prepare for analysis, each must be mixed, then two ahquots from each
cup are transferred to 2 mL sample cups. Place cup #1 in a rack. In a second rack place
two-2 mL cups labeled 1 and 1-. Use the 1 mL automatic pipet to mix the contents of 4
mL cup #1 by drawing 1 mL into the pipet tip and then dispensing it back into the 4 mL
Revised 9/30/89 " ~~~~
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Method IP-9 Reactive Gases/Particulate Matter
cup three times. Then use the same pipet to transfer 1 mL of the mixture to each of the
two labeled 2 mL cups. Place caps on the two 2 mL cups. After transferring the two
aliquots to 2 mL cups, rinse the automatic pipet tip in a flask of DDW. Repeat the transfer
procedure for each of the other working standard pairs.
19 2 Calibration of pH Meter
The pH meter requires temperature calibration whenever a new electrode is used. Use the
manufacture's procedure in the instrument manual. This calibration should be repeated
every three months while not in use. The pH meter is left with the power cord plugged
into the AC outlet, the mode control knob is left in the standby position, the electrode lead
is partially disconnected by pressing the plastic ring on. its outer edge, and the combination
electrode is immersed in a 4 M KC1 solution (a slit rubber stopper seals the bottle with the
electrode in it). Keep a record of the temperature calibrations in a lab notebook.
19.3 Pre-Analysis Calibration
19 J.I Use pH lab analysis log form 418 to record all date. While still in standby mode,
reconnect the electrode lead at the back of the pH meter.
1932 Fill three 4 mL cups with pH 7 buffer. Withdraw the electrode from the 4 M
KC1 bottle and wipe the tip gently with a Kimwipe® to remove the bulk of the solution.
Rinse the electrode with one cup of pH 7 buffer. Do not test pH of the first cup.
19.33 Immerse the electrode in the second cup of the pH 7 buffer. Use a small bottle
or other support to hold the cup up to the electrode while waiting for the meter reading
to equilibrate.
19.3.4 Test the pH by turning to the pH mode of the meter. Allow the reading to
stabilize for at least 30 seconds. Record the result on the log for "1st cup."
19.3.5 Turn to standby mode, and then test the last cup of pH 7 buffer. Record the
results on the log for the "2nd cup." If the pH value for the 2nd cup is not 7.00 ± 0.01,
adjust the "calib." knob to obtain a reading of 7.00. Note this adjustment on the log.
193.6 Fill three 4 mL cups with pH 4 buffer. With the meter in the standby mode,
remove the cup containing pH 7 buffer, wipe the tip of the electrode gently with a
Kimwipe*, and then rinse the electrode with the first cup of pH 4 buffer.
19.3.7 Test the next two cups of pH 4 buffer as above, recording the results on the log.
If the pH value for the 2nd cup is not 4.00 ± 0.01, adjust the "slope" knob to get a reading
of 4.00. If the value for the second cup was not 4.00 ± 0.03, the calibrations at pH 7 and
at pH 4 must both be repeated.
19.4 pH Test 0.01 N HC1O4 Solution
Note: The 0.01 N HC1O4 solution is used to prepare the ES solution which, in turn, is used
to prepare the EA solution. It is imperative that the pH value for the EA solution be 4.09
± 0.04. If this pH value is not achieved, then the 0.01 N HC1O4 solution must be
reprepared.
19.4.1 Calibrate the pH meter with pH 4 buffer.
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Method IP-9 Reactive Gases/Particulate Matter
19.42 Rinse the pH electrode with DDW. Wipe the tip of the electrode with a
19.4.3 fill three 4 mL cups with EA solution. Measure the pH of the test EA solution
as with the buffer solutions this value must be 4.09 ± 0.04.
19.4.4 If the above pH value is not achieved, follow the steps 18.1.3 -18.1.6 to reprepare
the solutions. Test the pH of the new solutions. Repeat as necessary to obtain a pH of
409 ± 004
19.4.5 Leave the electrode immersed in the "2nd cup" with the meter in the standby
mode until ready to start analysis of the working standards.
19.5 Analysis of Working Standard
Note: Immediately following the EA analysis, start testing the working standards.
19.5.1 With the pH meter still in the standby mode, remove the last cup from the
electrode, gently wipe the tip with a Kimwipe*, and then immerse the electrode into the
working standard cup #1. / , r r-i * \
Note: Only two cups are available for each working standard (also for filter extracts;.
Thus, pH measurement is made for both of the two cups for each sample. Also, the
electrode tip is not wiped between the 1st and 2nd cups of each sample.
.19.52 After testing the pH of cup #1, test cup #1-. Record the results of both on the
log sheet. . ,
19.53 With the meter in the stand-by mode, remove the #1- sample cup, wipe tne
electrode with a Kimwipe* and test one 2 mL cup of EA solution, rinse with DDW.
19.5.4 Test a 2nd cup of EA solution; record the results for both cups on the logsheet.
Discard the 1st cup of EA, but retain the 2nd cup to be used as the 1st cup for the next
EA test
19.5.5 Continue testing the remainder of the working standards, #1*, 1*-, ... 7, 7-, 7*,
7*-. Remember that the electrode tip is wiped both before and after each pair of test
solutions, but not in between two cups of the same sample.
Note: If there is trouble in obtaining constant pH values, it may be necessary to use a
magnetic stirrer to keep the contents to be measured uniform. If employed, ensure that
the sample cups are insulated from any temperature increase of the stirring platform which
may occur during extended use.
19.5.6 Use the mode control knob in the "temp." position to measure the temperature
of the test solutions every 5-10 samples and record the results on the logsheet.
19.6 Analysis of Filter Extracts
Following measurement of the pH of the working standards, measure the pH of the filter
extracts and record all results on the log. After all the filter extracts have been tested make
an additional test with the EA solution. At the end make a final test of pH 4 buffer. With
the mode control in the standby mode, shut down the pH meter by disconnecting the
electrode lead at the back of the meter, leaving the meter power cord plugged into the AC
line. Immerse the electrode tip in the bottle of 4 M KC1.
Revised 9/30/89 Pa8e 3S
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Method IP-9 Reactive Gases/Particulate Matter
20. Atmospheric Species Concentration Calculations
The system described in the previous sections collects nitric acid (HNO3), nitrous acid
(HNO2), sulfur dioxide (SO2), ammonia (NH3) particulate sulfate (SO4°), and particulate
nitrate (NO3~). Figure 1 illustrates the collection of each of these species. Nitric acid and
sulfur dioxide gases are collected on denuders one and two. Some SO2 gas is collected on
denuder three also. Nitrous acid gas is collected on denuders two and three. Ammonia
gas is collected on denuder four. Particulate sulfate and nitrate are collected on the first
(Teflon)* filter, while some of the particulate nitrate collected on the Teflon* filter can
evaporate and be collected on the second (nylon) filter. Also collected on the Teflon* filter
are fine particles which contain hydrogen ions (H+), though probably not free H^
Hydrogen ions are most likely present in the H3O+ form. The concentration of these H+
ions indicates the atmospheres acid aerosol content. It is necessary to prepare the Teflon*
filter extracts for pH analysis prior to 1C analysis for the particulate sulfate contents.
Special precautions must be taken to prevent contamination of the Teflon* filters by
ammonia before either of the analyses.
20.1 Assumptions of the Annular Denuder System
There are a number of assumptions which are made about performance of the annular
denuder system in order for validity of the calculations to be presented later in this section
to hold true. As discussed in Section 6, there are significant interferences which need to
be considered in order for accurate estimations of species concentrations to be made. The
assumptions are as follows:
• The first denuder stage collects 100% of sampled HNO3 as nitrate. (Since the
diffusivity of HNO3 is high, diffusion to the side walls is assumed to be very quick.)
• The second denuder stage collects 100% of sampled HNO2 as nitrite, which can oxidize
to nitrate.
• The first and second denuder stages together collect 100% of the SO2 as sulfite, which
can oxidize to sulfate.
Note: Before analysis, it is recommended to add hydrogen peroxide (H2O2) to oxidize
the sulfite (SO3~) to sulfate (SO4=) to simplify the calculations.
• The amounts of nitrite and nitrate collected on denuder 3 (d3) represent amounts of
interfering gases such as NO2 collected on denuder 2 (d2).
• The fourth denuder stage collects 100% of the sampled ammonia (NH3) as ammonium
ion (NH4+).
• The Teflon* filter (fl) is 100% efficient for particulate sulfate, nitrate and ammonia.
Particle losses are less than 1% on each denuder. This assumption may or may not
stand true depending on the concentrations of the components in the air sampled.
Modifications may be needed to avoid low (or underestimates of) acidic measurements.
For example, it may be necessary to add another filter stage to more accurately account
for the particulate ammonia content of the air sampled. If ammonium nitrate
(NH4NO3) was collected on the Teflon* filter, its probability of evaporation is high.
Therefore, a citric acid-impregnated filter downstream would correct for the loss from
the Teflon* filter. Also, interaction of ammonia and sulfuric acid neutralizes the filter
Revised 9/30/89 Page 36
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Method IP-9 Reactive Gases/Particulate Matter
and causes the acidic measurement to be biased. (Again diffusion rules the particle
loss assumption; particles have lower diffusivities than gases).
. The nylon filter (£2) collects any nitrate that evaporates from the Teflon* filter (fl).
202 Calculations Using Results from 1C Analysis
These assumptions lead directly to equations for computing atmospheric concentrations
from denuder measurements.
202.1 Figure 22 illustrates the equation for nitric acid quantification. In this equation,
C (HNCO is the concentration of nitric acid gas expressed in ng/m . Subscript g denotes
"gas" The computation depends on NO3' (dl), which is the measured amount nitrate in
lie collected on denuder 1. The factor 1.016 represents the ratio of molecular weights of
HNO, and NO,'. In the denominator, V is the sampled air volume expressed mm .
2022 Figure 23 illustrates how the concentration of nitrous acid is deduced. The
numerical factors 1.022 and 0.758 (both in 0g) are used to convert the measured nitrite and
nitrate to equivalent amounts of nitrous acid. Measured nitrate has to be included because
some of the collected nitrite may oxidize to nitrate during sampling or during sample
storage Because a small portion of NO2 may be collected on denuders 2 (d2) and 3 (d3),
the nitrite and nitrate amounts measured on denuder 3 (d3) represent corrections for NO2
and other interfering gases. .
202.3 Figure 24 illustrates how sulfur dioxide concentrations are deduced. Because
sulfur dioxide is collected on both stages dl and d2, the results for both stages are added.
To simplify the calculation, oxidize the collected sulfite to sulfate by adding H2O2to the
sample vial. Hence, the quantification of SO4= gas directly estimates sulfur dioxide. A more
complicated equation would result if the collected sulfite had not been fully oxided to
sulfate. Sulfate measurements are expressed in mg. Sulfur dioxide concentrations are
expressed in mg/m3. . .
202.4 Figure 25 illustrates the equation for ammonia quantification. Ihe numerical
factor 0944 is used to convert the measured ammonium ion to its equivalent amount ot
ammonia. Therefore the product of the factor and the NH4+ collected by d4 directly
estimates the ammonia concentration (C (NH3)).
202.5 Figure 26 illustrates how paniculate sulfate concentration (Cp(SO4 ) is computed.
The subscript p denotes "particle." This formula expresses the assumption that essentially
all of the paniculate sulfate is collected on the Teflon* filter (fl), and no evaporation
occurs.
L.U15. . , TTiic
202.6 Figure 27 shows how paniculate ammonium concentration is computed, mis
formula expresses the assumption that essentially all of the paniculate ammonia is collected
on the Teflon* filter (fl), and no evaporation occurs.
202.7 Figure 28 illustrates how the paniculate nitrate concentration is computed. Ihis
equation is similar to the one for sulfate except that nitrate measured on the nylon filter
(£2) must be included because nitrate collected on the Teflon* filter (fl) can evaporate.
Note- It is important to note that four of the measurements are not used. For example,
sulfate measured on the nylon filter represents a sulfate blank for nylon that is irrelevant
to sulfate collected on Teflon*. Also, nitrite collected on the nylon filter represents the
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Method IP-9 Reactive Gases/Particulate Matter
possibility that some NO2 is collected on the nylon filter, but that is not relevant to the way
that nitrate is determined in the denuder system. The remaining unused data represent low
concentrations and are also not relevant to deducing the concentrations of the atmospheric
species considered here.
20.3 Estimates of Errors In Concentrations Deduced From Denuder Data
Note: The assumptions and formulas used to calculate the uncertainty of the measurements
are illustrated in Section 20.3.3.
20.3.1 Figure 29 shows the formula used for the uncertainty in paniculate sulfate. It
includes errors in measuring sulfate and in deducing the air-volume sampled. It also
includes a 3% error to account for the possibility of 1% particle loss in each of the three
denuder stages. Error equations for the other species are shown in Section 20.3.3.
20.3.2 Assumptions on which error equations are based:
• X is the measurement error for species X.
• Measurement errors are random and uncorrelated among species.
• Possible particle-losses of 1% in each denuder introduces an overall uncertainty of
+ 3% for paniculate sulfate and nitrate concentrations.
• Gases such as H2S and CH3HS can be collected on the denuder stages, and bias the
results. Amounts collected on denuder stage 3 can be used to estimate the
uncertainties that result from such bias. Thus, SO4=(d3) is an estimate of the
uncertainty in the amount of SO2 collected on denuders 1 (dl) or 2 (d2).
20.33 Error equations:
For SO4=:
[5Cp(S04-)/Cp(S04=)]2 = [6S04=+(fl)/S04-+(fl)]2 + [0.03]2 + [6V/\f
For N03':
[6Cp(N03-)/Cp(N03-)]2 - [N03'(fl) + N03-(f2)] + [0.03]2 + [5V/V]2
For HNO3 and HNO2:
[5Cg(HN03)/Cg(HN03)]z = [SNCV(dl)/NCV(dl)]2 + [5V/V]2
[6Cg(HN02)/Cg(HN02)]2 = [6A/(VCg(HNO2)]2 + [6V/V]2
where:
A2 = (1.022)2 [6N02-(d2)2 + NCV(d3)2] + (0.758)2 [«NCV(d2)2 + NCV(d3)2]
20.4 Calculations Using Results from pH Analysis
Earlier determinations of pH have been based on the pH buffer concentrations, the activity
of the solution, and the antilog of the measured pH value. More recent studies have
steered away from the issue of activity by comparing the results of the standards, thus,
alleviating errors introduced by basing the activities of ions retained on filters on those
Revised 9/30/89 P^geli
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Method IP-9 Reactive Gases/Particulate Matter
retained in solution. The methodology developed from these more recent studies is
described herein. The end results are reported in terms of mass of equivalent of ions.
Appropriate values of accuracy and precision with respect to IT concentration for this
method are 10% and 5%, respectively, for sample pH values in the 4.00 to 7.00 range.
20.4.1 Summary of method - There are two parts to this methodology, determination of
the "nominal EQ," and determination of the "actual (EQN)." The nominal EQ * defined
as the equivalent /Jg H2SO4/m3 for a nominal 5.76 m3 sample volume (24 hours at 4 LPM).
The actual EQA is defined as the equivalent fig H2SO4/m3 based on the actual sample air
volume.
20.4.1.1 Determine the nominal EQN as follows:
20 411.1 To account for the difference between standards prepared with filters and
standards prepared without filters, adjust the measured concentration values for the working
standards (without filters) for each analysis day. .
20.4.1.12 Calculate the standard curve, using a linear regression of the equivalent
of v% H2SO4/m3 (for 5.76 m3 volume of sample) for each working standard vs the adjusted
concentration values for the working standards.
20.4.1.13 Use the standard curve to determine EQN for each sample inter.
20.4.1.1.4 Calculate the actual air flow rate to determine the actual air sample
volume. Divide the actual air sample volume into EQN to determine EQA.
20.4.1.2 Determine the actual EQA as follows:
20.4.12.1 The actual sample air volume, V, for each sample is calculated using data
from the field log sheet. This data includes the initial and final elapsed time, the initial
rotameter reading, and the rotameter I.D. No.
20.4.12.2 The calibration curve for the given rotameter reading is used to calculate
the flow for the sample (LPM). .
20.4.123 The nominal EQN is divided by the calculated flow to give the actual EQA.
20.42 Adjustment for filter vs. non-filter standards - This adjustment is necessary
because experiments showed that the measured acid concentration from filters doped with
H,SO4 stock standards yielded concentrations, as measured by the difference from EA
solution, which were about 3% lower than the values found for working standards (prepared
without filters from the same stock standards). The results gave the following relation (by
linear regression):
Cf = - 0.11 + 0.971 (Cnf) C1)
where*
Cf = difference in units of 10'5 N, calculated using the pH of each filter standard and the
pH of EA tested after that standard
Cnf = the same difference for non-filter standards (or the apparent net (strong acid
concentration of H2SO4)
Revised 9/30/89 Pase 39
A
70
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Method IP-9 Reactive Gases/Particulate Matter
For each working standard (non-filter), on a given analysis day, calculate the "apparent net
concentration of H2SO4" as follows:
- 1(TPHEA (2)
nf =
where:
pHWS = measured pH for a working standard (or apparent strong acid concentration for
H2SO4 - doped filter standards)
pHEA = measured pH for the EA solution (or apparent strong acid concentration for
non-filter, non-H2SO4 doped standards)
After calculating the Cnf values for each working standard, use equation (1) above to
calculate the adjusted values of Cf for each.
20.43 Determination of standard curve - For each working standard, the corresponding
EQN value (the equivalent of jig H2SO4/m3 [assuming a sample volume of 5.76 m ]) is
determined as follows:
EQN = m/5.76 (106 jig)/g (3)
Note: 5.76 is the volume for a sample collected for 24 hours at 4 LPM, in m3.
Note: It is the analyst's preference as to whether concentration or mass is calculated here
and used to create the standard curve. If mass is used, a nominal sample air volume is not
necessary. The value of m is determined as follows:
m = [1.000] [S/25] [5 x 10'5] [49] (4)
where:
1.000 = concentration of the commercial standard H2SO4, in units of
equivalents/L
S = volume of commercial standard H2SO4 used to prepare a given stock
standard solution, mL
25 = volume of each stock standard solution, mL
5 x 10"5 (50 uL) = is the volume of each stock standard solution used to prepare its
respective working standard, L
49 = equivalent weight of H2SO4, units of grams/equivalent
Note: When the value of S is 1 mL or greater for a final volume of 25 mL, the standard
curve illustrates non-linearity. This is due to incomplete dissociation of bisulfate. An
example table of the values of the nominal EQN for each working standard is shown in
Table 3. For each analysis day, the standard curve should be determined by calculating the
linear regression of EQN vs. Cf, with the result in the following equation:
EQN = intercept + [Cf] [slope] (5)
20.4.4 Determination of nominal EQN for filter samples - The apparent net strong acid
concentration of each sample filter extract, Cs, is calculated as with the working standards:
Cs = 10'pHS - 10-pHEA (6)
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Method IP-9 Reactive Gases/Particulate Matter
= measured pH of the sample filter extract (or apparent strong acid concentration
for sample filters extracts) .
pHEA = measured pH for the EA solution (or apparent strong acid concentration for
non-filter, non-H2SO4 standards)
Note- The C values for the filter extracts are directly comparable to the Cf values tor tne
working standards, since the Cf values have been adjusted for the ditferencem Apparent
acid concentration for tests made with filters and tests made without filters. Therefore, to
determine the nominal EQN values for filter samples, use equation (5) transformed as
follows:
EQN = Intercept + [Cs] [Slope] CO
20.4.5 Determination of actual EQA - The actual sample air value V, for each sample
is calculated using the data from the field log sheet. These data includes the.initial and
final elapsed times, the initial rotameter reading, and the rotameter I.D. No. Use the
calibration curve for the given rotameter to calculate the flow for the sample, in LPM.
Calculate the value of V as follows:
V = [F][TJ (8)
where:
F = flow from the calibration curve, LPM
T = net elapsed time, min
Since the nominal EQN values were determined assuming a flow of exactly 4 LPM and a
net elapsed time of exactly 24 hours, the assumed volume was 5.76 m3, therefore, calculate
the value of the "actual EQA" by:
EQA = [EQN]/V (9)
where:
EQA = units of 0g/m3
Nominal EQN as determined by Equations 3 and 4:
EQN = m/5.76 (106 /Jg/g)
where: ..
m = [1.000] [S/25] [5 x 10'5] [49] . .
1000 = concentration of commercial standard H2SO4, units of equivalents/L
s' = volume of commercial standard H2SO4 used to prepare a given stock
standard solution, mL
25 = volume of each stock standard solution, mL
5 x 10"5 (50 uL) = volume of each stock standard solution used to prepare its respective
working standard, L
49 = equivalent weight of H2SO4, units of grams/equivalent
Revised 9/30/89 Page 41
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Method IP-9 Reactive Gases/Particulate Matter
Working Standard S M EQN
# (mL) £g) fug/m3)
1 0.000 0 0.00
2 0.025 2.45 0.43
3 0.050 4.9 0.85
4 0.100 9.8 1.70
5 0.200 19.6 3.40
6 0.400 39.2 6.81
7 0.800 78.4 13.61
8 1.600 156.8 27.22
21. Variations of Annular Denuder System Usage
As mentioned in Section 3 and Section 4, the ADS as described previously, is used to
measure reactive acidic (SO2, HNO2 and HNO3) and basic (NH3) gases and particles found
in indoor air. The unique features of the ADS which separates it from established air
monitoring methods are the ability of sampling artifacts to be eliminated from the collected
gases and particles, and the preservation of the samples for subsequent analysis which is
accomplished by removing NH3 in the gas stream with a citric acid coated denuder, thus
reducing the probability of the paniculate acid sulfates (SO4*) captured on the Teflon®
filter from being neutralized. The ADS configuration described in Section 13 clearly
illustrates these unique features. The elutriator is designed to allow only particles with
<2.5 jim diameter into the system. The impactor is designed to reduce the possibility of
coarse particle infiltration even further. And finally, the sequence of the denuders reduces
interference of possible chemical reactions which could cause under-or over-estimations of
concentrations to be made. Although this configuration is recommended for measuring
these gases and particulates, it may be in the interest of the user to measure only one or
two of the chemical species. The following discussion will present possible variations of the
ADS to accommodate such usages.
21.1 Today, the ADS is being used in intercomparison studies to assess NH3 concentration
differences indoors and outdoors. The assembly used here consists of an elutriator-impactor
assembly, an annular denuder and a filter pack assembly. The elutriator-impactor assembly
and the annular denuder are both smaller than those described earlier. The filter pack is
available in the smaller size, but an adaptor is also available to assemble the smaller
annular denuder to the larger filter pack assembly. This system is referred to as the
personal sampler (see Figure 30). It is designed for sampling while attached to the shirt
of a worker. The personal sampler can be used to measure other chemical species in
indoor air by simply changing the reactive surface (coating) of the annular denuder and or
by changing the types of filters used.
21.2 Another variation of ADS application is simultaneous use in parallel with a fine
particle sampler. The fine particle sampler assembly is very similar to the annular denuder
assembly. The main difference is that a flow-straightener tube replaces the annular
denuder. The flow-straightener is a shorter version, 1-1/4 to 4 inches long, of the annular
Revised 9/30/89 " Pa8e 42
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Method IP-9 Reactive Gases/Particulate Matter
denuder and serves to create even air flow across the filters for the collection of paniculate
matter. Figure 31 illustrates an exploded view of the fine particle sampler. Again the
elutriator-impactor assembly and flow-straightener are available in smaller sizes with
accommodating filter pack assemblies. In addition, the ADS carrying and shipping cases
as well as the sampling box can be adjusted to accommodate the ADS and fine particle
sampler. Figure 32 illustrates the assemblies as they would appear in the sampling box
ready for sampling.
22. Method Safety
This procedure may involve hazardous materials, operations, and equipment. This method
does not purport to address all of the safety problems associated with its use. It is the
user's responsibility to establish appropriate safety and health practices and determine toe
applicability of regulatory limitations prior to the implementation of this procedure. This
should be part of the user's SOP manual.
23. Performance Criteria and Quality Assurance (QA)
Required quality assurance measures and guidance concerning performance criteria that
should be achieved within each laboratory are summarized and provided in the following
section.
23.1 Standard Operating Procedures (SOPs)
23.1.1 SOPs should be generated by the users to describe and document the following
activities in their laboratory: 1) assembly, calibration, leak check, and operation of the
specific sampling system and equipment used; 2) preparation, storage, shipment and
handling of the sampler system; 3) purchase, certification, and transport of standard
reference materials; and 4) all aspects of data recording and processing, including lists ot
computer hardware and software used.
23.1.2 Specific stepwise instructions should be provided in the SOPs and should be
readily available to and understood by toe personnel conducting toe monitoring work.
232 Quality Assurance Program
The user should develop, implement, and maintain a quality assurance program to ensure
that toe sampling system is operating properly and collecting accurate data. Established
calibration, operation, and maintenance procedures should be conducted on a regularly
scheduled basis and should be part of toe quality assurance program. Calibration
procedures provided in Sections 17 and 19, operation procedures in Sections 14 and 17, and
maintenance procedures in Section 17 of this method and toe manufacturer's instruction
manual should be followed and included in the QA program. Additional QA measures
(e g trouble shooting) as well as further guidance in maintaining the sampling system are
provided by toe manufacturer. For detailed guidance in setting up a quality assurance
program, toe user is referred to toe code of Federal Regulations (12) and the bFA
Handbook on Quality Assurance (13).
Revised 9/30/89 Pa8e 43
-------
Method IP-9 Reactive Gases/Particulate Matter
24. References
1. Waldman, J. M., Operations Manual for the Annular Denuder System Used in the
USEPA/RIVM Atmospheric Acidity Study, UMPNJ - Robert Wood Johnson Medical
School, Piscataway, NJ, August 28, 1987.
2. American Chemical Society Subcommittee on Environmental Chemistry, "Guidelines for
Data Acquisition and Data Quality Evaluation in Environmental Chemistry," Analyt. Chem.,
52:2242-2249, 1980.
3. Sickles, II, J. E., "Sampling and Analytical Methods Development for Dry Deposition
Monitoring," Research Triangle Institute report no. RTI/2823/00-15F, Research Triangle
Institute, Research Triangle Park, NC, July 1987.
4. Forrest, J., and L. Neuman, "Sampling and Analysis of Atmospheric Sulfur Compounds
for Isotopic Ratio Studies," Atmos. Environ., 7:562-573, 1973.
5. Stevens, R. K., et al., Abstract for ACGIH Symposium: on Adran COS in Air Sampling,
"Inlets, Denuders and Filter Packs to Measure Acidic Inorganic Pollutants in the
Atmosphere," Aislomer Conference Center, Pacific Grove, CA, February 16, 1986.
6. Appel B. R., Povard V., and Kothney E. L., "Loss of nitric acid within inlet devices for
Atmospheric Sampling," Paper presented at 1987 EPA/APCA Symposium: Measurement
of Toxic and Related Air Pollutants, Research Triangle Park, NC, 3-6 May 1987.
7. Braman R. S., Shelley T. J., and McClenny W. A., Tungstic Acid for Preconcentration
and Determination of Gaseous and Paniculate Ammonia and Nitric Acid in Ambient Air,"
Analyt. Chem., 54:358-364, 1983.
8. Perm, M., "Concentration Measurements and Equilibrium Studies of Ammonium, Nitrate
and Sulphur Species in Air and Precipitation," Doctoral Thesis, Department of Inorganic
Chemistry, Goteborg University, Goteborg, Sweden, 1986.
9. Perm, M., and Sjodin A., "A Sodium Carbonate Coated Denuder for Determination of
Nitrous Acid in the Atmosphere," Atmos. Environ., 19:979-985, 1985.
10. Riggin, R. M., Technical Assistance Document for Sampling and Analysis of Toxic
Organic Compounds in Ambient Air, EPA-600/4-83-027, U.S. Environmental Protection
Agency, Research Triangle Park, NC, 1983.
11. Stevens, R. K., and Rickman, E., Jr., "Research Protocol/Method for Ambient Air
Sampling with Annular Denuder Systems," prepared for U.S. Environmental Protection
Agency, Atmospheric Chemistry and Physics Division, Office of Research and Development,
Research Triangle Park, NC, ASRL-ACPD-RPM 003, January 1988.
12. 40 CFR Part 58, Appendix A, B.
13. Quality Assurance Handbook for Air Pollution Measurement Systems, Volume II -
Ambient Air Specific Methods, EPA 600/4-77-0272, May, 1972.
Revised 9/30/89 Page 44
-------
Method IP-9
Reactive Gases/Particulate Matter
Table 1. Estimated Detection and Quantification Limits
for the Annular Denuder System
Detection Limits
a) gaseous species
S02
HNO,
HONO
NH,
b) particuI ate
SO'
NO
,-3
1 hour
3.1
2.0
0.5
5.6
1.6
1.8
Sampling Period
1 dav 1 week
13
,08
.02
.25
0.07
0.08
02
01
01
0.04
0.01
0.01
Quantification Limits (/ig/m3)
a)
b)
gaseous species
SO,
HNO,
MONO
NH3
particulate
SO/
NO
'4.
1 hour
10.4
6.8
1.6
20.0
5.3
6.1
Sampling Period
1 dav 1 week
0.43
0.28
0.07
0.83
0.22
0.25
0.06
0.04
0.01
0.12
0.03
0.04
Samples analyzed by ion chromatography. Detection limits are taken as three
standards deviations above field blanks. Quantification limits are taken as ten
standard deviations above field blanks. Both the detection and quantification
limits were estimated assuming that the variance is independent of concentration.
Revised 9/30/89
Page 45
7/0
72,3
-------
Method IP-9 Reactive Gases/Particulate Matter
Table 2. Accelerator Jet Diameters and Corresponding
Reynolds Number (Re) for Selected Flow Rates
to Obtain 2.5 pM Aerodynamic D50 Separation
Flow Rate
L/min Jet Diameter Re
1.0 1.55 900
2.0 1.97 1400
5.0 2.65 2700
10.0 3.33 4200
12.0 3.55 4700
15.0 3.85 5500
16.7 4.00 6000
20.0 4.25 6600
Revised 9/30/89 Page 46
7/1
-------
Method IP-9
Reactive Gases/Particulate Matter
FILTER PACK
DENUDER #4
DENUDER#3
DENUDER #2
COUPLER ( TYPICAL )
DENUDER #1
COUPLER / IMPACTOR
r>
O
<*,
HCI, HN02
HNO3 , S02
O
co
A
HN03
SO 2
t
Figure 1. Schematic View of Annular Denuder Showing Species Collected
Revised 9/30/89 Page 47
-------
Method IP-9
Reactive Gases/Particulate Matter
TEMP.CONT.
AIR OUTLET
12YLT
NYLON
TEFLON
DENUDER*4
CITRIC ACID
COATING
DENUDER f 3
Na2C03
DENUDER f 2
NazC03 COATING
HOUR METER
FLOW
METER
TEMP. DENUDER ft
CONT. NaCI COATING
FAN
TIMER
TT\
AMP METER [ VACUUM GAUGE
FLOW ADJUSTMENT
Figure 2. Annular Denuder System
Revised 9/30/89
Page 48
7/3
-------
Method IP-9
Reactive Gases/Particulate Matter
FILTER PACK
NYLON
TEFLON
d2
COUPLER ( TYPICAL}-
d1
COUPLER / IMPACTOR
HCI, HN02
HNOs , SO2
Figure 3. Schematic View of Annular Denuder with Cyclone
Adaptor for Removal of Coarse Particles
Revised 9/30/89
Page 49
-------
Method IP-9
Reactive Gases/Particulate Matter
12Y]
TEMP. CONT.
AIR OUTLET
HOUR
METER
DENUDER 12
COATIN / FLOW
METER
DENUDER 14
CITRIC ACID
COATING
DENUDER 13
Na2CO 3
TEMP. CONT.FAN CYCLONE
AMP METER | VACUUM GAUGE
TIMER FLOW ADJUSTMENT
INLET
Figure 4. Annular Denuder System with Cyclone in Heated Sampling Case
Revised 9/30/89
Page 50
-------
Method IP-9
Reactive Gases/Particulate Matter
1mm ANNULAR SPACE
CROSS-SECTIONAL VIEW
INTERNAL SURFACE
TEFLON COATED
Figure 5. Internal Schematic of Annular Denuder
Revised 9/30/89
Page 51
7/6
-------
Method IP-9
Reactive Gases/Particulate Matter
ACCELERATION JET
ELUTRIATOR
GLASS ASSEMBLY
AIR
ALLUMINUM
rO> TEFLON
" ACCELERATION
JET
ELUTRIATOR
AIR
ACCELERATION JET REMOVAL TOOL
ALUMINUM AND TEFLON ASSEMBLY
Figure 6. Available Elutriator and Acceleration Jet Assemblies
Revised 9/30/89
Page 52
-------
Method IP-9
Reactive Gases/Particulate Matter
DC
LU
o
o
o
o
O
7
61-
5
4
3
2
1
T 1 T
THEORY OK
THEORY QUESTIONABLE
2.5micromDIA.
CUTRONT
100
80
60
40
20
•—OANETER
--••-- REYNOLDS NO.
i i 1
6 8 10 12 14
FLOW RATE, liter/min
Figure 7A
16 18 20
A
2 2.5 4 6
Aerodynamic Diameter, pm
Figure 7B
Figure 7. D50 for Acceleration Jet (Figure 7A) and
Teflon®-Coated Cyclone (Figure 7B)
8 10
Revised 9/30/89
Page 53
-------
Method IP-9
Reactive Gases/Particulate Matter
(IN)
TEFLON SEAT SUPPORT
Figure 8. Side View Impactor/Coupler Assembly
Revised 9/30/89
Page 54
7/f
-------
Method IP-9
Reactive Gases/Particulate Matter
PIN REMOVAL TOOL
IMPACTOR SUPPORT PIN
VITON -0M-RING
#30 THREADS
PIN HOLDER
ANNULAR DENUDER/
IMPACTOR (242 mm LONG)
*30 THREADS
CAP
Figure 9. Glass Annular Denuder with Inset Impactor Assembly
Revised 9/30/89 Page 55
-------
Method IP-9
Reactive Gases/Particulate Matter
n
11
ui
FRIT TOOL #3
TEFLON PIN
STAINLESS STEEL
FRIT HOLDER #3
Figure 10. Frit Removal from Pin
Revised 9/30/89
Page 56
-------
Method IP-9
Reactive Gases/Particulate Matter
STAINLESS
STEEL
POROUS
SCREENS
QUICK-RELEASE
PLUG
ALUMINUM FILTER
HOUSING OUTLET
VITON "0" RING
TEFLON
FILTERS
VITON "0" RING
FILTER HOUSING
INLET
DELRIN
SCREW SLEEVE
Figure 11. Filter Pack Assembly
Revised 9/30/89
Page 57
13,$
-------
Method IP-9
Reactive Gases/Particulate Matter
Figure 12. Annular Denuder Coating Procedure
Revised 9/30/89
Page 58
723
-------
Method IP-9
Reactive Gases/Particulate Matter
WALL CLAMP /
DRYER /
CLEANER
BOTTLE
FRIT
THERMOPLASTIC CAPS
W / TEFLON SEAL RINGS
AND HOSE BARBS
MANIFOLD
BACK-TO-BACK
CONNECTORS
AIR
T
Figure 13. Drying Train and Manifold
Revised 9/30/89
Page 59
-------
Method IP-9
Reactive Gases/Particulate Matter
Figure 14. Annular Denuder in Field-to-Lab Case
Revised 9/30/89
Page 60
-------
Method IP-9
Reactive Gases/Particulate Matter
LOR SHEET
Sample
Period
_M««^—
^^^H^MX
Dale
™^ ^^^
Time
siaa
Time
Step.
^^^B^—V
««*«««•
Duration
B^«^^B^-«iV
•••^••^••m™™
^ "
plow
1 frnin
^«a^i««i^—
Denuder
••HH^-^M^"^
Denuder
Samnle OB
Denuder
Sample SC
Nvlon
Filter
Sample *
Teflon
Filler
fiamnlg It
^nmmgnts
.^ — — ^ ^ •
"-'
Figure 15. ADS Field Test Data Sheet
Revised 9/30/89
Page 61
-------
Method IP-9
Reactive Gases/Particulate Matter
STAINLESS STEEL
FRIT TOOL #3
THERMOPLASTIC
COUPLER/IMP ACTOR
WITH TEFLON "O"-RINGS
TEFLON FRIT
REMOVAL TOOL
CUTAWAY VIEW
Figure 16. Side View Impactor/Coupler Assembly with Disc Removal Tools
Revised 9/30/89
Page 62
t'7
-------
Method IP-9
Reactive Gases/Particulate Matter
Delivery Mode
Separation Mode
Detection Mode
Data Mode
Eluent
Reservoir
Pump
Sample
Injector
HPIC AG4A
Guard Column
HPIC AS4A
Analtical
Column
Micromembrane
Suppressor
Column
Conductivity
Cell
1
i
Recorder
A^A/WvJWVw\A/vV\
Electronic
Integrator
1
Computer
Figure 17. Major Components of a C jmmercially Available Ion Chromatographer
Revised 9/30/89
Page 63
-------
Method IP-9
Reactive Gases/Particulate Matter
Denuder 3
(Na2C03)
Denuder 2
(Na2C03)
Denuder1
(Na Cl)
NO, / I S04
2.0
4.0
Solvent
Front
r— M I
6.0 Retention Time
(Minutes)
HN02 HNO,
(NOi) (NO',)
t
SO,
(so;j
Figure 18. Chromatograms of Denuder/Filter Extract
Performed by the Ion Chromatography
Revised 9/30/89
Page 64
-------
Method IP-9
Reactive Gases/Particulate Matter
Filter 2
(Nylon)
Filter 1
(Teflon)
2.0 4.0
I I
Solvent (NOi) (NOs)
I
Front
6.0 Retention Time
1 (Minutes)
(SO;)
Figure 18 (Cont'd). Chromatograms of Denuder/Filter
Extract Performed by the Ion Chromatography
Revised 9/30/89
Page 65
-------
Method IP-9
Reactive Gases/Particulate Matter
. CHANNEL
REPLICflTE3=
85=22=17
1. '33
PILE
NETHlTO 5.
85=22=17 CH= "fl"
RUN 1 INDE'X 1
HOI
TQTfll. -^
PPM
2,.
4- :
3. :
-1:1- 12:?
«REfl BC
RF
1--3-3 :3809:38-l «33252Q50.75
3-74 1114551i5 8i230:3038. 164
•5-13:3 115:31441 «13823874. '534
RRT
8-327
8. £15
1.
PERK HE:IGHT::;= :i 7:3=*=* :? :?s=*=* 3 440=*=* 4 437=** 5
RT SET 1. :33>5 3. 4334 5- 3244
Figure 19. Chromatogram of a Standard with
Nitrous Acid, Nitric Acid, and Sulfuric Acid
Revised 9/30/89
Page 66
-------
Method IP-9
Reactive Gases/Particulate Matter
analytical unit
reagent sequencer
computer
sampler
Figure 20. 4-Channel Traacs 800 System with Reagent Sequencer
Revised 9/30/89
Page 67
-------
Method IP-9
Reactive Gases/Particulate Matter
Wash Water
To Sampler
Heating
Bath
37 °C
nnnnn nnooo ooooo ooooo
Proportioning
Pump
Colorimeter
Wash Water
Sampler
Figure 21. Technicon Autoanalyzer Flow Diagram for Ammonia Analysis
Revised 9/30/89
Page 68
733
-------
Method IP-9
Reactive Gases/Particulate Matter
FILTER PACK
NYLON
TEFLON
d4
Citric Acid
d3
d2
d1
NaCI
C(HN03) =1.016
Figure 22. Nitric Acid Gas Measurement
Revised 9/30/89
Page 69
73 £
-------
Method IP-9
Reactive Gases/Particulate Matter
FILTER PACK
NYLON
TEFLON
d4
Citric Acid
d3
Ca(HNOJ = 1.022 [N0"(d2) - NO (d3)]/V
y ^ fc ™
+ 0.758 lNOl(d2) - NOl(d3)]A^
•5 «
Figure 23. Nitrous Acid Gas Measurement
Revised 9/30/89
Page 70
-------
Method IP-9
Reactive Gases/Particulate Matter
FILTER PACK
NYLON
TEFLON
d4
Citric Acid
d3
Na2C03
d2
Na2C03
d1
NaCI
C (SOJ = 0.667[SO!(d1) + SO!(d2)]/V
g 2 ^ *
Figure 24. Sulfur Dioxide Gas Measurement
Revised 9/30/89
Page 71
-------
Method IP-9
Reactive Gases/Particulate Matter
FILTER PACK
NYLON
TEFLON
d4
Citric Acid
d3
Na2C03
d2
Na2C03
d1
NaCi
C (NH_) = 0.944[NH+(d4)]/V
g 3 *t
Figure 25. Ammonia Gas Measurement
Revised 9/30/89
Page 72
-------
Method IP-9
Reactive Gases/Particulate Matter
FILTER PACK
NYLON
TEFLON
d4
Citric Acid
d3
Na2C03
d2
Na2C03
d1
NaCI
T) = [so;(fi)]/v
\P____2
Figure 26. Paniculate Sulfate Measurement
Revised 9/30/89
Page 73
-------
Method IP-9
Reactive Gases/Particulate Matter
FILTER PACK
NYLON
TEFLON
d4
Citric Acid
d3
d2
d1
NaCI
*) = [NH+(f1)]/V
Figure 27. Particulate Ammonium Measurement
Revised 9/30/89
Page 74
-------
Method IP-9
Reactive Gases/Particulate Matter
FILTER PACK
NYLON
TEFLON
Cp(N03) =
N03 (f2)]/V
d4
Citric Acid
d3
d2
d1
NaCI
Figure 28. Participate Nitrate Measurement
Revised 9/30/89
Page 75
-------
Method IP-9
Reactive Gases/Particulate Matter
FILTER PACK
NYLON
TEFLON
d4
Citric Acid
d3
Na2C03
d2
Na2C03
d1
NaC!
03)2 + (£V/V)2
Figure 29. Particulate Sulfate Measurement and Uncertainties
Revised 9/30/89
Page 76
-------
Method IP-9
Reactive Gases/Particulate Matter
Figure 30. Annular Denuder Personal Sampler
Revised 9/30/89
Page 77
-------
Method IP-9
Reactive Gases/Particulate Matter
rUTAWAY VIEW
QUICK RELEASE
PLUG
FILTER PACK
FILTER INLET COMPONENT
COUPLER
(TYPICAL)
FLOW STRAIGHTNER
(37mm LONG)
COUPLER/IMP ACTOR
ACCELERATION JET
ELUTRIATOR
AIR
VI
Figure 31. Fine Particle Sampler
Revised 9/30/89
Page 78
-------
Method IP-9
Reactive Gases/Particulate Matter
TEMP.CONT.
AIR OUTLET
HOUR METER
FLOW
METER
DENUDER
(TYPICAL)
TEMP
"CONTI
e>swrrJ
.CHES
COUPLER/
^..r, IMPACTORS SAMPLE
TEMP. INLETS
CONT.
FAN
AMP METER / VACUUM GAUGE
TIMER FLOW ADJUSTMENT
Figure 32. Annular Denuder System with Fine Particulate Sampler
Revised 9/30/89
Page 79
-------
Method IP-9, Appendix Reactive Gases/Particulate Matter
Spectra-Physics Integrator Program
for 1C Analysis
Revised 9/30/89 Pa8e 80
-------
Method IP-9, Appendix Reactive Gases/Particulate Matter
2 'SKIP INJECT THEN RESTART: BO TO 99
~ FI-2: F2=2: CA=1: '."COPY";: INPUT "V3=";: V9=l: V3=l: GO TO .io
5 FI=5: !"USE FILE 5": GO TO 1BOOO
6 INPUT V4
7 ON V4GO TO 24,65,3,5,30,255,220,229,205
•74 F'7=2: V3-0: CA=O
^5 FI=F-?- CS=1: IX=1: MO»0 : LC-1: RN=O: CW=. 13: 7FN"75" , 1
26 71 = 1.8: AC=1: AT=128 : PW=2OO: PT=500O: DP-3: MA=326O: MP=e,H
27 OF=-50: 71=.5: PW=6: P7=100O
29 ("CHECK PAPER AND CONDUCTIVITY ";
30 GOTO 98
31 IF RO-.01 THEN 33
32 RN—1*RC: '."NEXT RUN IS";RN;: RN=RN-1: GO TO 3O
~3 IF RC=0 THEN 2074
34 IF RC=999 THEN INPUT "SCALE=";V9: GOTO 30
35 IF RC=99 THEN ABORT
36 IF RC=1 THEM RA=1: GOTO 42
40 INPUT "INJECTIONS PER STATISTICS=";RA
42 V1=RN+1
43 FI=0: !"CHECK SAMPLER FOR LOAD AND RUN";
45 PLOT OFF: P7=5OOO: CA=O: INJECT : END
47 FI=F2: V2=RN+RC: !"SAMPLES FROM";V1"TO";V2"REPLICATES=";RA;
4R FI=F2: R7<4)«VB: R7(3)«V8*. 87: RT(2)=V8*.62: RT<1)=V8*.34
49 CA=V3: PH=2: 77 (B)=l .fe+VB: TT (9) =-2. 9+VB: 77 (10) =3. 0+V8
50 PLOT A: INJECT : END
^ ! $10"PEAK HEIGUT(N)="PHS(1)/1OOO,PHS <2)/1000,PHS(3)/1UOu
55 TD =AC(2): TG(RN)=AC(3): 71(RN)=AC(4)
59 IF RA=1 THEN TD(RN)=-9.9
60 IF IX=1 THEN ! ; "RT SET" ,RT (1) , RT (2) , RT (3) ,R7 (4) ELSE TD(RN)— «j
61 7A(RN)-LC(1): TZ(RN)=LC(2): TC(RN)=LC(3): TJ(RN)=LC(4)
62 IF RN=V2 THEN 190
64 GOTO 48
Revised 9/30/89 Pa§e 81
-------
Method IP-9, Appendix
Reactive Gases/Particulate Matter
65
93
99
101
190
191
192
193
194
205
210
212
214
215
216
218
219
220
229
233
255
356
360
400
410
2050
2074
8340
18635
FI=2: RN=V2: PLOT OFF: INJECT : END
!"TOTAL NEW INJECTIONS^";
INPUT RC;
IF RC=-99 THEN 2: ELSE 31
V5=V5+RN : !"LOOP=75UL;COL=AS4A; S/N09317;PAST CAL=";V5
!"EL=.O01S nA2co3;.0017nAhco3=12.9US;10US=1v;fLOW=1.7ML/M=12OOPSI
IF V3=0 THEN 210
!"X=ACTUAL +=CALCULATED": V5=0
TFN 1!T5",0 : ABORT: END
FI=F2: INPUT "SCALE=";V9
!TAB 15"PARTS PER MILLION (UG/ML)"
!" RUN NUMBER ",$9.03,CN(1),CN(2),CN(3),CN(4)
FDR K=V1 TO RN: !*9 K$9.3,TA(K)*V9,TZ*V9,TJ*V9
IF TD : C=C+ (TC (K) *V9) : D=D-(-TJ (K) *V9
NEXT K: ! TAB 15"SUM"$9.3 ;'A,B,C,D: END
FI=9: GOTO 194
FI=B: F2=B: CA=1: !"COPY";: INPUT "VB=";V8;: V9=l: V3=l: GOTO 25
INPUT "CHANGE END SAMPLE TO";V2: RC=V2-RN: GOTO 47
i"PEAK HEIGHTS=!1;: A=SIZE"PS": IF AMO THEN A=10
FOR K=l TO A : !$2 K *5 PSH(K)/100O"*#";
NEXT K: ! : END
FOR 1=1 TO 4 : ! KA(I),KB(I),KC(I),I: NEXT I: END
FOR 1=1 TO 4 : !I;: INPUT KA(I),KB(I),KC(I): NEXT I: END
STOP 64: END
GOTO 6
V="XF"GOSUB 865ONEXT !!GOTO 400
!*8;T;: GOTO 18640
Revised 9/30/89
Page 82
-------
Chapter IP-10
DETERMINATION OF RESPIRABLE PARTICUIATE
MATTER IN INDOOR AIR
1. Scope
Suspended particulate matter in air is generally considered to consist of all airborne solid
and low vapor pressure liquid particles that are airborne. Suspended paniculate matter in
air presents a complex multiphase system consisting of a spectrum of aerodynamic particle
sizes ranging from below 0.01 microns (/mi) up to 100 urn and larger. Historically,
measurement of paniculate matter (PM) has concentrated on total suspended particulates
(TSP), with no preference to size selection. Research on the health effects of TSP in
ambient and indoor air has focused increasingly on those particles that can be inhaled into
the respiratory system, i.e., particles of less than 10 urn aerodynamic diameter. It is now
generally recognized that, except for toxic materials, it is this fraction (< 10 /an) of the total
paniculate loading that is of major significance in health effects.
2. Applicability
2.1 Recent studies involving particle transport and transformation suggest strongly that
atmospheric total suspended paniculate (TSP) matter commonly occurs in two modes. The
fine or accumulation mode is attributed to growth of particles from the gas phase and
subsequent agglomeration, while the coarse mode is made up of mechanically abraded or
ground particles. Particles that have grown from the gas phase, either because of
condensation, transformation or combustion, occur initially as very fine nuclei 0.05 /mi in
size. Those particles tend to grow rapidly to accumulation mode particles around 0.5 /im
in size which are relatively stable in the air. Because of their initially gaseous origin, this
range of particles sizes includes inorganic ions such as sulfate, nitrate, ammonia,
combustion-form carbon, organic aerosols, metals (Pb), cigarette smoke by-products, and
consumer spray-products.
22 Consequently, based upon the health effects of coarse and fine particulate matter, a
method has been developed to determine both continuous and speciated coarse (< 10 /un)
and fine (<2.5 /mi) particulate matter hi indoor air. A Microenvironmental Exposure
Monitor (MEM) has been developed as a fixed site monitor. Similarly, Personal Exposure
Monitors (PEMs) have been developed to estimate personal exposure to particles. Finally,
a TEOM* continuous monitor is presented as a means of determining total mass on a real-
time basis.
Revised 9/30/89 Pa8e
-------
Method IP-10A
DETERMINATION OF RESPIRABLE PARTICULATE MATTER
IN INDOOR AIR USING SIZE SPECIFIC IMPACTION
1. Scope
2. Applicable Documents
3. Summary of Method
4. Significance
5. Definitions
6. Method limitations and Limits of Detection
7. Apparatus Description
7.1 Microenvironmental Exposure Monitor (MEM)
7.2 Personal Exposure Monitor (PEM)
7.3 Cahn Microbalance
7.4 Weighing Room Environment
8. Apparatus Listing
8.1 Microenvironmental Exposure Monitor
8.2 Personal Exposure Monitor
9. Filter Preparation and Initial Weighing
9.1 Overview
9.2 Cahn Microbalance Operational Protocol
9.2.1 General
9.2.2 Balance Zeroing
9.2.3 Balance Calibration
9.3 Initial Filter Weighing
9.4 Packaging Filters
10. Preparation of the MEM Impactor Assembly
10.1 General
10.2 Cleaning of the Stainless Steel Impactor Plates
10.2.1 Laboratory Environment
10.2.2 Field Environment
11. Sampling
11.1 Placement of Filters in the MEM
11.2 Initial Field Flow Check of Sampler
11.3 Placement of Sampler and Sampling
11.4 Final Field Flow Check of Sampler
11.5 Changing Impactors
12. Filter Recovery and Final Weighing
12.1 24-hour Filter Equilibration
12.2 Filter Inspection
12.3 Final Weighing
12.4 Independent Audit of Weighted Filters
Revised 9/30/89 Page 1
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Method IP-10A Respirable Particulate
13. Calculation
13.1 Mass Calculation
13.2 Volume Air Parcel Sampled
13.3 Concentration of Particles in Air Parcel Sampler
14. Sampling System Calibration
15. Method Safety
16. Performance Criteria and Quality Assurance
17. References
Revised 9/30/89 PaSe 2
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Method IP-10A
DETERMINATION OF RESPIRABLE PARTICULATE MATTER
IN INDOOR AIR USING SIZE SPECIFIC IMPACTION
1. Scope
1.1 Suspended paniculate matter in air is generally considered to consist of all airborne
solid and low vapor pressure liquid particles (1-3) that are airborne. Suspended paniculate
matter in air presents a complex multiphase system consisting of a spectrum of aerodynamic
particle sizes ranging from below 0.01 microns (/«n) up to 100 /im and larger. Historically,
measurement of paniculate matter (PM) has concentrated on total suspended particulates
(TSP), with no preference to size selection (4). Research on the health effects (5-7) of TSP
in ambient and indoor air has focused increasingly on those particles that can be inhaled
into the respiratory system, i.e., particles of aerodynamic diameter less than 10 nm. It is
now generally recognized that, except for toxic materials, it is this fraction (< 10 /Jin) of the
total paniculate loading that is of major significance in health effects (8).
1.2 The two processes by which particles are formed are the grinding or atomization of
matter (9-10), and the nucleation of supersaturated vapors, as illustrated in Figure 1. The
particles formed in the first process are products of direct emissions into the air, whereas
particles formed in the second process usually result from reaction of gases, then nucleation
to form secondary particles. Particle growth in the atmosphere occurs through gas-particle
interactions, and particle-particle infraction.
1.3 Recent studies (11-12) involving particle transport and transformation suggest strongly
that atmospheric respirable paniculate matter commonly occurs in two modes. The fine or
accumulation mode is attributed to growth of particles from the gas phase and subsequent
agglomeration, while the coarse mode is made up of mechanically abraded or ground
particles. Particles that have grown from the gas phase, either because of condensation,
transformation or combustion, occur initially as very fine nuclei 0.05 /mi in size. Those
particles tend to grow rapidly to accumulation mode particles around 0.5 /mi in size which
are relatively stable in the air. Because of their initially gaseous origin, this range of
particles sizes includes inorganic ions such as sulfate, nitrate, ammonia, combustion-form
carbon, organic aerosols, metals (Pb), cigarette smoke by-products, and consumer spray-
products.
1.4 Coarse particles, on the other hand, are mainly produced by mechanical forces such
as crushing and abrasion. Coarse particles therefore normally consist of finely divided
minerals such as oxides of aluminum, silicon, iron, calcium and potassium. Coarse particles
of soil or dust mostly result from entrainment by the motion of air or from other
mechanical action within their area. Since the mass of these particles are normally >3 /mi,
their retention time in the air parcel is shorter than the fine particle fraction. Table 1
outlines the chemical constituents of the fine and coarse modes.
1.5 The composition and sources of coarse particles are not as thoroughly studied as those
of fine particles. One reason is that course particles are more complex than fine particles
Revised 9/30/89 Page 3
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Method IP-10A Respirable Particulate
but similar to each other in chemical composition. It is possible, however, to recognize
dozens of particle types, based on microscopical examination; these range from soil
particles, limestone, flyash, oil soot to cooking oil droplets.
1.6 Outdoor concentrations of TSP, more specifically, are of major concern in estimating
air pollution effects on visibility, ecological and material damage; however, people spend
the majority of their time inside buildings or other enclosures.
1.7 Consequently, based upon the health effects of coarse and fine particulate matter, a
method (14-17) has been developed to determine both coarse (>2.5/mi to 10/zm) and fine
(<25/tm) particulate matter in indoor air. A Microenvironmental Exposure Monitor
(MEM) has been developed as a fixed site monitor. Similarly, Personal Exposure Monitors
(PEMs) have been developed (18-20) to estimate personal exposure to particles. The PEMs
can be connected to the participants lapel and are used in conjunction with personal pumps.
1.8 This method may involve hazardous materials, operations, and equipment. This
method does not purport to address all of the safety problems associated with its use. It
is the responsibility of whoever uses this method to consult and establish appropriate safety
and health practices and determine the applicability of regulatory limitations prior to use.
2. Applicable Documents
2.1 ASTM Standards
D1356 Definitions of Terms Relating to Atmospheric Sampling and Analysis.
D1605 Sampling Atmospheres for Analysis of Gases and Vapors.
D1357 Planning the Sampling of the Ambient Atmosphere.
22 Other Documents
U.S. Environmental Protection Agency Technical Assistance Document (21)
Laboratory Studies for Monitoring Development and Evaluation (22-31)
3. Summary of Method
3.1 For monitoring indoor air, two distinct samplers have been illustrated in this procedure.
The Microenvironmental Exposure Monitor (MEM) has been developed as a fixed site
monitor, while the Personal Exposure Monitor (PEM) has been developed to estimate
personal exposure to particles. In addition, the PEMs have been used in the Particle Total
Exposure Assessment Methodology (Particle-TEAM) Program underway by the U.S.
Environmental Protection Agency (32). One of the objectives of the Particle-TEAM is to
establish the level of human exposure to particles and relate exposure to sources of aerosol
matter through the application of the PEMs.
32 Both systems operate on the principal of impaction. A constant flow (4 Lpm)
particulate laden gas stream enters the impactor assembly. The design of the impactor
allows the particulate matters to be fractionated into the desired ranges of fine respirable
Revised 9/30/89
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Method IP-10A Respirable Particulate
[<2.5 fan] or inhalable fraction [< 10.0/nn]). The flow rate through the sample coupled with
the impactor design characteristics enables the particulate matter to be speciated. The 4
Lpm flow rate was chosen because it was technically achievable with both a battery powered
flow controlled pumping system (ideal for the PEMs) and a line powered system (ideal for
the MEMs). In a typical sampling program, the flow rate will allow a total sample volume
of 5.5 m3 per day, thus facilitating improved accuracy in gravimetric measurements for a
typical indoor particulate loading air parcel.
3.3 A volume of air is accurately drawn for a measured period of time through the
impactor assembly to a tared filter.
3.4 The total particulate matter loading is calculated from the weight gain of the filter and
the total volume of air sampled.
4. Significance
4.1 When sampling particles for subsequent chemical/elemental analysis and possible
association with human health effect, characterizing reliable size separation is important.
Size fractionation of deposited particles occurs in the respiratory tract during inspiration.
Further, physical and chemical processes result in bi- or tri-modal distribution of suspended
particles in the atmosphere.
42 Because alkaline particles tend to be greater than 3 pm in diameter and acidic particles
tend to be less than 1 Jim, a sharp size separation in this range would be desired to prevent
neutralization of acidic aerosols collected on a filter. Further, the distinct separation of
particle mass by size permits source resolution by multivariate statistical analysis techniques
using the elemental and chemical composition of the fine fraction particle mass.
43 For these reasons, it is imperative that a sampling protocol addressing the sampling
and analysis of speciated particulate matter in indoor air be developed.
5. Definitions
Note: Definitions used in this document and any user prepared Standard Operating
Procedures (SOPs) should be consistent with ASTM Method D1356. All pertinent
abbreviations and symbols are defined within this document at point of use. Additional
definitions, abbreviations, and symbols are located in Appendices A-l and B-2 of this
compendium.
5.1 Particulate mass - a generic classification in which no distinction is made on the basis
of origin, physical state, and range of particle size. (The term "particulate" is an adjective,
but it is commonly used incorrectly as a noun.)
52 Dust - dispersion aerosols with solid particles formed by comminution or disintegration
without regard to particle size. Typical examples include 1) natural minerals suspended
Revised 9/30/89 Page 5
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Method IP-10A . Respirable Particulate
by the action of wind, and 2) solid particles suspended during industrial grinding, crushing,
or blasting.
5.3 Smokes - dispersion aerosols containing both liquid and solid particles formed by
condensation from supersaturated vapors. Generally, the particle size is in the range ot
0.1 /im to 10 /rai. A typical example is the formation of particles due to incomplete
combustion of fuels.
5 4 Fumes - dispersion aerosols containing liquid or solid particles formed by condensation
of vapors produced by chemical reaction of gases or sublimation. Generally, the particle
size is in the range 0.01 /an to 1 pm. Distinction between the terms "smokes and fumes
is often difficult to apply.
5 5 Mists - suspension of liquid droplets formed by condensation of vapor or atomization;
the droplet diameters exceed 10 jim and in general the particulate concentration is not high
enough to obscure visibility.
5.6 Primary particles (or primary aerosols) - dispersion aerosols formed from particles that
are emitted directly into the air and that do not change form in the atmosphere. Examples
include windblown dust and ocean salt spray.
5.7 Secondary particles (or secondary aerosols) - dispersion aerosols that form in the
atmosphere as a result of chemical reactions, often involving gases. A typical example is
sulfate ions produced by photochemical oxidation of SO2.
5 8 Particle - any object having definite physical boundaries in all directions, without any
limit with respect to size. In practice, the particle size range of interest is used to define
"particle" In atmospheric sciences, "particle" usually means a solid or liquid subdivision of
matter that has dimensions greater than molecular radii (-10 nm); there is also not a firm
upper limit, but in practice it rarely exceeds 1 mm.
5.9 Aerosol - a disperse system with a gas-phase medium and a solid or liquid disperse
phase. Often, however, individual workers modify the definition of "aerosol" by arbitrarily
requiring limits on individual particle motion or surface-to-volume ratio. Aerosols are
formed by 1) the suspension of particles due to grinding or atomization, or 2) condensation
of supersaturated vapors.
5.10 Total suspended particulate (TSP) mass - the particulate mass that is collected by the
Sampler. (The system is classified in terms of the operational characteristics ot the
sampler).
5.11 Coarse and fine particles - these two fractions are usually defined in terms of the
separation diameter of a sampler. Coarse particles are those with diameters of 2.5 »m to
10 /im and the fine particles are those with diameters less than 2.5 /rai.
Note: Separation diameters other than 2.5 nm have been used.
Revised 9/30/89 Pa8e 6
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Method IP-10A Respirable Particulate
6. Method Limitations and Limits of Detection
6.1. The limitations on the test method are a minimum weight of 20 micro grams of
particles on the filter, and a maximum loading of 600 micro grams/cm and minimum of
20 micro grams/cm2 on the filter.
6.2 The test method may be used at higher loadings if the flow rate can be maintained
constant (± 5%) and degradation of the aerosol preclasifier performance is not adversely
affected.
6.3 The MEM and PEM samplers' limit of detection (LOD) is a function of the weighing
room environment and the precision of the microbalance used to perform mass
measurements.
6.4 Using the recommended equipment specified in this procedure, a 12-hour LOD of 8
/ig/m3 can be achieved for the PEM, and 4 /Jg/m3 for the MEM.
6.5 Overall precision is ± 2 /tg/m3 to ±25 /ig/m3 during dust loading studies (10 to 100
/tg/m3) at a flow rate of 4 L/min. for each sampler.
7. Apparatus Description
7.1 Mieroenvironmental Exposure Monitor (MEM) Description
7.1.1 As illustrated in Figure 2, the MEM is subdivided into four sections: 1) an inlet
section, 2) a three-piece inertial impaction section, 3) the upstream section of the filter
holder; and 4) the downstream section of the filter holder.
7.12 Inlet section - the inlet section has four large, circumferential slots for aerosol
to enter the MEM. These horizontal inlet slots prevent very large particles, perhaps those
greater than 100-/mi aerodynamic diameter, from entering the MEM and placing an
additional particle burden on the downstream impaction plate. The inlet section also acts
as a cover, preventing large particles from entering the MEM by gravity settling. The inlet
section should be shown to be unbiased with respect to the particle size distribution being
sampled.
7.1.3 Impaction section - the impaction section consist of three separate parts: 1) a
nozzle, 2) an impaction plate(s), and 3) a part designed for mounting the impaction plate.
Two versions of the impactor assembly are available. With a one stage impactor plate
assembly, aerodynamic particles of < 10 /mi are allowed to pass around the impactor. plate
and subsequently collected in the lower filter. With the two stage impactor assembly, as
illustrated in Figure 2, those particles <2.5 /mi are collected on the lower filter. A time
share option provides the capability of using two heads with one pumping system. In this
way, the total sampling time can be programmed to two samplers, enabling the collection
of <2.5 /im and <10 fim paniculate matter in the same general environment. These
features could be used to sample in two locations or to collect carbon on quartz filters or
acid aerosols through a unit equipped with an ammonia denuder.
Revised 9/30/89 PaSe 7
75*-
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Method IP-10A Respirable Particulate
7.13.1 Nozzle - a single circular nozzle with a converging inlet and cylindrical
throat to accelerate the aerosols through the nozzle to the filter. Two nozzle sizes are
available: a nozzle with a throat diameter of approximately 8 mm, is used for removing
paniculate matter with an aerodynamic diameter greater than 10 /mi; while smaller particles
are collected on the downstream filter and saved for analysis. An approximate 3 mm
diameter nozzle is used for collecting paniculate matter with an aerodynamic diameter
greater than 2.5 /mi; while smaller particles are collected on the downstream filter and
saved for analysis.
7.1.3.2 Impaction plate - a stainless-steel sintered disk is permanently mounted at
the center of the impaction plate, flush with the impaction plate's surface. The pores of the
sintered disk are filled with a light mineral oil in order to reduce bounce when the particles
impact. The oil also wicks up through the particle deposit by capillary action so that a
sticky surface continues to be available to incoming particles. The airstream containing the
remaining smaller particles flows around the impaction plate through three large annular
slots.
7.1.4 Upstream section of the filter holder - the upstream section of the sampler
provides a flow-straightening zone directly downstream of the impactor plate so that
uniform particle deposition on the filter is obtained.
7.1.5 Downstream section of the filter holder - in addition to acting as the downstream
side of the filter holder, this section contains a plenum through which the filtered air exits
via a side-mounted exit tube. It is also the MEM's base, which provides a surface on which
the MEM can sit in the correct orientation. ,VT^T,
7.1.6 Filter mounting and support - a 2-/mi pore-size, PTFE (Teflon*), 41 mm filter
disk with a polyolefin ring (Teflo #R2JO37 Gelman or equivalent) is mounted in a 2-inch
x 2-inch standard Beckman-type frame and is used as the filtration medium. The
downstream side of the filter is supported by a cellulose backing material (millipore AP-
10 or equivalent). The two sections of the filter holder forming the filter assembly each
have silicon rubber gaskets. Two draw latches hold the filter assembly together,
compressing the two rubber gaskets, the cellulose backing material, and the polyolefin ring.
This arrangement seals the filter assembly and prevents bypassing of-the aerosol around the
edge of the filter. The filter should be non-hygroscopic and should have a collection
efficiency greater than 99% for the particle laden air stream of interest. The filter should
be 37 mm in diameter.
Note: As an example, some glass fiber and most membrane filters with nominal pore size
of 2 micrometers will nearly always fulfill this requirement. The equilibrated filter is
preweighed by the user. The weight of the filter holder is not used in any determination
of weight gain in this test method. The filter holder material must not contribute to any
weight change of the filter.
7.1.7 Flow calibration section - to measure the volumetric flow through the MEM in
the field, the inlet section is replaced with an adapter that connects via rubber tubing to a
calibrated rotameter.
Revised 9/30/89 ~~ Pa8e 8
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Method IP-10A Respirable Paniculate
7.1.8 Pump - a sampling pump with a flow rate that can be determined accurately to
± 5%. Pulsation in the pump flow must be within ± 10% of the mean flow. The pump
must maintain the flow constant to within ± 5% during the sampling period. The pump
must be quiet enough so as to not cause undue disturbance in the area of use when being
used indoors. The pumping unit has four components: a pump, a mass flow meter, a flow
control circuit, and a timer. The system should be designed to provide constant flow by
means of a voltage control system. The voltage control system should be designed to keep
the flow at a constant 4 Lpm. The pump should be capable of maintaining up to a vacuum
of 50 inches of water at the 4 Lpm flow rate. This is important since air flow to the
impactor must not change as the filter loading increases. The mass flow meter should
consist of a heated filament and an electrical circuit that measures the flow by determining
how much heat is removed per second. If the flow is reduced (perhaps due to increased
pressure drop across the impactor), the feedback circuit should apply a greater voltage to
the pump to bring the flow back to the set point. A fan should be used to dissipate heat
generated by the pump. The box cover should be closed and the fan running during use
to maintain the accuracy of the control circuit.
12 Personal Exposure Monitor (PEM) Description
7.2.1 The PEM is illustrated in Figure 3 and consists of three sections: 1) an inlet-
nozzle section, 2) an impactor plate, and 3) exit section.
122 Inlet and nozzle section - aerosol enters through six nozzles located on the inlet
section's upstream surface, which is perpendicular to the direction of flow. Two inlet-nozzle
sections are available: one has a throat diameter of approximately 1.8 mm for paniculate
matter cut size of < 10 /im, and the other has a throat diameter of approximately 1.3 mm
for paniculate matter cut size of <2.5 pm.
7.2.3 Annular impactor plate - a stainless-steel sintered annulus is permanently
mounted in the impaction plate, flush with the impaction plate's surface. The pores of the
sintered annulus are filled with a light mineral oil in order to reduce bounce when the
particles impact. The oil also wicks up through the particle deposit by capillary action so
that a sticky surface continues to be available to incoming particles. The airstream
containing the remaining smaller particles flows through the circular opening in the center
of the impaction plate. The downstream circular edge of the impaction plate compresses
the upstream face of the filter and backing material.
7.2.4 Exit section - the retaining lip of the exit section compresses the downstream
face of the filter and backing material against the impactor plate edge, thereby preventing
leakage and filter bypass. The exit section has an exit plenum and side-mounted exit tube,
which connects by tubing to the pump. -_.-,
72.5 Filter and support - a 2-/xm nominal pore diameter, PTFE (Teflon®), 37 mm
membrane filter disk with polyolefin ring (#R2JO37 Teflo, Gelman or equivalent) is used
as the filtration medium. It is supported on its downstream face by cellulose backing
material (Millipore AP-10 037 or equivalent).
Revised 9/30/89 Pa8e 9
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Method IP-10A __ Respirable Paniculate
12.6 Flow calibration section - to measure the volumetric flow through the PEM in
the field, an adapter, which connects via rubber tubing to a calibrated rotameter, is placed
over the inlet nozzle section. . .
7 2.1 Pump - a 145 mm x 50 mm, tough, light, alloy case, which originally housed the
Casella AFC 400 pump unit, which contains the muffled double acting diaphragm pump,
integral motor, and pulse dampener from the Casella AFC 400; the remainder of the
components were removed and replaced with sound-deadening material.
72.8 Electronics section - flow should be maintained constant within a tolerance ot
5% by means of an electronic control circuit using current proportional feedback. When
the pressure drop across the filter increases, this system should automatically sense the
rising current demand by the motor and adjust its voltage to compensate. The electronics
case should also house a digital electronic elapsed timer, the LED that indicates when the
pump is running, and the electronics that automatically shut off the pump if the battery is
wcslc
72.9 Battery section - the battery pack should contain 3 or 4 lithium 9-volt batteries
with snap-on connectors, allowing quick battery replacement.
7.3 Cahn Microbalance
73.1 The Cahn Model 30 balance is capable of weighing up to 3.5 g with an accuracy
of ± 0.5 fig. It operates on the principle of balancing the sample with torque motor input.
The electric current flowing in the torque motor produces an equal and opposite force on
the balance beam when the beam is at the reference position, identified by a photocell
detection system. The current is directly related to the sample weight through the
calibration process.
132 The same analytical microbalance and weights must be used for weighing inters
before and after sample collection.
7.4 Weighing Room Environment
The weighing room should be a temperature and relative humidity controlled environment.
Temperature should be maintained within the range of 17° to 23°C. Relative humidity
should be maintained between 38% and 42%. Weekly strip chart recordings of temperature
and humidity should be maintained on a hygrothermograph. Temperatures should be read
from a calibrated maximum-minimum thermometer and relative humidity should be
calculated from a calibrated motor aspirated psychrometer. The weighing area should be
cleaned with paper towels and deionized distilled water each day before weighing. Forceps
should be cleaned once a week with detergent in a sonic bath and then rinsed in deionized
distilled water. Approximately once a month, the balance chamber and pans should be
cleaned with diluted ammonium hydroxide and each cleaning should be noted in the
weighing room log. Filters, weights, and pans should be handled only with non-serrated tip
forceps The Cahn balance should be left on continuously because it requires six hours to
warm up for stable operation. Polonium 210 alpha sources should be replaced at one year
intervals from date of manufacture. The replace date should be engraved on the source by
Revised 9/30/89 ae 10
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Method IP-10A Respirable Paniculate
the manufacturer, and noted in the weighing room log book. The filters should be
conditioned in the weighing room for at least 24 hours before they are weighed. Each filter
should be passed over a deionizing unit before weighing.
8. Apparatus Listing
8.1 Microenvironmental Exposure Monitor (MEM)
8.1.1 Sampler - William Turner, Air Diagnostics and Engineering, Inc., R.R. 1, Box
445, Naples, Maine. «-,„,,» u
8.12 Barometer, capable of measuring atmospheric pressure to ± 0.13 kPa, best source.
8.13 Stopwatch, capable of measuring to ±0.1 s, best source.
8.1.4 Weighing room, with temperature and humidity control to allow weighing with
a micro balance to ±5 micro grams.
8.1.5 Analytical micro balance, capable of weighing to ±5 fig.
Note: Particular care must be given to the proper zeroing of the balance.
8.1.6 Buret, capacity of 1 L, used as a soap bubble meter for calibration of the
sampling unit. At flows greater than 5 L/min., a transfer standard must be employed which
is traceable to a primary standard. Examples of transfer standard include wet test meter,
dry gas meter, mass flow meter, rotameters, and linear flow meter.
8.1.7 Plane-parallel press, capable of giving a force of at least 1000N (may be required
if plastic filter holders are used that must be pressed together after insertion of the filter).
8.1.8 Tapered tube flow meter, with precision ±2% or better within the range of the
flow rate used. It shall be possible to connect the suction side of the flowmeter to the inlet
of a leakproof container which contains the sampling head (in order to measure the flow
rate before and after sampling).
8.1.9 Thermometer, dry bulb, 0 to 50°C with divisions every 0.1°C.
8.1.10 Manometer, 0 to 250 mm of water for measuring the pressure drop across the
sampling head.
8.1.11 Flexible tube, the length of the tube is dependent on how the sampling unit is
placed. A length of 1 to 10 m is suitable if the pump is separated from the sampling head.
8.1.12 Inlet adapter or leakproof container (holds partial vacuum of 4 psi for 5 min.)
of suitable size to contain the sampling head. ,
8.1.13 Impactor base - ability to hold two types of Membrana Inc., Ghia., 2 x 2 ri *t
filters holders. .
8.1.14 Filters - 37 mm, 2.0 pm pore size, Membrana Inc., Ghia., filters.
8.1.15 Removable filter disks, i.e., 2.0 urn pore size PTFE disks with polyolefm nngs
and special flat spots mounted in 2" x 2" standard Beckman frames. (Ghia #R2PJO41 with
special cut). These filters have historically been used in the Beckman type automatic
dichotomous sampler by the U.S. EPA.
8.1.16 A one-week timer with 84 set points in 2-hour increments and battery backup.
8.1.17 Impactor classifier - 10 and 2.5 /mi cut size.
Revised 9/30/89 Pa8e n
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Method 1P-10A Respirable Particulate
82 Personal Exposure Monitor (PEM)
82.1 Sampler - Virgil Marple, MSP Corp., 1313-5th St. SE, Suite 206, Minneapolis,
Minnesota 55414. , _. ,. , ..-.
822 Filter - 2 /rai nominal pore diameter, PTFE, 37 mm membrane filter disk with
Dolvolefin ring (#R2JO37 Teflo, Gelman or Equivalent). .
82.3 Filter support - cellulose backing material, Millipore AP-10 037 or equivalent.
82.4 Pump - Casella AFC 400 pump unit or DuPont P125-A constant flow pump.
82.5 Analytical micro balance - refer to Section 8.1.5.
82.6 Buret - refer to Section 8.1.6.
9. rater Preparation
9.1 Overview
9.1.1 All filters are conditioned in the balance room for at least 24 hr. before initial
or final weighing to reduce the humidity effects on the filter weights. The 37 mm filters
should be stored in individual petri dishes after initial weighing.
9.12 A Cahn microbalance with electronic data transfer capability should be used to
weigh the 37 mm filters used in the PEM and MEM samplers. A Cahn Model 31 balance
should be connected to a Compaq portable computer through a serial port Filter numbers
are printed in bar code and assigned to filter containers. In operation, the filter number
are scanned with a bar code reader and the filter placed on the balance pan. A key is then
pressed on the computer keyboard to indicate that the filter is in position for weighing.
The computer sends the balance a request to weigh. The balance responds with weight and
stability code. The operator is signaled by a tone and a message on the computer screen
when weighing is completed. The operator then removes the filter and places it back in its
container The process is repeated for each filter to be weighed. The initial weight, time,
and data are written to the data file by the computer.
9.1.3 After the filter has been used, it is brought back for conditioning and fma
weighing The weighing procedure is the same as for initial weighing. The computer will
check the data file for the initial weight entry. The final weight will be matched with the
initial weight for that filter number in the data file. The computer subtracts the initial
weight from the final weight to determine the paniculate catch, which is used to calculate
the particulate concentration (in /ig/m3) at each sampler location. After weighmg, the
filters are carefully returned to the petri dishes for archiving or further analyses. Because
the date and time are saved in the data file with each reading, a chronological history is
therefore available for additional verification.
9 14 The filters must be pre-weighed before use in a temperature and humidity
controlled weighing room. Since the objective of the sampling system is to determine mass
particle loading of the indoor air, the filters do not need to be pre-treated.
9.1.5 Insure that the weighing room meets the specifications as outlined in Section I A.
Revised 9/30/89 Page
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Method IP-10A Respirable Particulate
92 Cahn Microbalance Operational Protocol
9.2.1 General - initiate a weighing session by typing operator name, balance room
temperature, and relative humidity into the Compaq computer. Ensure that identical
stirrups are attached to the "A" hang down loop and the "tare" hang down loop of the
balance beam. . „
Note: The maximum weight that can be measured in this range is 250 mg. xenon ;>/
mm filters should weigh in the 80-100 mg range.
Note: An ionizing, static-eliminator unit should be in the bottom of the weighing chamber.
922 Balance zeroing - after checking that the two stirrups contain no sample and are
clean close the balance door and release the pan brake by pressing the "Brake" button.
Press zero (0) and then ENTER on the computer. Wait for a computer tone, which
indicates that weighing is completed.
9.23 Balance calibration - remove a 200 mg calibration weight from its container
(using plastic tweezers) and place it on the sample stirrup ("A" loop). Close the balance
door Press "200" and then ENTER on the computer. Wait for the computer tone, which
indicates that weighing is completed. Repeat the above procedure with a 90 mg calibration
weight. Return the 90 mg calibration weight to its container.
9.3 Initial Filter Weighing
93.1 Put on a clean pair of lint-free gloves. Disposable latex gloves should not be
used because of possible filter contamination with talcum powder inside the gloves.
9.32 Select a packet of pre-conditioned (minimum of 24 hours inside the weighing
chamber), clean 37 mm Teflon* filters.
933 Select a series of pre-labeled petri dishes.
93.4 Using Teflon* tweezers, pick up the top filters and examine them over a black
surface for holes or tears. Discard any filter with a hole or tear.
93.5 Pass each clean filter several times over the top of the static eliminator unit in
the bottom of the weighing chamber.
93.6 Place the clean filter on the balance stirrup and close the door. Allow the weight
display to stabilize. , , , ., t_ v. A
93.7 Select a pre-numbered and labeled petri dish. Scan the label with the bar code
recorder. Press the V key (for weigh) and then ENTER on the computer. Wait for the
computer tone, which indicates weighing is completed.
93.8 Open the balance door. With tweezers, remove the filter from the balance pan
and load it into the filter support.
93.9 Return the filter and its support to the corresponding petri dish, close, and secure
with masking tape.
93.10 Place the tared filter, with petri dish, in a stack ready for field sampling.
93.11 Complete steps 9.3.4 through 9.3.10 for each filter to be initially weighed. After
every tenth filter weighing, check the balance zero. The stable electronic readout should
be 00.000 ± 00.004 mg. Check the balance calibration with 200 mg and 90 mg calibration
Revised 9/30/89 Pa8e 13
-------
Method IP-10A Respirable Particulate
weights as illustrated above. The stable electronic display should read 90.000 ± 00.002 mg.
If the balance zero and/or 200 mg or 90 mg standard weight calibration checks fall outside
the limits described above, rezero/recalibrate the balance as outlined above, and reweigh
the last ten filters. If the balance zero and 90 mg check are acceptable, continue to weigh
the 37 mm Teflon* filters. ...
93 12 At the end of the weighing session, enter the balance scan, relative humidity,
and temperature into the computer. Recheck the balance zero and 200 mg and 90 mg
standard weights as outlined above. .
93 13 Following the completion of a weighing session, a second individual as an
auditor should select 10 percent of the filters (minimum of two) for reweighmg. The
second person should enter his or her name into the computer and complete the above
steps for each filter to be reweighed. After all the selected filters have been rewdghed,
compare the initial weights recorded for each filter by both the auditor and the primary
operator. If the difference between the two measurements exceeds 10 /ig, the session is
declared invalid, and the filters must be reweighed. .
93.14 The first filter weighed in any batch is the batch blank and is stored in a petn
dish in the weighing room. The batch blank is reweighed at the end of each batch and if
it differs by more than 7 fig from the first weight, all the filters must be reweighed. If by
more than 5 /*g but less than 7/ig, then all filters back to the last zero are reweighed.
9.4 Packaging Filters
9.4.1 After weighing, the filters are placed in the frames (with the flat edge of the
filter matching the flat edge of the frames). A ring is then pushed in place on top of the
filter Care should be taken that the ring does not buckle and lies flat on top of the biter.
9.4.2 The filters are recorded in the field notebook with filter type, bar number, falter
identification and initial weight.
10. Preparation of the MEM Impactor Assembly
Note: The following discussion relates to the MEM impactor assembly. All instructions
are applicable to the PEM impactor assembly.
10.1 General
10.1.1 The preparation of an impactor takes place in three stages: 1) all impactor
plates must be cleaned before use, 2) plates must be oiled, and 3) placed into the impactor
underneath the nozzles. . ,,
10.12 The filter backings and the filters themselves are placed inside the base ot the
impactor. After assembly, the impactor is now ready for use.
10.2 Cleaning of Stainless Steel Impactor Plates
Note: The following protocols are designed for both laboratory and field cleaning
situations.
Revised 9/30/89 Pa8e 14
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Method IP-10A Respirable Paniculate
102.1 Laboratory Environment
102.1.1 Remove impactor plates from impactor and place in beaker or plastic
tube for cleaning. Mix laboratory detergent (Liquinox or equivalent) according to
manufacturer's directions in hot (40-50°C) tap water just prior to washing. Make enough
to immerse all plates to be cleaned.
102.12 Add enough detergent solution to cover all plates in the beaker or tub.
102.1.3 Soak for 10 minutes with intermittent gentle agitation. Remove them
from the beaker.
Note: Rough handling will damage plate surface. Do not put them hi an ultrasonic bath.
102.1.4 Check for any remaining visual deposit on the surface of the plates. If
deposit remains, go back to Section 10.2.1.3 and repeat washing. If still not removed,
deposit may need to be brushed off from each plate in the same detergent solution with a
firm bristle brush.
102.1.5 Place clean but soapy plates into another beaker or tub. Rinse 2 or 3
times with hot tap water or until all trace of detergent is removed.
102.1.6 Rinse next with distilledrdeionized water. Let sit for 6 minutes. Rinse a
second time with distilled-deionized water.
102.1.7 Drain well. Place rinsed plates in a well-ventilated container (stainless
steel or aluminum cage, or screen bottom plastic tub) and dry at 50-60°C MAXIMUM for
30 minutes or until dry.
Note: Do not exceed this temperature.
102.1.8 Store the cleaned, dry plates in a closed container. A zip lock bag is
sufficient if handled gently.
1022 Field Environment
1022.1 Place the plates in a tub with two scoops of a powder detergent and cover
the plates with hot water, making sure that the detergent is dissolved.
10222 Let soak for 30 minutes, agitating frequently.
1022.3 Rinse the plates thoroughly, drain, and place them in a clean tub and
repeat Section 10.2.2.1 and Section 10.2.2.2.
1022.4 After the second washing, rinse the plates again, drain, and place them
in a clean tub to rinse.
1022.5 Place the tub in a sink with the faucet running, let the water fill the tub
and overflow into the sink for a few hours or until there is practically no more oil on the
surface of the water. The plates should be agitated occasionally and the tub checked to
see that its walls have not become oily or the oil may get onto the plates.
1022.6 When the water appears to be cleared of oil, drain the plates and place
them in a single layer, sintered disk side up, on a large cookie sheet.
1022.7 Bake them in the oven at 200°F for about 3 hours, or until none of the
plates appear damp.
1022.8 Turn off the oven and leave the plates to cool in the oven.
Revised 9/30/89 Page 15
-776
763
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Method IP-10A Respirable Particulate
10.2.2.9 When the plates cool, place them in a clean zip-lock bag marked
"CLEAN"
10.2.2.10 There should be no dirt on the plates and no water in the cintered disk.
If the cookie sheets are not large enough for the number of plates chosen, the excess wet
plates can be left in a sealed zip-lock bag until the first batch is out of the oven.
103 Oiling of Impactor Plates
103.1 After drying, remove the plates from the zip-lock bag.
1032 Place the plates on a clean, dry surface.
10.33 With the aid of an eye dropper, deposit light mineral oil on the surface ot
the impaction plate. Apply until excess is observed. .
10 3.4 Using a pair of tweezers, tilt the plate to one side to allow excess mineral
oil to drain from the plate. If after proper drying and application of the oil, the oil pools
up on a plate, it is permissible to wipe off all the excess oil from the plate and still use the
Note: The objective is to clean the plates of dirt and excess water to coat each plate with
a uniform layer of oil.
103.5 Place the clean, oiled plates into the MEM sampler and secure.
11. Sampling
11.1 Placement of Filters in the MEM
11.1.1 Place the tared filter and filter support in the filter holder, close firmly with the
two over-center draw latches. ,.,
Note: The filter holder consists of a base and a cover that presses the plastic tilter slide
between two gaskets. . . .
1112 The assembly should be suitably covered to avoid contamination prior to use.
Note: If other MEM assemblies are available, replace the unit as a whole without
transferring filters under field conditions. .
1113 Clean and inspect the interior of the preclassifier (cover). If the inside surfaces
are visibly scored, replace the classifier to insure that the design characteristics of the
impactor are not altered.
11.1.4 Attach sampling pump unit to the MEM.
112 Initial Field Flow Check of Sampler
11.2.1 Run the sampler for approximately 10 minutes to stabilize the flow rate.
11.2.2 Detach the top of the impactor and replace it with a calibration adapter.
Connect the adapter, using a small piece of tubing, to the calibrated rotameter. Start pump
and record initial flow rate on the Field Data Sheet.
Note: Insure flow rate is acceptable to the monitoring protocol.
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Method IP-10A _ _ Respirable Particulate
1123 Disconnect the rotameter. With the pump still running, close off the filter inlet.
Flow should stop in 10 to 15 seconds or less if the system is leak free. If not, examine all
connections and flexible tubing for leaks.
112.4 Check the meter box assembly for proper operation.
Placement of Sampler
113.1 The sampling head should be located in the area in which the particulate
concentration is desired. During placement of the sampling head, care should be taken to
prevent any extraneous debris from entering the head during sampling. Care should also
be taken to avoid any restriction of the inlet. The sampler should be placed on a flat, stable
surface at least 2 to 5 feet off the floor to.prevent reentrainment of settled particles.
1132 Initiate sampling by turning the pump on; allowing the pump to warm-up and
set the flow rate according to the manufacture's instructions.
1133 Record the flow rate and the start time on the Field Data Sheet which is
provided in Figure 4.
Note: If the flow rate changes during sampling by more than ± 5%, record the cnange
and the time of change (annotating the lapsed time). Reset the flow rate. If unable to
reset the flow rate to the original setting, terminate sampling and note the reason for
termination.
113.4 At the end of the sampling period, record the final flow rate and the stop time
on the Field Data Sheet. Terminate sampling by turning the pump off.
113.5 If the sampler has an elapsed timer, record the elapsed time on the Field Data
Sheet.
113.6 Calculate the sampling time (Final tune - Initial time) to the nearest tenth ot
an hour.
Note: If the standard deviation of the run time is greater than 20% of the estimated run
time, during the 24 hour sampling period, record the deviation on the Field Data Sheet.
11.4 Final Field Flow Check of Sampler
11.4.1 Check the final flow rate by attaching a calibrated rotameter to the outlet of
the MEM unit.
11.42 Turn the unit on and record final flow rate on Field Data Sheet.
Note: The initial and final flow rates should be within ± 10%.
11.5 Changing Impactors
11.5.1 Change the sampled impactor by disconnecting the hose and reconnecting to
the new, clean impactor.
11.52 Record impactor identification number, filter identification number, base
number and filter batch number on the new Field Data Sheet.
11.5.3 Once again, connect a calibrated rotameter to the impactor and record initial
flow rate on the Field Data Sheet.
11.5.4 If applicable, re-set programmable timer to desired setting.
Revised 9/30/89 " ~ PagTl?
•7 7*
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Method IP-10A Respirable Paniculate
11.5.5 If you have a limited supply of impactors, you can change the filters and the
impaction plates in the field. You should have a box in which to store and transport the
filters. NEVER touch the filters during changing. If you touch a filter, the sample captured
on it may be no longer valid.
11.5.6 The following procedures are recommended if one wishes to change niters in
the field or in the laboratory.
11.5.6.1 Carefully swab the outer surface of the filter assembly with a lintless paper
towel moistened with water before opening the filter holder to minimize sample
contamination.
11.5.62 Open the filter holder and carefully remove the filter from the holder with
the aid of filter tweezers. Handle the filters very gently by the edge to avoid loss of dust.
Transfer the filter to a petri dish with cover or suitable holder. Do not turn the filter
upside down. Record all pertinent information on the Field Data Sheet.
11.5.6.3 Return dishes to weighing room for 24 hour equilibration.
11.5.6.4 If the whole filter assembly is returned to the laboratory, it should be
returned in a suitable container designed to prevent sample damage in transit.
11.5.6.5 For each set of 10 or less samples, submit a blank sample. The filters
and filter holders to be used as blanks are handled in the same manner as the samples
except that no air is drawn through them. Label these as blanks.
12. Filter Recovery and Final Weighing
12.1 24 hour Filter Equilibration Period
12.1.1 After sampling, filters are returned from the field as a complete batch. As the
filters are unpacked, the date received and the condition of the filters are noted on the
accompanying Field Data Sheet and laboratory logbook. The filter containers are then
placed on a tray with the covers loosened.
12.1.2 The trays are placed in a protected area of the filter room and allowed to
equilibrate for a minimum of 24 hours. Final weighing of a filter must be performed on
the same balance as the original weighing. The balance is zeroed and calibrated as before,
and date, relative humidity, temperature, blank mass, and tare mass are recorded on the
sample weighing form.
123, Filter Inspection
122.1 Scan the bar code label on the petri dish of the first 37 mm Teflon® filter to
be weighed.
1222 Using Teflon* tweezers, carefully remove the filter from its container.
1223 Inspect the filter for holes and tears. Enter any tear/hold or other comment
in the computer or on the Filter Data Sheet.
12.3 Final Weighing
12.3.1 Place the filter on the balance stirrup and close the balance door.
Revised 9/30/89 ~~ ~ Pa^e~18
-------
Method IP-10A Respirable Paniculate
1222 Press V and ENTER on the computer key board. Wait for the computer tone,
which indicates that weighing is completed. .
123.3 Open the balance door. Using tweezers, place the filter back into the
corresponding petri dish, cover, and stack for archiving.
12.3.4 Complete Sections 12.3.1 through 12.3.3 for each filter during the final weighing
process. After every tenth filter weighing, check the balance zero as in Section 9.2.2. The
electronic readout should be 00.000 ± 00.004 mg. Check the balance calibration with a 200
mg and a 90 mg calibration weight as in Section 9.2.3.
12.4 Independent Audit of Weighted Filters
12.4.1 Following the completion of a weighing session, a second individual as an
auditor should select 10 percent of the filters (minimum of two) for reweighing.
12.42 After all the selected filters have been reweighed, compare the final weights
recorded for each filter by the auditor and the primary operator.
12.43 If the difference between the two measurements for any filter exceeds 10 ng,
the session is declared invalid, and the filters must be reweighed.
12.4.4 If the difference in independent final weights is less than 10 /*g, the auditor
should enter his or her name into the computer, indicating valid weights. The 37 mm
Teflon* filters should then be archived for future evaluation.
13. Calculation
13.1 Mass of Particles found on the sample filter:
Ms = (mz - nij) - m3
where:
Ms = mass found on the sample filter
n^ = tare weight of the clean filter before sampling, ng
m2 = the weight of the sample-containing filter, Mg
m, = the mean value of the net mass change found on the blank filters, Mg
Note: The blank filters must be subjected to the same equilibrium conditions.
132 The sampled volume is:
Vs = Q x t/1000
where:
Vs = the volume of the air sampled, m
Q = the mean indicated flow rate of air sampled, L/min
t = the sampling time, min
1000 = conversion from L to m3
Note: There are no temperature or pressure corrections for changes in sampled volume
since it is critical that the flow rate required for the preclassifier be set at the time and
location of sampling. Additional adjustments to the tared filter weight may be necessary
Revised 9/30/89 " "
o
-------
Method IP-10A Respirable Paniculate
to improve the method's accuracy at very low filter weights. These can be developed by
re-weighing the blank tared filter weight periodically.
13.3 The concentration of the paniculate matter in the sampled air is expressed in micro
grams/m3.
C = K x MS/VS
where: 3
C = mass concentration of paniculate matter, /ig/m
K = a dimensionless correction factor for the preclassifier (supplied by the manufacturer
if not equal to 1.0)
Ms = mass found on the sample filter (see Section 13.1), pg
VSS = the volume of air sampled, (see Section 13.2), m
14. Sampling System Calibration
14.1 The primary calibration involve the MEM or PEM samplers with sampling head, a
bubble tube and pressure drop meters.
142 Assemble the calibration system as illustrated in Figure 5.
Note- Since the flow rate given by a pump is dependent on the pressure drop across the
sampling device (filter and inlet), the pump must be calibrated while operating with a
representative sampling inlet and filter.
143 Calibration of the sampling unit should be performed at approximately the same
temperature and pressure that the sample will be collected; otherwise, appropriate
temperature and pressure connections must be applied to the volume flow rate.
14.4 Place the sampling head, with the same type of filter to be used to collect the sample,
in the calibration test apparatus. Connect the sampling head to the outlet of the test
apparatus.
14 5 Turn on the pump and moisten the inside of the bubble meter by drawing bubbles
up the meter until the bubbles are able to travel the entire length of the buret without
bursting.
14.6 Adjust the sampling unit to provide the desired flow rate.
14.7 Start a soap bubble up the buret and measure with a stopwatch the time it takes the
bubble to pass through a graduation of 1.0 L.
14 8 Repeat Section 14.7 at least three times, calculate the flow rate by dividing the volume
of air between the preselected marks of the buret by the time required for the soap bubble
to traverse the distance and average the results. If the measure flow rate is outside the
specification, readjust as in Section 14.6, and repeat Sections 14.7 and 14.8.
Revised 9/30/89 20
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Method IP-10A Respirabie Particulate
14.9 Record the date of the calibration, the temperature, and barometric pressure at the
time of the calibration on the Field Data Sheet and in the laboratory notebook.
15. Method Safety
This procedure may involve hazardous materials, operations, and equipment. This method
does not purport to address all of the safety problems associated with its use. It is the
user's responsibility to establish appropriate safety and health practices and determine the
applicability of regulatory limitations prior to the implementation of this procedure. This
should be part of the user's SOP manual.
16. Performance Criteria and Quality Assurance (QA)
16.1 Standard Operating Procedures (SOPs)
16.1.1 SOPs should be generated by the users to describe and document the following
activities in their laboratory: assembly, calibration, leak check, and operation of hte specific
sampling system and equipment used, preparation, storage, shipment, and handling of the
sampler system, purchase, certification, and transport of standard reference materials and
all aspects of data recording and processing, including lists of computer hardware and
software used. . ,, ,
16.12 Specific stepwise instructions should be provided in the SOPs and should DC
readily available to and understood by the personnel conducting the monitoring.
162 Quality Assurance Program
The user should develop, implement, and maintain a quality assurance program to ensure
that the sampling system is operating properly and collecting accurate data. Established
calibration, operation, and maintenance procedures should be conducted on a regularly
scheduled basis and should be part of the quality assurance program. Calibration
procedures provided in Section 14, operation procedures in Sections 9-12, and maintenance
procedures in Section 10 of this method and the manufacturer's instruction manual should
by followed and included in the QA program. Additional QA measures (e.g., trouble
shooting) as well as further guidance in maintaining the sampling system are provided by
the manufacturer.
162.1 Sections 7.1 and 7.2 instruct the user to purchase instrumentation designed and
calibrated to fractionate the particles in the gas stream. _
1622 Section 7.1.8 requires sampling pump to be accurate to ±5% and maintain flow
to ±5% during the sampling period.
162.3 Section 7.4 requires the weighing room to be environmentally controlled:
relative humidity maintained at 40 ±2 percent and temperature set at 20 ±3°C. In
addition, a neutralizer is required to remove static charge on the filters.
162.4 Section 9.1.1 requires filters to be conditioned in the weighing room for at least
24 hrs. before initial and final weighing.
Revised 9/30/89 PaSe 21
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Method IP-10A Respirable Particulate
162.5 Section 9.2.2 requires the Cahn Microbalance to be zeroed and calibrated before
and after a weighing session. The zero should be 00.000 ±00.004 mg, while the calibration
should be within ±00.002 mg of standard.
162.6 Section 9.3.11 requires a check of zero after every tenth filter weighing.
162.7 Section 93.14 requires that the first filter weighed in any batch is the batch
blank. The blank filter is reweighed at the end of each batch and if it differs by more than
00.007 mg from the first weight, all filters must be reweighed. If by more than 00.005 mg,
then all filters back to the last zero are reweighed. _
16.2.8 All filters must be recorded on the Field Data Sheet with filter type, bar
number, filter identification and initial weight.
16.2.9 Section 112 requires an initial field flow check of the sampler.
162.10 Section 11.3.6 requires the run time to be within ±20% of estimated run time
162.11 Section 11.4 requires a final field flow check of the sampler. The initial and
final flow rates should be within ±10%. .
16212 Section 12.4 requires 10% of the filters (minimum of two) to be reweighed by
a second, independent person. Differences between the two can not be any greater than
10 /ig. If > 10 Mg, session is declared invalid.
162.13 The Cahn Microbalancer must be audited once per month.
162.14 Section 14 requires the total sampling system be calibrated m the laboratory
prior to field deployment. u^n,,*:™
16215 The latest copy of the Quality Assurance Handbook for Air Pollution
Measurement Systems (33) should be consulted to determine the level of acceptance of
zero and span errors. ,
162.16 For detailed guidance in setting up a quailty assurance program, the user is
referred to the code of Federal Regulations (8) and the EPA Handbook on Quality
Assurance.
17. References
1. Meszaros, E. "The Size Distribution of Water Soluble Particles in the Atmosphere,"
Idojaras (Budapest) 75:308-314, 1971.
2. National Academy of Sciences, Airborne Particles, 1977.
3. Fuchs, N. A., The Mechanics of Aerosols, Pergamon Press, New York, NY, 1964,408 pp.
4 U S Environmental Protection Agency, National Primary and Secondary Ambient Air
Quality Standards, Appendix B - Reference method for the determination of suspended
particulates in the atmosphere (high volume method), 40 CFR 50:12-16, July 1, 1979c.
5 Ferris, A. G., "Health Effect of Exposure to Low Levels of Regulated Pollutants - A
Critical Review," JAPCA, 28:482-497, 1978.
6. Dockery, D. W., and Spengler, J. D., "Indoor-Outdoor Relationships of Respirable
Sulfates and Particles," Atmos. Environ., 15:335-343, 1981.
Revised 9/30/89
Page 22
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Method IP-10A Respirable Paniculate
7. Mitchell, R. L, Williams, R., Cote, R. W., Lanese, R. R., and Keller, N. D., "Household
survey of the incidence of respiratory disease in relation to environmental pollutants," WHO
Symposium Proceedings: Recent Advance in the Assessment of the Health Effects of
Environmental Pollutants, Paris, June 24-28, 1974.
8. Federal Register Vol. 49, No. 55, Tuesday, March 20, 1984, Environmental Protection
Agency, 40 CFR, Part 53, Page 10430, Appendix J - Reference Method for the
Determination of Paniculate Matter as PM10 in the atmosphere, Proposed Rules Docket
No. A-28-43.
9. Hidy, G. M., and Brock, J. R., "An Assessment of the Global Sources of Tropospheric
Aerosols," Proceedings of the Int. Clean Air Congr. 2nd, 1970, pp. 1088-1097.
10. Hidy, G. M., and Brock, J. R., The Dynamics ofAerocolloidal Systems, Pergamon Press,
New York, NY, 1970.
11. Lee, R. E., Jr., and Goranson, S., "A National Air Surveillance Cascade Impactor
Network: Variations in Size of Airborne Paniculate Matter Over Three-year Period,"
Environ. ScL TechnoL, 10:1022, 1976.
12. Appel, B. R., Hoffer, E. M., Kothny, E. L., Wall, S. M., Haik, M., and Knights, R. L.,
"Diurnal and Spatial Variations of Organic Aerosol Constituents in the Los Angeles Basin,"
Proceedings: Carbonaceous Particles in the Atmosphere, March 20-22,1978, T. Novokov, ed.,
Lawrence Berkeley Laboratory, University of California, LBL-9037, 1979. pp. 84-90.
13. Nagda, N. L., Rector, H. E., and Koontz, M. D., Guidelines for Monitoring Indoor Air
Quality, Hemisphere Publishing Corporation, New York, NY, 1987.
14. Turner, W. A., Spengler, J. D., and Marple, V. A., "Indoor Aerosol Impactor," EPA
National Symposium on Recent Advances in the Measurement of Air Pollutants, Raleigh,
NC, May 1985.
15. Koontz, M. S., and Nagdo, N. L., "Exposure to Respirable Particulates: A Comparison
of Instrumentation for Microenvironmental Monitoring," Geomet Report Number IE-1624
January 21, 1986.
16. Marple, V. A., Rueon, K. L., Turner, W., and Spengler, J. D., "Low Flow Rate Sharp
Cut Impactors for Indoor Air Sampling: Design and Calibration," JAPCA, 37:1303-1307,
1987.
17. Marple, V., Liu, B., Behm, S., Olson, B., and Wiener, R. W., "A New Personal Impactor
Sampler Inlet," presented to The American Industrial Hygiene Conference, San Francisco,
CA, May, 1988.
18. Kamens, R., Wiener, R., Lee, C., and Leith, D., "The Characterizatin of Aerosols in
Residential Environments," Proceedings of the 1988 EPA/APCA Symposium on Measurement
of Toxic and Related Air Pollutants, May 1988, Raleigh, NC.
Revised 9/30/89 Page 23
77'
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Method IP-10A Respirable Particulate
19. Kamens, R., Lee, C, Wiener, R. W., and Leith, D., "A Preliminary Study to
Characterize Indoor Particles in Three Homes," Final Report to PEI, Inc., Cincinnati, OH,
Contract #790-87, 1988.
20. Wiener, R. W., "Measurement and Evaluation of Personal Exposure to Aerosols,"
unpublished, U.S. Environmental Protection Agency, Environmental Monitoring Systems
Laboratory, MD-56, Research Triangle Park, NC, 1988.
21 Riggin, R. M., Technical Assistance Document for Sampling and Analysis of Toxic
Organic Compounds in Ambient Air, EPA - 600/4-83-027, U.S. Environmental Protection
Agency, Research Triangle Park, NC, 1983.
22. Reischl, G. P., The Collection Efficiency of Impaction Surfaces: A New Impaction
Surface," Stave-Reinholt. Luft 38:55, 1978.
23. Spengler, J. D., Reed, M. P., Lebret, E., Chang, B. H., Ware, J. H., Speizer, F. E., and
Ferris, B. G., "Harvard's Indoor Air Pollution/Health Study," presented at 79th APCA
Annual Meeting, June, 1986.
24. Bowman, J. D., et al., The Accuracy of Sampling Respirable Coal Mine Dust," Draft
NIOSH Report, 1983.
25. Briant, J. K., and Moss, O. R., "The Influence of Electrostatic Charge on the
Performance of 10mm Nylon Cylones," American Industrial Hygiene Conference, Detroit,
MI, 1983.
26. Liu, B. Y. H., Pui, D. Y. H., and Rubow, K. L,, Characteristics of Air Sampling Filter
Media in Aerosols in the Mining and Industrial Work Environments, Vol. 3, Chapter 70, pp.
989-1038. V. A. Marple and B. Y. H. Liu, eds., Ann Arbor Science, 230 Collingwood, P.
O. Box 1425, Ann Arbor, MI 48106, 1983.
27. John, W., and Reischl, G., "Measurements of the filtration efficiencies of selected filter
types," Atmos. Environ., 12:2015-2019, 1978.
28. Liu, B. Y. H., and Lee, K. W., "Efficiency of membrane and mucleopore filters for
submicrometer aerosols," Environ. ScL Technol., 10:345-350, 1976.
29. Liu, B. Y. H., and Pui, D. Y. H., "On the performance of the electrical aerosol
analyzer," J. Aerosol Sci, 6:249-264, 1975.
30. Liu, B. Y. H., Pui, D. Y. H., Rubow, K L., and Kuhlmey, G. A., "Research on Air
Sampling Filter Media," University of Minnesota Particle Technology Laboratory Progress
Report EPA Grant R804600, Minneapolis, May, 1978.
31. Lundgren, D. A., Carter, L. D., and Daley, P. S., "Aerosol mass measurement using
Piezoelectric crystal sensors," Fine Particles: Aerosol Generation, Measurement, Sampling and
Analysis, B. Y. H. Liu, Ed., Academic Press, New York, 1976.
Revised 9/30/89 Page 24
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Method IP-10A Respirable Participate
32. "Particle Total Exposure Assessment Methodology (Particle-TEAM) Program," U.S.
Environmental Protection Agency, Research Triangle Park, NC, 27711.
33 Quality Assurance Handbook for Air Pollution Measurement Systems, Volume II, Ambient
Air Specific Methods, EPA 600/44-77-0272, May, 1977.
Revised 9/30/89 Pa8e 25
773 fi
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Method IP-10A
Respirable Participate
Table 1. Chemical Constituents of the Coarse/Fine Mode
Classification of Major Chemical Species
Associated with Atmospheric Particles
Fine
Fraction
(<2.5 am)
Coarse
Fraction
(2.5-10 urn)
Both Fine
and Coarse
Fractions
Variable
S04=, C (soot),
organic (con-
densed vapors),
Pb, NH4+, As,
Se, H+
Fe, Ca, Ti, Mg,
K, P04% Si, Al,
organic (pollen,
spores, plant
parts)
N03', CT
Zn, Cu,
Ni, Mn,
Sn, Cd,
V, Sb
Revised 9/30/89
Page 26
7X7
-------
Method IP-10A
Respirable Particulate
HOT
VAPOR
CHEMICAL CONVERSION
OF GASES TO LOW
VOLATILITY VAPORS
1
CONDENSATION
I
PRIMARY PARTCLES
LOW
VOLATILITY
VAPOR
I
HOMOGENEOUS
NUCLEATION
COAGULATION
i
CONDENSATION GROWTH
OF NUCLEI
WIND BLOWN DUST
+
EMISSIONS
+
SEA SPRAY
+
VOLCANOS
+
PLANT PARTICLES
0.002
ttl 1 2
PARTICLE DIAMETER, micrometer
. TRANSIENT NUCLEI OR
* AITKEN NUCLEI RANGE
4
ACCUMULATION fc
RANGE
4 M£c
MECHANICALLY GENERATED
AEROSOL RANGE
COARSE PARTICLES-
Figure 1. A Postulated Atmospheric Aerosol Formation Process
Revised 9/30/89
Page 27
7SS
-------
Method IP-10A
Respirable Paniculate
/
^^ ~
J- ,ft,l 1
U ,r,
/d
1 ( )
^^
I
• w -
i
i
f /
i
i
i
L
F'
j-
\
t
-<-
\
\
/
/-UPPER BODY
^^MPACTION PLATE
(with oil)
.-^-LOWER BODY
IMPACTION PLATE
(with oil)
/-37mm FILTER OR
/2"x2" FILTERSLIDE
jS*^
FILTER HOLC
t
'{
| v^uvcn
-\ y
V - J- IT II TC"P I.JOI T
". T_— ^ r ILI t.r< TtULL
\\ VA. RASE
U i(
Figure 2. Schematic of Microenvironmental Exposure Monitor (MEMs)
Revised 9/30/89 ~~ Pa8e 2S
-------
Method IP-10A
Respirable Paniculate
(c) Single hole version
Figure 3. Schematic of Personal Exposure Monitor (PEMs)
[Examples illustrate exploded view of multiple orifices (a and b) and single orifice (c)
approach. Each inlet consists of an impactor classifier, to remove particles larger than the
predetermined cut size, and a filter to collect the remaining particles.]
Revised 9/30/89
Page 29
-------
Method IP-10A
Respirable Particulate
DETERMINATION OF RESPIRABLE PARTICULATE MATTER
GENERAL
Project:
Site: _
Location:
Sample Code:
EQUIPMENT
Pump
Pump Model:
Serial No.:
Lab Calibration Date:
Flow Rate Set Point:
Calibrated by:
SAMPLING DATA
Start
Time:
Flow Rate:
Temperature:
Pressure:
Avg. Flow Rate: .
Date:
Location of Sampler:
Operator:
Sampler
Sampler: Particle fraction
MEM 2.5 fan
PEM 10.0 im
Both
Stop
Run Time:
(± 20% of estimate)
Total Sample Vol.:
Flow Maintained Rate:
(± 5%)
Time
Flow
Rate(Q)
mL/min
Ambient
Temperature
°C
Barometric
Pressure
mm Hg
Relative
Humidity,?.
Comments
Figure 4. Field Sampling Data Sheet
Revised 9/30/89
Page 30
-------
Method IP-10A Respirable Particulate
FILTER DATA
Filter I.D. No.:
Filter Bar No.:
Filter Case No.:
Filter Recorder in Laboratory Notebook:
WEIGHING ROOM
Atmosphere
Relative Humidity: 40 + 2%
Temperature: 20 ± 3*C
Neutralizer:
Activity
Filters conditioned at least 24 hours:
Cahn Balance Zero: ± 00.004 mg
After every 10™ filter:
Cahn Balance Calibrated
. 200 mg ___ ± 00.002 mg
. go mg ___ ± 00.002 mg
Blank filter weight: ,
Reweigh at end: ± 00.007 mg
10% of filters reweighed:
(no greater than 00.010
mg difference)
Cahn Balance last audited: (once per month)
Figure 4 (cont'd.). Field Sampling Data Sheet
Revised 9/30/89 Page 31
-------
Method IP-10A
Respirable Particulate
FLOW RATE
VALVE
1000 ml
BUBBLE
TUBE
SAMPLING HEAD
OR
TEST APPARATUS
AIR IN
DISH WITH
BUBBLE SOLUTION
PRESSURE DROP
METER (0-50 in H20)
PRESSURE DROP
VALVE
PUMP
Figure 5. Calibration Assembly for Personal Sampling Pump
Revised 9/30/89
Page 32
-------
Method IP-10B
DETERMINATION OF RESPIRABLE PARTICUIATE MATTER
IN INDOOR AIR USING A CONTINUOUS
PARTICUIATE MONITOR
1. Scope
2. Applicable Documents
3. Summary of Method
4. Significance
5. Definitions
6. Interferences
7. Apparatus
8. Assembly of Sensor Unit
9. Assembly of the Sensor Unit and The Data Processing
Unit
10. Exchanging The Filter Cartridge
10.1 Loading The Filter Cartridge
10.2 Removing The Filter Cartridge
11. Instrument Operation
11.1 Preparation of Computer
11.2 Instrument Start-Up
11.3 Instrument Shut-Down and Shipping
12. Instrument Variable Settings
12.1 Setting Sampling Parameters
12.2 Instrument Frequency Clipping
13. Confirmation of Instrument Calibration
14. Main Display Screen
14.1 Top Line of the Main Display Screen
14.2 Bottom Line of the Main Display Screen
14.3 X-Axis and Y-Axis Scales
14.4 Variables Selected for Plotting
14.5 Main Numeric Display
14.6 Automatic Execution Setting
15. Method Safety
16. Performance Criteria and Quality Assurance (QA)
17. References
Appendix - TP3 Programming
Revised 9/30/89 Page
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Method IP-10B
DETERMINATION OF RESPIRABLE PARTICUIATE MATTER
IN INDOOR AIR USING A CONTINUOUS
PARTICULATE MONITOR
1. Scope
1.1 This document describes the protocol for the Operation of a continuous paniculate
mass monitor which directly measures particulate mass at concentrations between 5 /ig/m
and several g/m3 on a real time basis.
12 The instrument calculates mass rate, mass concentration and total mass accumulation
on exchangeable filter cartridges which are designed to allow for future chemical and
physical analysis. In addition, the instrument provides hourly and daily averages.
13 The methodology detailed in this document is currently employed by such U.S. research
organizations as the Argonne National Laboratory, R J. Reynolds Tobacco Company and
Philip Morris, Inc. for indoor and outdoor air quality studies, aerosol behavior studies, and
cigarette smoke behavior studies.
2. Applicable Documents
2.1 ASTM Standards
D1356 Definitions of Terms Related to Atmospheric Sampling and Analysis
22 Other Documents
Technical Manuals (1-2)
Laboratory and Field Studies (3-12)
3. Summary of Method
31 Particle-laden air is drawn in through a heated air inlet followed by an exchangeable
filter cartridge, where the particulate mass collects. The inlet system may or may not be
equipped with the optional sampling head which pre-separates particles at either a 2.5 or
10 tan diameter.
32 The filtered air then proceeds through the sensor unit which consists of a patented
microbalance system and an automatic flow controller.
33 As the sample stream moves into the microbalance system (filter cartridge and
oscillating hollow tube), it is heated to the temperature specified by the software.
3 4 The automatic flow controller pulls the sample stream through the monitor at flow
rates between 0.5 and 5 Lpm. The hollow tube is attached to a platform at its wide end
and is vibrated at its natural frequency.
35 As particulate mass gathers on the filter cartridge, the tubes's natural frequency of
oscillation decreases. The electronic microbalance system continually monitors this
frequency.
Revised 9/30/89 Page 3
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Method IP-10B Respirable Paniculate
3.6 Based upon the direct relationship between mass and frequency, the instrument's
microcomputer computes the total mass accumulation on the filter, as well as the mass rate
and mass concentration, in real time.
3.7 The data processing unit contains software which allows the user to define the
operating parameters of the instrumentation through menu-driven routines.
3.8 During sample collection the program plots total mass, mass rate and/or mass
concentration on the computer screen in the form of scales. The program allows two y-axis
scales to be displayed and up to 10 variables to be plotted simultaneously. In addition, the
scales and variables used in plotting the data may be changed during collection without
affecting stored data. Figure 1 illustrates the assembled TEOM sensor unit and data
processing unit.
4. Significance
4.1 Suspended paniculate matter in indoor air is generally considered to consist of all
airborne solid and low vapor pressure liquid particles. Suspended particulate matter in
indoor air presents a complex multiphase system consisting of a spectrum of aerodynamic
particle sizes ranging from below 0.01 microns (/un) up to 100 /mi and larger. Historically,
measurement of particulate matter (PM) has concentrated on total suspended particulates
(TSP), with no preference to size selection. Research on the health effects of TSP in
ambient and indoor air has focused increasingly on those particles that can be inhaled into
the respiratory system, i.e., particles of aerodynamic diameter less than 10 /mi. It is now
generally recognized that, except for toxic materials, it is this fraction (< 10 /mi) of the total
particulate loading that is of major significance in health effects.
42 Particles are formed by two processes: 1) the grinding or atomization of matter (13-
14), and 2) the nucleation of supersaturated vapors. The particles formed in the first
process are products of direct emissions into the air, whereas particles formed in the second
process usually result from reaction of gases, then nucleation to form secondary particles.
Particle growth in the atmosphere occurs through gas-particle interactions, and particle-
particle (coagulation) interaction.
4.3 Recent studies (15-16) involving particle transport and transformation suggest strongly
that atmospheric particles commonly occur hi two distinct modes. The fine or accumulation
mode is attributed to growth of particles from the gas phase and subsequent agglomeration,
while the coarse mode is made up of mechanically abraded or ground particles. Particles
that have grown from the gas phase, either because of condensation, transformation or
combustion, occur initially as very fine nuclei 0.05 /an in size. These particles tend to grow
rapidly to accumulation mode particles around 0.5 /tm in size which are relatively stable in
the air. Because of their initially gaseous origin, this range of particle sizes includes
inorganic ions such as sulfate, nitrate, ammonia, combustion-form carbon, organic aerosols,
metals (Pb), cigarette smoke by-products, and consumer spray-products.
4.4 Coarse particles, on the other hand, are mainly produced by mechanical forces such as
crushing and abrasion. Coarse particles therefore normally consist of finely divided
Revised 9/30/89 ~~~ Pa8e 4
7/3
-------
Method IP-lOB Respirable Paniculate
minerals such as oxides of aluminum, silicon, iron, calcium, and
of soil or dust result from entrainment, by the motion of air or
action within their area. Since the mass of these particles is normally > 3 fan, their
retention time in the air parcel is shorter than the fine particle fraction.
4.5 The composition and sources of coarse particles are not as thoroughly studied as those
of fine particles. One reason is that coarse particles are more complex and similar in
chemical composition. It is possible, however, to recognize dozens of particle types, based
on microscopical examination; these range from soil particles, limestone, flyash, oil soot to
cooking oil droplets.
4.6 Outdoor concentrations of TSP, more specifically, are of major concern in estimating
air pollution effects on visibility, ecological and material damage However Pfople spend
the majority of their time inside buildings or other enclosures; ^*™£*£™<£££
therefore, indoor concentrations dominate average exposure. To the extent that mdoor
concenStions are different from the outdoors, population exposures are different from
those estimated by outdoor monitors.
4.7 Consequently, based upon the health effects of coarse and fine particulate matter a
continuous particulate monitor has been developed to allow mass measurement of
particulate concentration on a real-time basis.
4.8 The monitor utilizes the filter-based measurement system for providing real-time mass
monitoring capability.
5. Definitions
Definitions used in this document and any user prepared SOPs should be consistent with
ASTM D1356. All abbreviations and symbols are defined with this document at the point
of use.
6. Interferences
61 The instrument's primary operating mechanism is the microbalance system which relies
upon changes in the frequency of an oscillating tapered element to determine changes in
the particulate mass collected. Because of this characteristic the instrument .should b
isolated from mechanical noise as much as practical. It should be located in the area to
be measured so that external objects are not likely to contact or jar the instruments
enclosure or the air sampling tube. Additionally, the instrument should be located ini an
environment with nunimal temperature fluctuations. The unite can operate effectively in
environments with temperatures ranging between 12°C and 52°C.
62 Although the instrument may retrieve a sample from indoor or outdoor environments
it is important that the sample stream temperature is mauitained within as narrow bound,
as possible. Large abrupt temperature fluctuations (7-8°F/minute) of the sample stream
may cause measurement accuracy to decrease due to the inlet systems inability to adjust he
temperature of the sample to that specified by the software before travelling to the
microbalance system. Sample temperature can range from ambient to oiru
Revised 9/30/89 Page 5
-------
Method IP-10B Respirable Particulate
Note: For aerosols such as cigarette smoke that may contain substantial fractions of
dissolved semivolatiles, heating the aerosol may decrease the apparent mass and may
introduce errors into subsequent chemical analyses. As a precaution the TEOM may be
operated at low inlet temperatures (-30°C to 35°C).
7. Apparatus
The TEOM* Ambient Particulate Monitor is comprised of two main components (see
Figure 1): the TEOM* Data Processing Unit and the TEOM* Sensor Unit. However,
when purchased, these units are not fully assembled. Therefore, the following section
describes the components contained in these two main units which are available separately
as needed.
7.1 Enclosure cabinet - the enclosure cabinet (see Figure 2) houses a mass flow controller
with an inline filter cartridge and silicone tubing, an electronic circuit chamber with the
appropriate wiring for electricity and frequency signal output (inside left-covered by a
plexiglass board).
7.1.1 Located on the outside right panel are the power, signals, microcomputer
input/output and vacuum connections. The front of the metal door houses the ON/OFF
switch and the pressure gauge which controls the mass flow controller. The inside of the
door holds the silicone tubing which connects to the flow controller. The top wall of the
enclosure cabinet contains a square hole (-3 in.) in the left side into which the
sensor/preheater assembly fits.
1.12 The inside right side holds a toggle restraining clamp which secures the
sensor/preheater unit when moving the unit small distances (R&P proprietary product).
72 Sensor/preheater assembly - the sensor/preheater assembly (see Figure 3) consists of
the inlet and the microbalance.
72.1 The inlet consists of two concentric hollow (black) metal tubes. The outer tube
is -12" long and -3" in diameter. The tip of the outer tube is configured to accommodate
a 1/2" tubing for sampling or an additional sampling head, which separates particles by
diameter allowing either <2.5 /mi diameter or <10 /un diameter particles to enter the system.
The base of the outer tube is welded to a rectangular metal mounting plate which is fixed
to the top outside wall of the enclosure cabinet. The inner tube is connected to the outer
tube at only one location to allow the microbalance to be suspended in the enclosure
cabinet. The base of the inner tube is connected to the microbalance top outer wall. The
connection accommodates an air temperature probe assembly which controls the
temperature of the inner tube of the inlet.
722 The microbalance is a rectangular metal enclosure which houses a metal cylinder
(the sensor head) the size of the inner inlet tube. The metal cylinder contains an oscillating
tapered element, an electronic feedback system, and a filter cartridge. The tapered element
is attached to a platform at its wide end (bottom) and has a small metal tip onto which the
filter cartridge sits. The electronic feedback system consists of an amplifier board which
maintains the elements oscillation and the electronics which allow frequency signals to be
Revised 9/30/89 ~~ Pa8e 6
-------
Method IP-10B Respirable Particulate
transcribed to mass units. At the bottom of the microbalance, a silicone tube which is
connected to the mass flow controller, carries the air sample. Also attached to the bottom
is the electrical cord. When purchased the whole unit is accompanied by a hardware
manual which describes in detail the assembly and use procedures.
7.3 Filter cartridge - the filter cartridge (see Figure 4) is a half-inch diameter thin
aluminum base (foil-like) assembly. The foil is crimped around the filter edges to contain
it. Attached to the aluminum base is a water-resistant plastic cone which fits onto the
metal tip of the oscillating element.
7.4 Filter exchange tool - the filter exchange tool (see Figure 4) is ajour-inf? ^
aluminum tube. The lower part of the tool has two perpendicular cojnections The top
connection is an aluminum disc which is slightly smaller than one-hatf inch in diameter.
It is made to fit over the filter face when assembling and disassembling. The bottom
connection is a "U-shaped" fork. The tines of the fork straddle the cone of the filter
cartridge during assembling and disassembling.
7.5 Inline filter cartridge - standard filter cartridge, available from Fisher-Scientific.
7.6 Carbon-vane vacuum pump - oil-free pump with constant vacuum, available from
Fisher-Scientific.
7.7 Microcomputer and keyboard - recommended IBM-compatible. The software should
be able to plot real-time data on the screen and should give the user a number of options
for saving data on disk, printing data, or transmitting information to other devices using
analog o? digital signals. The use of both hard disk and floppy disk systems should be
available.
Note- The TEOM« is marketed and manufactured by Rupprecht and Patashnick Co., Inc.,
8c5porate Circle, Albany, NY, 12203. The following discussion addresses the receiving
and setting-up of the monitor.
8. Assembly of Sensor Unit
The TEOM* Sensor Unit consists of two components: 1) the enclosure cabinet, and 2) the
sensor/preheater assembly.
8.1 Remove both components from their shipping boxes. Set the enclosure cabinet upright
in the designated location for the required sampling. Try to locate the enclosure cabinet
at the source of the sample if possible (see Figure 2 for cabinet configuration).
Note- If the use of a sampling line cannot be avoided, keep its length to an absolute
minimum and avoid sharp bends. Sampling line will cause some reduction in particulates
reaching the microbalance. This, in turn, causing an underestimation of the sample content
to be made.
82 Lav the sensor/preheater assembly flat on a table so that the shipping brace (the angle
bracket painted red) faces upward. Remove the screws holding the shipping brace. When
L bracket is removed, the air preheater tube flexes and allows the TEOM« Sensor Head
Revised 9/30/89 Page 7
-------
Method IP-10B Respirable Particulate
to drop until the air preheater tube touches the outer (3" ID) tube. Figure 3 illustrates the
sensor/preheater assemblies.
83 Replace the cable and tubing support that connect the two side plates of the TEOM*
Sensor Head using the 8-32 x 1/2" screws that were removed.
8.4 Make sure the TEOM* Sensor Head restraining clamp (the small orange handled
toggle clamp) connected to the bottom right of the Sensor/preheater assembly is hi its open
(undamped) position.
8.5 Carefully lift the sensor/preheater assembly. Hold it so that the air preheater tube is
vertical and above the TEOM* Sensor Head. The long flange of the mounting plate
should face left (i.e., the handle for opening the TEOM« microbalance should face toward
you).
8.6 Carefully lower the sensor/preheater assembly through the square opening in the top
of the enclosure cabinet (see Figure 3), making sure that the ribbon cable and vacuum
tube precede the TEOM* Sensor Head through the opening, line up the holes in the
mounting flange with the threaded holes in the top of the enclosure, and secure with
provided #10-32 x 3/8" screws.
8.7 Route the ribbon cable over the top of the power supply cover, which is behind the
plexiglass printed circuit board cover, and plug its end (3-pronged) connector into the
mating 25 pin connector (P12) at the printed circuit board cover.
8.8 Push the 1/4" vacuum tubing into the two support clips on the side of the large acrylic
guard. Push the end of the hose over the free end of the inline filter which precedes the
mass flow controller.
Note: Observe that the sensor unit contains an inline filter cartridge to protect the mass
flow controller from being contaminated or blocked by particles contained in unfiltered air.
8.9 Check that the TEOM* Sensor Head is free to move in all directions-left, right, and
forward and back. This is necessary to isolate the Head from any outside vibrations (i.e.
it should be completely suspended within the enclosure cabinet). The only connection of
the Sensor Head is in the heated air inlet where the inner tube is connected to the outer
tube (see Figure 3).
9. Assembly of the Sensor Unit and the Data Processing Unit
9.1 Examine the front and side panels of the TEOM* Sensor Unit. Ensure that the power
switch located on the front panel (door) is off. This switch should not be turned on until
the TEOM* hardware is set up and Section 2 of the TEOM* Software Manual has been
read (see Appendix).
Note: The black panel on the right side of the sensor unit contains all the external
connections needed for power, signals, and vacuum pumps. Examine, also, the input/output
connectors located on the side and back of the microcomputer.
Revised 9/30/89 Pa8e 8
-------
Method IP-10B Respirable Particulate
92 Attach the black coaxial cable between the BNC connector on the TEOM* Sensor
Unit labelled "Freq Sig" and the BNC connector on the R&P Counter Board (see Figure
Note- The BNC connector marked "Freq Sig" transmits the frequency output from the
TEOM* Sensor Unit. The expansion card in the highest numbered slot (slot 4 in the
Compac II personal computer) is the R&P Counter Board. This board contains a BNC
connector for receiving the frequency signal from the TEOM* Sensor Unit. The nme-pin
connector located on this board is not used in the TEOM* Series 1200 Ambient Particulate
Monitor.
93 Attach the analog cable between the two 9-pin connectors on the TEOM« Sensor Unit
and the 37-pin connector on the analog board in the microcomputer.
Note- The nine-pin connectors allow analog data to pass between the TEOM* Sensor Unit
and the microcomputer. The expansion card in the next-to-highest numbered slot (slot 3
in the Compac II personal computer) is an analog input/output board with digital
input/output capabilities.
9.4 Attach a 3/16" (inside diameter) hose from the barbed hose connector on the right side
panel of the TEOM* Sensor Unit to the port of a suitable oil-free vacuum pump.
Note: The pump should be capable of maintaining approximately 20" Hg vacuum at a 4
Lpm flow rate. Pulsations from the vacuum line should be kept at a minimum. A small
carbon vane pump of 1/10 hp or greater is suitable. Place the sample pump away from the
TEOM« Sensor Unit to minimize the coupling of pump vibrations into the TEOM Sensor
Unit.
9.5 Attach the printer (optional) to the microcomputer with a parallel printer cable.
Note- The 15 pin "D" connector provides the user with analog input/output capabilities for
user defined functions. Three channels of analog input and output are available for
definition by the user. All analog signals are scaled from 0 to 5 VDC For example, the
user may choose up to three variables (such as mass concentration or total mass) to be
output to a chart recorder or data acquisition system by entering the appropriate value in
the Configuration Definition Routine (see Appendix or Section 6 of the TEOM* Software
Manual). It is also possible to input three independent signals (for instance humidity and
ambient temperature) into the TEOM* Sensor Unit. These inputs may be changed into
engineering units, and plotted and/or saved on disk simultaneously with the TEOM* data.
9.6 Attach the power cords to the TEOM* Sensor Unit and microcomputer. Plug the
power cords of the TEOM* Sensor Unit, microcomputer and optional printer into electric
sockets with the appropriate voltage. Contact R&P, your distributor or representative if you
have any questions about the voltage for which your instrument is configured. Do not apply
power until instructed to do so in Section 11.1 or in Section 2 of the TEOM* Software
Manual.
Revised 9/30/89 Pa«e 9
-------
Method IP-10B Respirable Particulate
10. Exchanging the Filter Cartridge
Upon arrival of a new TEOM* series 1200 Ambient Particulate Monitor, the
sensor/preheater unit will not be equipped with a filter cartridge. Therefore, it is necessary
to follow the filter exchange procedures outlined below to prepare the instrument for
operation. The new instrument comes with a box of 20 blank filter cartridges. Before
proceeding with the exchange, some special precautions must be taken:
• Do not exchange filter cartridges when the TEOM« Series 1200 Ambient Particulate
Monitor is taking data, i.e. when it is in the Collection Mode. Filter cartridges should
be exchanged either when the instrument is in the Initialization Mode, or when both
the TEOM® Sensor Unit and microcomputer are turned off.
. Do not handle new TEOM« filter cartridges with fingers. Use the filter tool provided
with the instrument to exchange filters.
• Keep the sample pump running to facilitate filter exchange.
10.1 Loading the Filter Cartridge
10.1.1 Locate the TEOM* microbalance lever with the black ball in the down position
(see Figure 3). Carefully rotate this lever upward. The TEOM* Sensor Head will swing
forward into its filter changing position, exposing the filter cartridge.
Note: When the TEOM* Sensor Head is in this open position, the tapered element
automatically stops vibrating to facilitate filter exchange.
10.1.2 Remove a clean filter cartridge from its shipping/storage box using the filter
exchange tool. The tools upper metal disc should cover the filter's surface while the lower
tines of the fork should straddle the hub of the filter base.
10.13 Hold the filter exchange tool in line with the tapered element and lightly insert
the hub of the filter cartridge onto the tip of the tapered element. Ensure that the filter
is seated properly. The tools metal disc should be centered over the filter before pressure
is applied. Apply downward pressure to set it firmly in place. This will reduce the chances
of distorting the crimped filter (see Figure 4).
10.1.4 Remove the filter exchange tool by retracting it sideways until it clears the filter.
Do not disturb the filter.
10.1.5 Gently move the ball-ended lever to the down position to close the head. Allow
the springs to pull it closed for the last centimeter so that the distinct sound of a metal-
to-metal contact is heard.
Note: Do not let the TEOM* microbalance slam closed from the full open position.
10.1.6 Close and latch the door to the instrument enclosure cabinet. Keep the door
open for as short a time as possible to minimize the temperature upset to the system.
10.1.7 Allow the unit to stabilize for one half-hour before taking data.
10.2 Removing the Filter Cartridge
Note: Filter lifetime depends upon the flow rate used, and the nature and concentration
of the paniculate sampled. The lower the flow, the longer the filter life. The filter lifetime
is determined by the pressure drop across the filter, as shown by the vacuum gauge on the
front panel of the TEOM* Sensor Unit. TEOM* filter cartridges must be exchanged when
Revised 9/30/89 ~~ Pagelo
-------
Method 1P-10B _ _ _ Respirable Particulate
the pressure drop reaches 15" Hg. This generally corresponds to a total mass accumulation
of 5 to 10 mg. The automatic flow controller inside the TEOM" Sensor Unit cannot
maintain the flow rate desired by the user when the pressure drop exceeds this level.
10.2.1 Using the filter exchange tool (see Figure 4), remove the filter cartridge from
the sensor head. Carefully insert the lower fork of the tool under the filter cartridge so that
the tines of the fork straddles the hub of the filter cartridge. The tool's upper metal disc
should be centered over the filter's surface but not touching it. Gently lift the filter from
the tip of the tapered element with a straight pull upwards.
Note: Never twist the filter cartridge to remove it or apply sideways force to the tapered
element (see Figure 4).
10.2 2 Store the used filters or discard as necessary. .
1023 Remove a clean filter cartridge from its shipping/storage box using the exchange
tool Grasp the clean filter as instructed in Section 10.1.2. Do not touch the filter cartridge
10.13 through Section 10.1.7 to insert
the clean filter cartridge onto the sensor head and restore the instrument back to the
operation mode.
11. Instrument Operation
Before the instrument start-up procedures are implemented, follow the instructions detailed
below or those through Section 2.5 of the TEOM« Software Manual.
11.1 Preparation of Computer
11.1.1 Hard disk systems - make sure that diskette drive A does not contain a diskette.
Remove any diskette that resides in diskette drive A. .
11 12 Floppy disk systems - insert the TEOM« Program Diskette in diskette drive A.
Insert the TEOM« Data Diskette or any formatted diskette with free storage capacity in
diskette drive B. . , , ,. ,<,
11.13 When TP3 is not automatically executed, then it can be executed through MS>-
DOS.
1LL3.1 For hard disk systems choose the proper disk drive: C: < Enter >; select the
appropriate subdirectory: CD \TP3 ; start Fpgram execution: TO^trument
Name - where InstrumentName is the model number of the TEOM« monitor,
such as 1200. For example, type TP3 /1200 to start executing TP3 for the TEOM
Ambient Particulate Monitor. ^.et«r*
11.13.2 For floppy disk systems choose the proper diskette drive: A: , start
program execution: TP3/Instrument Name - where Ir*tnimentName >x ,the : model
number of the TEOM« monitor, such as 1200. For example, type TP3 /1200 to start
executing TP3 for the TEOM* Ambient participate Monitor.
Note- If an improper instrument name is entered, the instrument informs the user witn a
special screen. In this case, the program halts execution and waits for the user to press any
Revised 9/30/89 ~ . Pa*e U
-------
Method IP-10B Respirable Paniculate
key before re-entering MS-DOS. If this condition is encountered, refer to Section 11.1.3.1
and/or 11.1.3.2 for instructions to re-start the program.
11.1.4 Once TP3 has begun execution, it displays a message for several seconds
indicating that it is loading additional files. The system screen is then displayed. This
screen gives information on the vendor. The next screen displays a copyright notice to the
user.
11.1.5 After this input, the computer shows the main display screen [see Figure 6(a)].
The precise layout of this screen can vary from one type of TEOM* instrumentation to
another. The mam display screen is displayed by the computer during nearly every phase
of instrument operation. All real-time data plotted and displayed by the instrument appear
on this screen. Figure 6(b) illustrates the components of the main display screen.
Note: Do not turn on power to the TEOM* Sensor Unit unless the preceding steps have
been taken and the TP3 software is running on the computer. Operating the instrument
while not under computer control may lead to overheating and damage.
112 Instrument Start-up
112.1 Turn on the TEOM* Sensor Unit at the power switch located in the lower right-
hand corner of the unit's front face.
1122 Turn on the sample pump. Allow 2 hours (24 hours for highest accuracy) for the
TEOM* monitor to warm up to its user-defined temperature set points and achieve its flow
rate before beginning data collection. Pre-filtered (Ballston Filter 9933-05-CQ) air should
be drawn through the instrumentation during the initial warm-up period. These filters are
the same diameter as the inlet of the outer metal tube and are very similar to the inlet
filter which precedes the mass flow controller. Each pre-filter fits directly onto the silicone
"sampling" tubing which covers the outer metal inlet. Other filters which are similarly made
can be used as long as they are demonstrated equivalent.
Note: The baseline performance of the TEOM* monitor hi terms of mass concentration
is shown in Figure 7. These data were taken after the device had operated continuously
for a long period of time, with pre-filtered air drawn through the system and under stable
ambient and sample stream temperatures. The data file shown in this figure is
1200BASE.PRN, which is provided as part of the instrument's software.
1123 Turn on the optional printer.
112.4 When a baseline is achieved similar to that of Figure 7, remove the pre-filter
from the heated air inlet-silicone tubing assembly while the vacuum is still being applied.
This initiates sampling.
113 Instrument Shut-Down and Shipping
113.1 Turn off the TEOM* Sensor Unit at the power switch located in the lower right-
hand corner of the unit's front face.
1132 Turn off the sample pump and the optional printer.
1133 When sampling at another location nearby, the sensor/ preheater assembly must
be secured before moving the Sensor Unit. Close the sensor head restraining clamp located
at the lower right side of the microbalance unit and inside right side of enclosure cabinet.
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Method IP-10B Respirable Particulate
This secures the sensor head to the side of the enclosure cabinet to prevent damage during
transport. . ,
Note: Do not transport the assembled sensor unit large distances or by commercial earner
in the assembled condition.
11.3.4 Transport the assembled sensor unit by hand or cart to the new sampling location.
Open the restraining clamp when the instrument is set up at its new location.
11.3.5 When transporting by commercial carrier, the sensor/preheater assembly must
be removed from the instrument enclosure cabinet. The reverse, of the assembly
instructions should be foUowed to disassemble the sensor unit components (see Section 8).
Each component should be packed separately in the original containers using suitable
packing materials such as foam or bubble wrap.
12. Instrument Variable Settings
12.1 Setting Sampling Parameters
The software provided with the TEOM* Series 1200 Ambient Particulate Monitor contains
three pre-defined configurations:
• plots mass concentration on the computer monitor during data collection
. plots mass concentration and 24-hour averaged mass concentration on the computer
monitor during data collection . .
. plots mass concentration and total mass on the computer monitor dunng data
collection ,. ,
All of these configurations store the date, time, mass concentration and. total mass on disk
when data files are created by the program. .
Note- Configurations U to Z are reserved for the TEOM* demonstration software. Do
not create configurations with these names. These configurations may be changed and new
configurations may be added by the user in the Configuration Definition Routine (Section
6 of the TEOM« Software Manual). Slots 13 to 18 of the Configuration Definition Routine
allow the user to change the values for operating temperatures and flow rate (See Appendix
or Section 6 of the TEOM» Software Manual). Since these settings are unique for each
type of TEOM* instrumentation, they are defined below specifically for the TEOM Senes
1200 Particulate Mass Monitor:
Configuration .
Line Description Permissible Ranee
13 Sample Flow Rate -5.0 to 0,
0.5 to 5.0 L/min
14 TEOM* Housing Temp 0, 25 to 60°C
15 Air Tube Temperature 0, 25 to 60°C
16 TEOM* Cap Temperature 0,25 to 6(TC
17 Enclosure Temperature 0, 25 to 50°C
18 Not Defined
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Method IP-10B Respirable Paniculate
The values of these settings are recorded in data files sorted on disk, and are also included
in the numeric printouts of data files enabled by the F2 key.
12.1.1 Sample flow rate (slot 13) - the sample flow rate is the rate (Lpm) at which the
paniculate-laden sample is drawn through the TEOM* monitor. A negative value causes
the flow controller to open its valve fully, allowing for external control of the flow rate. In
this case the instrument computes mass concentration based upon the absolute value of the
negative number entered. A value of 0 closes the valve of the flow controller, stopping the
sample flow through the system. A positive value between 0.5 and 5.0 L/min automatically
sets the flow controller to the entered flow rate.
12.12 Housing temperature (slot 14) - the value of this slot determines the temperature
at which the TEOM* housing in the Sensor Unit is to be maintained. A value of 0
specifies that the temperature of the TEOM» housing is not to be controlled. A value
between 25 and 60°C automatically causes the instrument to control the TEOM* housing
temperature at the indicated temperature.
12.13 Air tube temperature (slot 15) - the value of this slot determines the temperature
at which the sample air flow is maintained, as measured by a probe in the air stream. A
value of 0 specifies that the temperature of the air tube is not to be controlled. A value
between 25 and 60°C automatically causes the instrument to control the temperature of the
air at the indicated temperature.
12.1.4 Cap temperature (slot 16) - the value of this slot determines the temperature at
which the cap of the TEOM* microbalance is maintained. A value of 0 specifies that the
temperature of the cap is not to be controlled. A value between 25 and 60° C automatically
causes the instrument to control the temperature of the cap at the indicated temperature.
This value is normally set to be the same as the TEOM* housing temperature (Slot 14)
12.1.5 Enclosure temperature (slot 17) - the value of this slot determines the
temperature at which the interior of the enclosure is maintained. It should normally be set
to 45° C. A value of 0 specifies that the temperature of the enclosure is not to be
controlled. A value between 25 and 50° C automatically causes the instrument to control
the temperature of the enclosure at the indicated temperature.
122 Instrument Frequency Clipping
Because the TEOM* Series 1200 Paniculate Mass Monitor is ordinarily used to measure
relatively long term changes in paniculate concentrations, the instrument's clipping
capability is normally turned on.
122.1 The instrument's clipping routine is used to lessen the effects of outlying
frequency values (isolated "bad" data points) on mass calculations that can be caused by
mechanical or electrical disturbances. When the clipping capability is turned on, a "window
is formed around the average frequency value (adjusted for slope).
12.2.2 If the next raw frequency value lies within the window, the frequency value is not
affected and the span of the window is decreased by the decimal percentage prescribed by
"inclip" (see below).
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Method IP.10B Respirable Peculate
If the next raw frequency value lies outside the window, the fr^^ ^u*aw
de'S'percem^prScribed by "outclip" (see below). "Inclip" and "outclip"
Showing values in the TEOM« Series 1200 Particulate Mass Monitor.
Inclip 0.02
Outclip 0.02
13. Confirmation of Instrument Calibration
Note- The procedure below enables the user to confirm the calibration of the TEOM«
SbdSce set by the manufacturer, lliere is no. need for frequent calibration checks
^Them^s detection characteristics of the TEOM« system's tapered element do not
as the mass detection^cnara ^ ^^ used ^ th Automotwe
Sory ofT New York State Department of Environmental Conservation
™e calibration of the TEOM* monitor. The procedure allows the user to
curacv of the instrument's calibration constant, K,,, calculated by the
Solves a comparison of the mass indicated on a gravimetric.balance with
that indicated bv the TEOM« monitor for a given calibration mass. The calibration mass
ha SSIisk ofpilflex filter material 3 mm (l/8«) in diameter. ™^"^
to punch out circular Pallflex disks is a vacuum tweezer assembly which is also used to
transport the Pallflex discs.
13.1 Punch circular discs out of Pallflex filter paper (type T60A20) vsing the disc punching
instrument. A calibration dot 3 mm in diameter weighs approximately 100 mg.
133 Determine the mass of the calibration dot on a gravimetric laboratory balance that
has microgram sensitivity.
133 Establish a baseline for total mass on the microcomputer screen with the sample flow
rate set, for example, at 3 Lpm.
onto the center of the TEOM* filter cartridge. This is done
the vacuum tweezer. Close the TEOM« microbalance to
£
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Method IP-10B Respirable Particulate
13.7 Compare the masses determined gravimetrically and by the TEOM* system, and
calculate a revised calibration constant, K,,, if necessary:
K,, (revised) = K0 (original) x Mass (gravimetric)/Mass (TEOM* Monitor)
13.8 If desired, revise the calibration constant, K,,, stored in the TEOM* monitor.
14. Main Display Screen
Note: This section describes the commands that manipulate the information shown on the
main Display Screen. An understanding of this Section is important for the effective use
of the TEOM* monitor. Figure 8 identifies the components of the main display screen.
14.1 Top Line of the Main Display Screen
14.1.1 Current configuration - each configuration has a single-letter name ranging from
A to Z. When the computer is turned on, configuration A is automatically loaded into
memory (see Figure 8). If a listing of the current configurations is desired or if a different
configuration is to be loaded, consult Appendix for the correct procedures.
14.12 Operating mode - the operating mode indicates the current operating status of
the TEOM* monitor. The instrument runs in the following modes.
14.12.1 The instrument is in the Initialization (INTT) Mode when it is first turned on,
and after the main display screen has been cleared and the Initialization Mode chosen by
pressing F3_. .
14.122 The instrument collects, plots and displays mass rate, mass concentration and
total mass data when in the Collection Mode. Press £1 when in the Initialization Mode to
enter the Collection Mode.
14.12.3 The instrument enters the Stop Mode after data collection has been stopped
with the F2 key. The image on the main Display Screen may be printed while in the Stop
Mode by pressing F9.
14.12.4 In the Replot Mode the user may replay data files stored on disk. Enter this
mode by pressing F7 either in the Stop Mode (to replot the newest data file) or in the
Initialization Mode (to replot any data file stored on disk).
14.12.5 The FJ> key is used in the Stop and Replot Modes to print the image on the
main display screen. When the F9_ key is pressed while in the INTT Mode, the user may
choose to print the numeric contents of any data file stored on disk.
Note: Because of the time required to print a screen image or the contents of a data file,
the heating circuits in the TEOM* Sensor Unit are turned off during printing. The user
may have to allow for temperatures to stabilize again before resuming data collection.
14.13 Data file name - all data file names have a .PRN extension even though this is
not shown on the main display screen. This built-in program feature ensures file
compatibility with all versions of Lotus 1-2-3* spreadsheet software. A listing of data files
currently stored on disk may be obtained by entering ALT+D (hold down the ALT key and
press D) when in the INTT Mode.
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Method IP-10B Respirable Particulate
14.1.4 Current time - this part of the screen displays the current time of day. If this
clock time is incorrect, exit from TP3 into MS-DOS by pressing E1Q. Then type TIME
followed by . The computer then displays the current time and gives the user a
chance to enter a new time. Re-enter TP3 from MS-DOS by entering the commands shown
m lIlTcu^ent date - this part of the screen displays the current date. If tite date setting
is incorrect, exit from TP3 into MS-DOS by pressing F10, Then type DATE followed by
The computer then displays the current date and gives the user a chance to
enter a new date. Re-enter TP3 from MS-DOS by entering the commands shown in Section
11.1.
142 Bottom Line of the Main Display Screen
142.1 Yl-axis label - the Yl-axis Label displays the name of the variable whose scale
is shown on the left-hand Y-axis. The abbreviations used to designate variables are listed
m 14^22 Error code - this field indicates whether a hardware malfunction has been
detected by the instrument. An error code 0 represents no malfunction. The instrument
detects the following types of error conditions:
Error Code Description
0 No error condition
1 Error condition on R&P Counter Board
2 Error condition on analog input board
4 Error condition on analog output board
8 Error condition on digital input board
16 Error condition on digital output board
32 Unsupported programming feature used
64 Tapered element not oscillating or
improper cable attachment
In the case of multiple simultaneous errors, the error code consists of the sum of the
current error conditions. For example, the error code 65 indicates that an error condition
has been detected on the R&P Counter board (code 1) and that the computer is not
receiving a frequency signal from the TEOM« microbalance (code 64). Pressing F3_ resets
the error code to 0. . , ,
1423 Status code - the status code conveys information about the calculation ot data
and the amount of disk space available for saving data. This field is blank under most
operating conditions. A status code display most commonly occurs just after El has been
pressed m the INTT Mode to begin data collection (codes M and R). In this case, the
status display gives the user feedback that data collection has begun and indicates when the
computer has calculated the first valid data point. Because total mass, mass rate and mass
concentration calculations are based upon averaged raw data, a certain time elapses
between the start of data collection and the calculation of the first valid data point. Total
mass data are plotted and displayed as 0 until a sufficient number of raw frequency data
Revised 9/30/89 Page 17
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Method IP-10B _ _____ _ Respirable Particulate
points have been collected for calculation, likewise, mass rate and mass concentration data
are plotted and displayed as 0 until the appropriate number of total mass data points have
been processed.
Status Code Description
M Total mass, mass rate and mass concentration are plotted
and displayed as 0--data not yet valid.
R Total mass values are valid. Mass rate and mass
concentration are not yet valid, and are plotted and
displayed as 0.
D The data disk has reached its maximum capacity. The
current data file has been closed in an orderly fashion
but data are no longer being stored on disk.
blank Normal condition. If the instrument is in the Collection
Mode, total mass, mass rate and mass concentration data
are valid.
14.2.4 Y-axis selection - the arrow in this field indicates which Y-axis is the current
Y-axis, i.e., which axis is influenced by commands that change the display of Y-axes. If the
arrow points to the left, the Yl-axis (left) is the current Y-axis and is affected by Y-axis
commands. Conversely, if the arrow points to the right, the Y2-axis (right) is the current
Y-axis and responds to Y-axis commands. Press F5 to change the current Y-axis. This
command toggles between the Yl-axis and Y2-axis. The following Y-axis commands act
only upon the current Y-axis.
Command Results
Shift +Fn Display the selected Y-axis scale
Up Arrow, Shift Y-axis up/down by one division
Down Arrow
PG UP, PG DN Shift Y-axis up/down by one page
2, 5, 0 Expand Y-axis scale by factors 2, 5, 10
ALT+2, ALT+5, Contract Y-axis scale by factors of 2, 5, 10
ALT+0
Home Reposition Y-axis scale to center next Y-point
14.2.5 User input field - the user input field displays prompts and accepts inputs from
the user. A number of function key commands, such as O, EL Ei, E& and F1Q require
input from the user. When a prompt appears in the User Input Field, the instrument awaits
the user's input before continuing its operation. All user inputs must be followed^by
< Enter > in order to be accepted by the computer. Prompts which include the message "(Y
or N)" require that a Y or N be entered by the user followed by < Enter >. The F£
command allows the user to change the variables shown in the Main Numeric Display and
Short Numeric Display at any tune. After F£ is pressed the computer displays the message
Revised 9/30/89 Page
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Method IP-lOB Respirable Particulate
"Command:". In response, enter the location at which the variable is to be displayed
(explained below), followed by . The computer then prompts the user with fte
message "Entry:". Then type the Program Register Code for the desired variable (see Table
1), followed by . The location of the desired variable is determined by the
following codes:
Code Description
0 Short Numeric Display
1_42 Main Numeric Display. The Main Numeric Display may
contain up to 14 lines of information, with three variables
displayed per line. The locations are numbered from
bottom to top hi the following manner:
Code Description
Top Line . . •
• • •
10 11 12
789
456
Bottom Line 1 2 3
Note- Certain models of TEOM« instrumentation do not have a Main Numeric Display.
For example, the following key sequence causes raw frequency data to be displayed in the
Short Numeric Display:
Ffi 0 < Enter > 86 < Enter >
142.6 Short numeric displays - this field displays the current value of a variable selected
by the user. Variables may be displayed at this location in two ways:
• follow the procedure described above in Section 14.2.5, or
. If the variable to be shown in the short numeric display is represented by a function
key enter CTRL + Fn (hold down CTRL and press the desired function key), .bor
example, enter CTRL + F5 to show real-time mass rate values in the short numeric
display.
142.7 Y2-axis label - the Y2-axis Label displays the name of the variable whose scale
is shown on the right-hand Y-axis. The abbreviations used to designate variables are listed
in Table 1.
143 X-Aris and Y-Axis Scales
Figure 8 identifies the location of the X-axis and Y-axis scales of the main display screen.
1431 X-axis scale - the X-axis scale always displays time. By making the appropriate
selection in the configuration definition routine (see Appendix), time can be displayed as
either the elapsed time of data collection or time-of-day. The format may be either
hh:mm:ss (hours:minutes:seconds) or dd:hh:mm (days:hours:minutes). The span ot the
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Method IP-10B Respirable Particulate
X-axis scale may be changed in the Initialization, Collection and Replot Modes in the
following manner:
Command Result
Left Arrow, Decrease/increase span by a
Right Arrow factor of 2.
CTRL + Left Arrow, Decrease/increase span by
CTRL + Right Arrow increments determined by the
program.
These commands may be entered in any order and as often as desired. When they are
used in the Collection or Replot Modes, the graphical display area is cleared.
1432 Y-axis scales - the main display screen can display as many as two Y-axis scales
at the same time. The Yl-axis is located to the left and the Y2-axis to the right of the
bottom line of the main display screen (Section 14.2.4). A number of commands may be
used to change the current Y-axis scale (see 14.2.4). These commands all function in the
Initialization, Collection and Replot Modes.
1432.1 For examples, follow these steps to display the scale for mass concentration
on the Y2-axis: 1) press F_5, if necessary, to point the Y-axis selector toward the Y2-axis,
and 2) enter SHIFT + F6 to display the mass concentration scale. This command is a
toggle switch. Executing it again turns off the current Y-axis scale.
14322 The Up Arrow. Down Arrow. PGUP and PGDN commands allow the user
to reposition variables vertically by shifting the scale of the current Y-axis either up or
down. These keystrokes may be pressed in any order and repeated as often as desired.
14323 The 2, 5, Q, ALT +2. ALT +5 and ALT + 0 commands change the scaling
of the current Y-axis by factors of 2, 5, and 10. They may be executed in any order, and
as often as desired.
1432.4 The Home command is useful when a plotted variable such as total mass is
about to go off the screen. Pressing Home in this case repositions the current Y-axis scale
so that the next data point is plotted in the middle of the screen.
14.4 Variables Selected for Plotting
The variables currently selected for plotting in the Collection and Replot Modes are shown
directly above the graphical display area (see Figure 8). These settings may be turned on
and off any time the main display screen appears on the monitor. Variables may be added
to or deleted from the list of plotted variables by entering an appropriate ALT +Fn
command. For example, press ALT + F6 to add or subtract mass concentration from the
list of plotted variables.
14.5 Main Numeric Display
This field displays the current values of selected variables. Its format varies from one
model of TEOM® instrumentation to another. The main numeric display may be scrolled
Revised 9/30/89 Pa8e 20
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Method IP-10B Respirable Particulate
up and down using the CTRL + UP and CTRL + DN commands. The variables shown
here may be changed by the user according to instructions in Section 14.2.5.
14.6 Automatic Execution Setting
The operation of the TEOM« monitor may be directed from a remote location using the
digital input capability of the computer. When the automatic execution setting is on, the
TEOM» monitor executes the steps of the instrument cycle according to the values ot
digital inputs 0 and 1. The instrument's automatic collection capability may be turned on
and off only in the Initialization Mode. Enter ALT + A to toggle this remote operation
ability on and off (see Figure 9). The value of digital inputs 0 and 1 cause the instrument
to execute the following steps of the instrument cycle when the automatic execution
capability is turned on:
Digital Digital
Input 0 Input 1 Description
0 0 The instrument awaits a digital input
1 0 Corresponds to Fl: Begin data collection, enter Collection
Mode
0 1 Corresponds to F2: Stop data collection, enter Stop Mode
1 1 Corresponds to FjJ (when in Stop Mode): Clear screen,
enter INTT Mode or
Corresponds to F2 and E2 (when in Collection Mode): Stop
data collection and clear screen, enter INTT Mode.
Generally, a digital input of 0 corresponds to ground, while an input of 1 refers to 5 VDC.
Allow up to 5 seconds for the instrument to respond to the above digital input commands.
These settings and the locations of the inputs can vary from one type of TEOM monitor
to another. Refer to the TEOM« Hardware Manual, or consult with R&P or your
distributor, to determine the location and proper handling of these digital inputs.
15. Method Safety
This procedure may involve hazardous materials, operations, and equipment. This method
does not purport to address all of the safety problems associated with its use. It is the
user's responsibility to establish appropriate safety and health practices and determine the
applicability of regulatory limitations prior to the implementation of this procedure. I his
should be part of the user's SOP manual.
16. Performance Criteria and Quality Assurance (QA)
Required quality assurance measures and guidance concerning performance criteria that
should be activated within each laboratory are summarized and provided in the following
section.
Revised 9/30/89 PaSe 21
8/3
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Method IP-10B Respirable Particulate
16.1 Standard Operating Procedures (SOPs)
16.1.1 SOPs should be generated by the users to describe and document the following
activities in their laboratory:
• assembly, calibration, leak check, and operation of the specific sampling system and
equipment used;
• preparation, storage, shipment, and handling of the sampler system;
• purchase, certification, and transport of standard reference materials; and
• all aspects of data recording and processing, including lists of computer hardware and
software used.
16.12 Specific stepwise instructions should be provided in the SOPs and should be
readily available to and understood by the personnel conducting the monitoring work.
162 Quality Assurance Program
The user should develop, implement, and maintain a quality assurance program to ensure
that the sampling system is operating properly and collecting accurate data. Establish
calibration, operation, and maintenance procedures should be conducted on a regularly
scheduled basis and should be part of the quality assurance program. Calibration
verification procedures provided in Section 13, operation procedures in Section 11,, and the
manufacturer's instruction manual should be followed and included in the QA program.
Additional QA measures (e.g., trouble shooting) as well as further guidance in maintaining
the sampling system are provided by the manufacturer. For detailed guidance in setting up
a quality assurance program, the user is referred to the code of Federal Regulations (18)
and the EPA Handbook on Quality Assurance (19).
17. References
1. Rupprecht & Patashnick Co., Inc., TEOM9 Hardware Manual (TEOMPLUS9 Software
Version 3), Albany, NY, April, 1988.
2. Rupprecht & Patashnick, Co., Inc., TEOM9 Mass Monitoring Instrumentation: TEOM9
Software Manual (TP3), Albany, NY, April, 1988.
3. Patashnick, H., and Rupprecht, G., "Microweighing Goes on Line in Real Time,"
Research & Development, June, 1986.
4. Patashnick, H., and Rupprecht, G., "Advances in Microweighing Technology," American
Laboratory, July, 1986.
5. Walters, S., "Clean-up in the Colliery," Mech. Eng., 105:46, 1983.
6. Whitby, R., et al., "Real-Time Diesel Particulate Measurement Using a Tapered Element
Oscillating Microbalance," Soc. Automotive Eng., Paper 820, 463, 1982.
7. Whitby, R., Johnson, R., and Gibbs, R., "Second Generation TEOM* Filters: Diesel
Particulate Mass Comparison Between TEOM* and conventional Filtration Methods," Soc.
Automotive Eng., Paper, 850, 403, 1985.
Revised 9/30/89 Pa8e 22
$/
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Method IP-lOB Respirable Particular
8 Hales, J. M., and May, M. P., Transient Cycle Emissions Reductions at Ricardo -1988
and Beyond," Soc. Automotive Eng., Paper 860, 456, 1986.
9 Patashnick, H and Rupprecht, G., "A New Real Time Aerosol Mass Monitoring
LSmtnr %ie'TEOM«; Proc: Advances in Particulate Sampling and Measurement,
Daytona Beach, FL, 1979, EPA-600/9-80-004.
10. Wang, J. C. R, Patashnick, H., and Rupprecht, G, "New Real Tm>e Isokinetic Dust
Mass Monitoring System,"/. Air Pollution Control Assn., 30(9):1018, 1980.
11 Wang J C F et al "Real-Time Total Mass Analysis of Particulates in the Stack of
an industrial'power PlamV'/. Air Pollution Control Assn., 33(12):1172, 1983.
12. Patashnick, H., Rupprecht, G, and Schuerman, D. W., "Energy Source for Comet
Outbursts," Nature, 250(5464) July, 1974.
13. Hidy, G. M, and Brock, J. R., "An Assessment of me Global Sources of Tropospheric
Aerosols", Proceedings of the Int. Clean Air Congr. 2nd, 1970, pp. 1088-1097.
14 Hidy, G. M, and Brock, J. R., The Dynamics of Aerocolloidal Systems, Pergamon Press,
New York, NY, 1970.
1S T£e R E Jr and Goranson, S., "A National Air Surveillance Cascade Impactor
Network: V^tions^a SizTc^ Akbo'rne Particulate Matter Over Three-Year Period,"
Environ. ScL Technol, 10:1022, 1976.
16 Appel, B. R, Hoffer, E. M., Kothny, E. L., Wall, S. M., Haik, M., and Knights;, RM,
•Siumaland Spatial Variations of Organic Aerosol Constituent in *e ^f^^
Proceedings: Carbonaceous Particles in the Atmosphere March 20-22 1978^ T. Nonokov,
ed., Lawrence Berkeley Laboratory, University of California, LBL-9037, 1979, pp. 84 yu.
17' Nagda, N. L., Rector, H. E., and Koontz, M. D., Guidelines for Monitoring Indoor Air
Quality, Hemisphere Publishing Corporation, New York, NY, 1987.
18. 40 CFR, Part 58, Appendix A, B.
19 Quality Assurance Handbook for Air Pollution Measurement Systems, Volume II -
Ambient Air Specific Methods, EPA 600/4-77-0272, May 1977.
Revised 9/30/89 Page
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Method IP-10B
Respirable Participate
Table 1. Program Register Codes
Code Title Description Comments
Mass Rate
80
83
MROO
MR
Mass Concentration
81 MCOO
84 MC
Total Mass
82 TMOO
85 TM
TE Frequency
86 FROO
87 FR01
88 FR
89 SD
Clipping
97
98
CLIP
CLWI
Time and Date
90 XTIM
91
92
93
REPS
CTIM
CDAT
Diagnostics
95 ERR*
Mass Rate (g/sec)
Mass Rate (g/sec
or selectable)
Mass Cone
Mass Cone (mg/m
or selectable)
Total Mass (g)
Total Mass (g or selectable)
Use for disk storage
Use for plotting and
printing
Use for disk storage
Use for plotting and
printing
Use for disk storage
Use for plotting and
printing
Use for disk storage
Raw Frequency (Hz)
Clipped Frequency (Hz)
Average Frequency (Hz)
Std Dev of Frequency (10 sec) Indicates stability of
instrument
Clipping Indicator
Size of Clipping Window (Hz)
Current Experimental Time
(sec)
Calculation Repetitions
Clock Time
Clock Date
Current Error Code
0 = Inactive; 1= Active
Automatically saved on
disk
Number of program loops
Format: O.HHMMSS
(hours, min, sec)
Format: O.MMDDYY
(month, day, year)
Automatic
148
149
Instrument Operation
D100 Digital Input 0
D101 Digital Input 1
With instrument in
Automatic Setting, these
inputs control operation
TP3 refers to variables (such as mass concentration) by numbers called Program
Register Codes. These Program Register Codes are common to all TEOM®
instrumentation. Certain TEOM® monitors make use of additional codes.
Consult Appendix A of the TEOM® Hardware Manual for a complete listing of
codes applicable to your particular TEOM® instrument model.
Revised 9/30/89
Page 24
-------
Method IP-10B Respirable Particulate
Table 2. Description of Stored Data Files
Line(s) Description
1 The time and date at which the data collection cycle was begun,
expressed Tn the following format: 1 + mmddyyhhmm (1 + month, day,
year, hour, minute).
2 The unique calibration constant for the TEOM® monitor It is used
during replotting to calculate total mass, mass rate and mass
concentration from raw frequency data stored ,°" dl.snk:triim!ni
calibration does not change during the lifetime of the instrument.
3 The rate at which the computer gathers raw frequency data from the
TEOM® Sensor Unit. Typical instrument settings are one data point
every 1.68 and every 0.21 seconds.
4 The rate at which data are saved to disk in seconds.
5 The length of time over which raw frequency data are averaged to
compute total mass values.
6 The length of time over which total mass values are averaged to
compute mass rate and mass concentration.
7-12 Instrument settings such as the sample flow rate and temperatures
The definition of these settings can vary from one type of TEOM®
instrument to another.
13-20 The Program Register Codes (see Table 1) and names of the variables
stored in columns 1-8 of the data file.
Revised 9/30/89 Page 2S
k
-------
Method IP-10B
Respirable Participate
DATA PROCESSING
UNIT
Figure 1. Assembled TOEM® Continuous Particulate Monitor
Revised 9/30/89
Page 26
-------
Method IP-10B
Respirable Particulate
Ribbon
Cable
Vacuum Tubing
Support Clips
Plexiglass
Printed Circuit
Board Cover
Automatic Mass
Flow Controller
Figure 2. Enclosure Cabinet
Revised 9/30/89
Page 27
-------
Method IP-10B
Respirable Particulate
FILTER
CARTRIDGE
OSCILLATING
TUBE
MICRO
BALANCE
SYSTEM
AIR-TEMP
PROBE
ASSEMBLY
FILTER
EXCHANGE
LEVER
RIBBON CABLE
3- PRONGED CONNECTOR
Figure 3. Sensor/Preheater Assembly
Revised 9/30/89
Page 28
-------
Method IP-10B
Respirable Particulate
Filter
Exchange
Tool
REMOVAL
Figure 4. Loading/Removing Filter Cartridge Assembly
Revised 9/30/89
Page 29
-------
Method IP-10B
Respirable Particulate
P16
Barbed
Hose Fitting
(Vacuum Pump)
Fuse
DATA PROCESSING
UNIT
Compaq II
Expansion Slots
Figure 5. Electrical Connections Associated with the
TEOM® Sensor Unit and Data Processing Unit
Revised 9/30/89
Page 30
-------
Method IP-10B
Respirable Particulate
1
\
A J IHIT J ] TO** Monitor [ 13:45:36 J 03-31-1988 ]
MR
7.500E-08 •
0:00:00 0:02:00 0:OU:00 0:06:00
[* i °l H 1 i J
Mode I
" f A I ca
l.OOOE-0
7.50OE-C
S.OOOE-0
2.3001-0
O.OOOE+0
-2.500E-0
0
I-
idieator
Data F
J.J IES
(a) Main Display Screen
Lie Naoe
Plottwl Variable
01 1
IB3M* Monitor f 13:M:3S J 03-31-1988
' KR
:00:OO 0:02:00
-rp
; 1 > 1
0:04:00 0:06:00
i 1
Status Indicator Dier Input Fi«ld
(b) Components of the Main Display Screen
Figure 6. TEOM® Display Screen
Revised 9/30/89
Page 31
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Method IP-10B
Respirable Particulate
T12MSE 1 ™* ftHl)ient Honitop f14l|B7!i7 T
HC
80,000 •
60,060 •
40,000 •
20,000 '
0,666 •
-20,000 '
0,0;
HMNI*MHH**NHmtMI«MMMIIHI*MMHI*NIIHI*>IHM»HI*MMH
M**MHm*M*imilfll»HN«MM*Hlf«*l*HMIfMMI*MMMMMI*MltH
T" '* ^f»«nt "yuitftr*
):00 0,16:00 1,0!
i t iv j^Aj-Tfl/VT.
3:08 1,08:68
XTIH 109335 CLIP 0 CLWI 8.0TO8
T3 0,06 FLOW 6,00 SD 8,08E+88
HC 1 01 l< 1 1 J
Figure 7. Baseline Performance of the TEOM® Monitor
Revised 9/30/89
Page 32
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Method IP-10B
Respirable Particulate
Yl-Axis
Main Numeric
Display
Yl-Axis Label
Current Configuration
Operating Mode
Data File Name
Current Date
Current lime
I A T CPU. [
Instrument Name
TEST01
1 TEOM* Monitor [ I3:h5;36 j 03-31-1988 [
MR
TM
l.OOOE-07
7.500E-08
5.000E-08
2.500E-08
O.OOOE+00
-2.500E-08
0:00:00
0:02:00
0:0b:00
l.OOOE-OS
8.000E-06
6.000E-06
4.000E-06
2.000E-06
O.OOOE+00 '
0:06:00
MR
tTT
O.OOOE+00
MC O.OOOE+00 TM O.OOOOE+00
0 I M I < ICommand: 0 Entry: 86| HC +O.OOOE+00 | TH
User Input Field
Y-Axis Selection
Status Code
Error Code
Short Numeric Display
Y2-Axis
Y2-Axis Label
Figure 8. Components of the Main Display Screen
of the TEOM® Particulate Monitor
Revised 9/30/89
Page 33
-------
Method IP-10B
Respirable Participate
Automatic Collection Capability Turned On
Graphical
Main Numeric
Varis
[ A I INIT T 1
AUTO
bles Selected for Plott
TEOM* Monitor
1 MR TM-
0:00:00 0
O.OOOE+00
MR | 0 1 H 1 < 1
ing
1 U:l>5:36 T 03-31-1988 1
AUTO
-.02:00 0:0l>:00 0:0
MC O.OOOE+00
8.000E-06
6.000E-06
ii.OOOE-Oe
2 OOOE-06
0 OOOE+OC
TM O.OOOOE+00
1 MC +O.OOOE+00 1 TM
— -
Y2-Axis Scale
X-Axis Scale
Figure 8. Components of the Main Display Screen
of the TEOM® Particulate Monitor (cont'd)
Revised 9/30/89
Page 34
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Method IP-10B, Appendix __ Respirable Paniculate
TP3 Programming
1. Description of the Instrument Cycle
This Section describes the steps involved in executing the instrument cycle of the TEOM«
monitor. The instrument cycle is composed of the following modes:
Initialization Mode (INIT) The instrument is in the INTT Mode when it is switched
initialization Moae ^ j ^ ^^ ^ been deared
Collection Mode (COLL) During the COLL Mode the TEOM« monitor collects
collection jviouc ^ ; ^^ ^ ^& concentration and total mass data. The
instrument plots and displays the information on the
screen and saves data on disk.
Stoo Mode (STOP) The instrument enters the STOP Mode after the user
btop Moae ^iur, ^ instructed the computer to stop data collection. In
this mode, the user can print an image of the main
display screen for future reference. After the screen is
cleared in the STOP Mode, the monitor returns to the
INIT Mode.
The function key commands used to switch the instrument from one operating mode to
another are shown below:
Fl INIT Mode ------ > COLL Mode
F2 COLL Mode ------ > STOP Mode
F3 STOP Mode ------ > INIT Mode
Note: There is a Quick Reference Card which is supplied with the TEOM« monitor when
purchased which provides a convenient summary of commands.
1.1 Executing the Instrument Cycle
Execution of these commands can only be done if the computer is equipped with the
appropriate expansion boards.
1.1.1 Data collection (enter COLL Mode) -press El to start data collection. Entry into
the COLL Mode is indicated by the mode indicator on the top line of the main display
screen [see Figure 6(b)]. In this mode, the instrument collects, plots and displays mass rate,
mass concentration and total mass data. .
Hole: If the instrument is configured to save data on disk, it requeste a data _ file name m
rteUser Input Field after El is pressed. In this case, enter one of these options followed
by < Enter >.
Revised 9/30/89 Page 35
-------
Method IP-10B, Appendix Respirable Particulate
• A data file name up to 8 characters long composed only of letters and numbers
• The number Q. In this case the computer automatically assigns a data file name
according to the present date and time in the format:
mmddhhmm.PRN
where:
mm is the current month
dd is the current day
hh is the current hour
mm is the current minute
1.1.1.1 If the instrument is successful in creating-the data file, the file name appears
on the top line beside the COLL cell, of the main display screen [see Figure 6(b)]. All data
files written by TP3 are given the extension .PRN for direct use with Lotus 1-2-3*
spreadsheet software.
1.1.1.2 The Status Code on the bottom of the screen shows that data collection has
begun. The status code M indicates that data collection has begun, but that the first total
mass data point has not yet been calculated. A status code R means that total mass data
are being computed, but that valid mass rate and mass concentration data have not yet been
generated, the delays in computation are due to the averaging times selected for total
mass, mass rate and mass concentration in the current configuration.
1.1.13 A blank status code indicates that valid data are being calculated for total
mass, mass rate and mass concentration. If the status code D appears, the data disk has
run out of capacity and data are no longer being saved. The program always closes data
files in an orderly manner so that they are available for later evaluation
1.1.1.4 The variables plotted on the main display screen are indicated by the variable
names shown just above the graphical display window of the main display screen. The
definitions of the variable names may be found in Table 1.
1.1.2 Stop data collection (enter STOP Mode) - press F2 to stop data collection. Entry
into the STOP Mode is indicated by the Mode indicator on the top line of the main display
screen [see Figure 6(b) - STOP should replace COLL]. In this mode, the user may print
an image on the main display screen by pressing F9_. The user also has the option of
returning to the INTT Mode or entering the Replot Mode.
1.1.3 Printing or restarting (enter INIT Mode) - press F3 to clear the screen and enter
the INIT Mode. If data were stored on disk during the COLL Mode, the instrument asks
the user in the User Input Field if he wants to enter the INIT Mode. Enter Y followed
by < Enter > in response to this prompt to enter the INIT Mode. Entry into the INIT
Mode is indicated by the Mode Indicator on the top line of the main display screen. From
the INIT Mode, the user is able to execute commands to print data files, replot data, start
another instrument cycle, or exit from the program. Refer to this Appendix, Section 1.1
to begin another instrument cycle.
Revised 9/30/89 Page 36
-------
Method IP-10B, Appendix __ Respirable Particulate
12 Exiting the Program
The instrument must be in the INTT Mode to stop program execution and enter MS-DOS
Press F10 to exit from TP3 and enter MS-DOS. The instrument then asks in the user Input
Field whether you want to exit from the program. Enter a Y followed by to leave
sure that power has been turned off at the TEOM« Sensor Unit when the unit
is not being controlled by the TP3 software.
2. Using Stored Data
2.1 Storage Format
All data files created by TP3 have the following attributes: t
. The file name may be up to 8 characters long (letters and numbers), and is followed
by the extension .PRN. ., , . , ._, f
. Data files are stored in ASCII format, making them compatible with a wide range of
commercially-available spreadsheet and word processing software. The files can also
be read by programming languages such as BASIC, C and Pascal.
. The first 20 lines of each data file convey descriptive information about the
instrument's hardware and software settings. .
. The remaining part of the data file is made up of two or more columns containing
real-time values for the variables stored on disk. The first column always contains the
experimental time in seconds. *,-,,. j «i A
Table 2 lists the information contained in the 20 lines of the data files, the data file named
BASELINE.PRN is provided in the C/TEOMDATA subdirectory (hard flsk systems) or
on the TEOM* Data Diskette (floppy disk systems). The subdirectory C:\TP3 i (or toe
provided floppy) also contains a LOTUS 1-2-3" template spreadsheet name AUTO3.WK5>
to aid in date analysis. The customer must own a copy of LOTUS 1-2-3® software to use
the provided template file.
22 Replotting Stored Data in TP3
2.2.1 Data files may be replotted within the TP3 software by entering the Replot Mode.
Data points may be replotted only if they have been saved on diskette or hard disk. The
setting that causes the computer to store data on disk is part of the instruments
configuration. This parameter may be changed by entering the Configuration Definition
Routine from either the INTT or Replot Mode.
222 The Replot Mode can be entered from either the STOP Mode or the INIT Mode.
Press EZ when in the STOP Mode if the data file currently in the computer's memory is to
be replotted. The TEOM* monitor enters the Replot Mode after this command is
executed Press EZ when in the INIT Mode to load a data file for replotting into the
computer's memory. Then enter the name of the data file to be replotted (without the
extension .PRN). The system then enters the Replot Mode. The same plotting, displaying
and scaling commands are available in the Replot Mode as in the INIT and Collection
Revised 9/30/89 Page 37
-------
Method IP-10B, Appendix Respirable Paniculate
Modes. However, the Fl, F2, and F2 command sequence used to guide the instrument
cycle for data collection have different functions in the Replot Mode.
222.1 The Fl command starts or re-starts the replotting of data. This command has
no effect, however, if the replotting pointer has reached the end of the data file.
Note: Only those variables saved on disk may be replotted. All other variables are given
a value of 0. The list of variables stored on disk during data collection is determined in the
Configuration Definition Routine.
2222 The F2 command stops the replotting of data. After replotting has stopped,
the F9_ command may be executed to print an image on the main display screen.
Note: Replotting may be resumed after F2 is entered by pressing FJL again.
2223 The F3_ command clears the .screen and repositions the replotting pointer to
the beginning of the data file. It also gives the user the option to re-enter the INIT Mode.
Enter N_ to remain in the Replot Mode, or Y to re-enter the INIT Mode. Additional data
files may be replotted by re-entering the INIT Mode and then executing the F7 command.
3. Configuration Definition Routine (CDR)
By entering the Configuration Definition Routine the user may define up to 26 different
configurations. Each configuration has a single-letter name ranging from A to Z. When
the computer is turned on, configuration A is automatically loaded into memory. To obtain
a listing of the currently-defined configurations, enter ALT + C (hold down the ALT key
and press £) when in the INIT Mode. The resulting display shows the full name of the files
that store the operating parameters. These file names are made up of the instrument name,
for example 1100 for the TEOM* Paniculate Mass Monitor, and the configuration name
ranging from A to Z. Press any key to return to the main display screen. Press F4 to load
a different configuration into memory when in the INIT Mode or Replot Mode. AFter F4
has been pressed, the computer displays "Input New Config Name:" in the User Input
Field. In response, enter the single-letter name of a different currently-defined
configuration followed by < Enter >. The new configuration is then loaded into the
computer's memory, and the settings of the new configuration are reflected on the main
display screen. The name of the current configuration is changed in accordance with the
user input.
3.1 Executing the CDR
The CDR can be executed when either in the INIT Mode or the Replot Mode. Press F_8_
when in the Initialization Mode. Press F8_ when in the Replot Mode. This keystroke will
only function if the replotting pointer is at the beginning of the data file, i.e., if you have
just entered the Replot Mode or if you have just cleared the screen in the Replot Mode by
pressing F3_. The computer then lists the currently-defined configuration files in the
TEOM* system. These file names are made up of the instrument model number, followed
by single-letter configuration names. Press any key to continue.
Revised 9/30/89 Pa8e 38
-------
Method IP-10B, Appendix Respirable Paniculate
32 Displaying the Configuration Screens (E1-F4)
The CDR allows the user to change the values of up to 80 program parameters displayed
on four different screens. Screen 1 appears on the monitor when the routine is first
executed The number of the current screen is shown in the bottom right-hand corner of
the display The name of the current configuration appears in the lower left-hand corner
of the screen. Keys El through B display screens 1 through 4. These commands may be
entered in any order and as often as desired. Each screen contains 20 lines (slots) ol
information. Each of these Slots contains a description of a parameter, as well as the
current value of the parameter.
33 Changing a Parameter's Value.
Follow the steps below to change the value of a parameter, for example slot 0 (X-axis
span): To change the value of parameter "X-axis span", slot 0 must appear on the computer
monitor. If this is not the case, press El to choose screen 1. Press E6 to obtain the
computer prompt "Slot:". Enter the number of the slot to be changed followed by
< Enter > In this case, type Q Mowed by < Enter >. The computer responds by displaying
":". Type the new parameter value followed by < Enter >. To change the span of the X-
axis to 3 minutes, enter 3_ followed by < Enter >.
3.4 Saving the Present Configuration
Press E2 to save the current configuration on disk. (This keystroke saves changes made to
the present configuration.)
3.5 Creating or Switching to Another Configuration
Press £8 to create or switch to another configuration. The computer displays the prompt
"Enter File Name:". To create a new configuration, enter the single-letter name of a
configuration that does not presently exist, followed by . The new configuration
initially takes the parameter values of the configuration presently loaded in the computer,
or to load another configuration into the computer's memory, enter the single-letter name
of an existing configuration, followed by < Enter >.
Note- The ES command does not save changes made to the current configuration before
loading a new configuration or loading a different existing one. Press E2 to save changes
made to the current configuration before executing the ES command.
3.6 Printing Configuration Information
Turn the printer on. Make sure that it is "on line", and that its print head is at the top of
a new page. Press F9 to print the contents of the current configuration. When the F9 key
is pressed in the INTT Mode, the user may choose to print the numeric contents of any data
file stored on disk. The instrument is in the Print Mode during all of these printing
operations.
Revised 9/30/89 Pa8e 3»
-------
Method IP-10B, Appendix Respirable Particulate
Note: Because of the time required to print a screen image or the contents of a data file,
the heating circuits in the TEOM® Sensor Unit are turned off during printing. The user
may have to allow for temperatures to stabilize again before resuming data collection.
3.7 Exiting the CDR
Press F10 to exit to the main display screen and save the current configuration.
Revised 9/30/89 Page 40
-------
COMPENDIUM APPENDICES
Appendix A
Appendix B
Appendix C-l
Appendix C-2
Abbreviations and Symbols
Definitions of Terms
Procedure for Placement of Stationary
Active Samplers in Indoor Environment
Procedure for Placement of Stationary
Passive Samplers in Indoor Environment
Revised 9/30/89
Page
-------
Appendix A
Abbreviations and Symbols
ACGIH
AIHA
ASHRAE
ASTM
B(a)P
°C
cm
-_2
cm
CO
coc
EPA
°F
ft
ft2
g
HPLC
in
in2
L
L/min
m
min
mg
mm
m3
Jim
n
NBS
ng
NIOSH
nm
NO
NO2
NOX
PAH
ppm
ppm-hrs
QA
QC
RH
American Conference of Governmental Industrial Hygienists
American Industrial Hygiene Association
American Society of Heating, Refrigeration and Air Conditioning
Engineers
American Society for Testing Materials
benzo-a-pyrene
degrees Celsius
centimeter
square centimeters
carbon monoxide
chain of custody
U.S. Environmental Protection Agency
degrees Fahrenheit
foot
square feet
gram
high performance liquid chromatography
inch
square inches
liter
liters per minute
meter
minute
milligram
millimeter
cubic meter
micrometer
nano (10~9)
National Bureau of Standards
nanogram
National Institute for Occupational Safety and Health
nanometer
nitric oxide
nitrogen dioxide
nitrogen oxides
polynuclear aromatic hydrocarbons
parts per million
parts per million-hours
quality assurance
quality control
relative humidity
Revised 9/30/89
Page 3
-------
Appendix B
Definition of Terms
Accuracy
Active device
Air monitoring module
Analyzer
Blank
Calibration
Collection efficiency
Collector
Fall time
Interferences
Lag time
The difference between the measured value and the true value
that has been established by an accepted reference method
procedure. In most cases, a value is quoted by the
manufacturer and no description is given to indicate how this
value was obtained.
An instrument that employs a power source with a pump to pull
the air across a sensing element or collector.
An assembly of air monitoring devices that are collected into
one package to facilitate handling as a unit.
An analytical sampling device that determines the value of a
pollutant concentration almost instantaneously.
A sample of the pollutant collection medium that is not
exposed to air sampling but that is analyzed as part of the
quality assurance program.
The method for determining the instrument response to known-
concentration gases (dynamic calibration) or artificial stimuli
(static calibration).
The fraction of the incoming pollutant or parameter that is
measured by the instrument.
A sampling device that collects a pollutant for subsequent
laboratory analysis of pollutant concentration.
The time interval between the initial response and a 90 percent
response (unless otherwise specified) after a step decrease in
the inlet concentration. This measurement is usually, but not
necessarily, the same as the rise time.
Any substance or species that causes a deviation of instrument
output from the value that would result from the presence of
only the pollutant of concern.
The time interval from a step change in the input concentration
at the instrument inlet to the first corresponding change in the
instrument output.
Revised 9/30/89
PageS
-------
Appendix B
Definition of Terms
Linearity
Long-term
integrated
Lower detectable
limit
Microenvironment
Monitor
Multi-
parameter
capability
Passive
Personal monitors
Portable monitors
Protocol
Quality assurance
Quality control
Expresses the degree to which a plot of instrument response
versus known pollutant concentration falls on a straight line.
A quantitative measure of linearity may be obtained by
performing a regression analysis on several calibration points.
Techniques that produce an accumulated sample over an
extended time period, such as a week.
The smallest quantity of concentration of sample that causes a
response equal to twice (sometimes 3 or 4 times) the noise
level. (Not to be confused with sensitivity, which is response
per unit of concentration.)
A general location such as residence, office, car, bus, church, or
supermarket that individuals move through during a 24-hour
period of activity.
The instrument or device used to measure air quality of
meteorological parameters. Monitor also refers to the act of
using the instrument or device.
Ability to measure other pollutants or parameters.
A sampling or analytical device that relies on diffusion to bring
a pollutant in contact with a collector or an analyzer.
Instruments for measuring pollutant concentration that can be
worn conveniently on a person.
Instruments that can be readily transported from one sampling
location to another for personal or area sampling.
Detailed scientific directions for performing a program.
A system of activities that provides assurance that the quality
control system is performing adequately.
The activities performed that provide a quality product.
Revised 9/30/89
Page 6
-------
Appendix B
Definition of Terms
Range
Repeatability
Reproducibility
Response time
Retention time
Rise time
Sampling
Short-term integrated
Span drift
•
Stationary monitor
The lower and upper detectable limits. (The lower limit is
usually reported as 9.0 ppm. This is somewhat misleading and
it would be better, however, to report it as the true lower
detectable limit.)
The degree of variation between repeated measurements of the
same concentration.
The degree of variation obtained when the same measurement
is made with similar instruments and many operators. In most
cases, a value is quoted by the manufacturer and no description
is given to indicate how this value was obtained.
The time interval from a step change in the input concentration
at the instrument inlet to a reading of 90 percent (unless
otherwise specified) of the ultimate recorded output. This
measurement is the same as the sum of lag time and rise time.
The time interval from a step decrease in the input
concentration at the instrument inlet to the first corresponding
change in the instrument output.
The time interval between the initial response and a 90 percent
response (unless otherwise specified) after a step increase in the
inlet concentration.
The process of withdrawing or isolating a representative portion
of an ambient atmosphere, with or without the simultaneous
isolation of selected components for subsequent analysis.
Techniques for sampling frequencies that are generally on the
order of hours to 1 day. Resulting data are capable of
describing some aspects of short-term peaks.
The change with time in instrument output over a stated time
period of unadjusted continuous operation when the input
concentration is a stated value other than zero. (Expressed as
percent of full scale.)
An instrument that cannot be readily transported. This may be
because of size, weight, the need to operate in a laboratory
environment, fragility, or high maintenance requirements.
Revised 9/30/89
Page 7
-------
,. „ Definition of Terms
Appendix B
Warm-up time The .elapsed time necessary after startup for the instrument to
p meet stated performance specifications when the instrument has
been shut down for at least 24 hours.
Zero air Air which has been treated to ensure purity and lack of
contaminants, that may be used to establish a zero reference
point for an air quality analyzer.
Zero drift The change with time in instrument output over a stated time
period of unadjusted continuous operation when the input
concentration is zero. (Expressed as percent of full scale.)
Revised 9/30/89 Page 8
-------
Active Sampler Placement
PROCEDURE FOR PLACEMENT OF STATIONARY ACTIVE
SAMPLERS IN INDOOR ENVIRONMENTS
1. Scope
There are no standard practices available for selecting sampling areas for •indoor
envkonSente ThHrocedure is intended to provide general guidelines in siting and
SS^Sn^ST-mplei. indoors. The purpose of this document is to ensure
consistency of sampling site selection in indoor atmospheres.
2. Applicable Documents
2.1 ASTM Standards
D1356 Definition of Terms Relating to Atmospheric Sampling and Analysis
22 Other Documents
22.1 Wadden, R. A, and Scheff, P. A., Indoor Air Pollution Ch^erizatior,Predi ction
and Control, ISBN: 0-471-8763-9, Wiley Interscience Publishing Co., New York, NY, 1983.
222 Nagada, et al. Guidelines for Monitoring Indoor Air Quality, Hemisphere
Publishing Corp., New York, NY, 1987.
3. Summary of Method
3 1 Indoor air is collected by a stationary sampling system. The sampled air is either
analyzed directly or stored in an appropriate container for later analysis.
3 2 Guidelines are given for determining sampling site location.
4. Procedure
4 1 The sampling inlet/probe of the stationary sampler should be located in an area that
best re^reS peSlutant concentrations experienced by the individuals occupying the
area The 3m7 locations may be in a general area such as a basement or warehouse.
5S^teS?i3fic moniLing, samplers c
-------
Appendix C-l Active Sampler Placement
4.
4.3 Once indoor sampling areas have been identified, inlet/probe locations may be
determined. When selecting inlet/probe locations, the following areas should be avoided:
areas of direct sunlight
areas with noticeable drafts 7
areas directly influenced by return or supply ducts
areas that are directly impacted from outdoor sources
exterior corners and walls
probe heights below 1 m or above 2 m unless vertical gradients are being measured
4.4 Sampler instrumentation is also an important factor in selecting probe location.
Samplers should be situated to minimize interference with indoor air. For unoccupied
areas, major consideration should be given to sample flow rates (i.e., to avoid sampling
system cleaning the air or contributing local exhaust) and heat sources. For occupied areas,
especially residences, available space is an important issue.
4.5 New analyzers are compact for placement indoors and are configured to operate from
battery power or to operate from household electric supply without interfering with normal
occupancy. These systems generally require repackaging for use in the field. For systems
with multiple analyzers and sophisticated data recording devices, a container is useful for
transport and security. Before placing such an instrument indoors, the following questions
should be answered:
• How many people will be needed to transport the monitoring package?
• What is the size of the smallest doorway through which the system is to be carried,
including vehicles used to transport the package from place to place?
• Can a toddler pull or push it over?
• Will the size of the package interfere with normal use of the area by its occupants?
• Will the sampling system emit noise or odors that may be considered offensive to
occupants?
4.6 If the system is to be operated from wall current, electric power is important for two
reasons. The first is heat generated during operation of transformers, pumps, etc. If
packaging confines natural ventilation around the instruments, the casing should provide for
compensatory air movement with small fans or other devices. If sampling inlets are very
close to the cabinetry, sampling results may be biased. The second aspect of electric power
is the system amperage and grounding requirements. If monitoring is to take place in
occupied structures, available circuits will be at a premium. A blown fuse or tripped
breaker leads to lost data and guilt-ridden, if not infuriated, occupants. There are many
structures that still have two-prong outlets; a "cheater plug" does not necessarily ensure a
grounded connection. Inexpensive test devices are available to verify ground connections.
Revised 9/30/89 Page 10
-------
,. „ - Passive Sampler Placement
Appendix C-2 . _
PROCEDURE FOR PLACEMENT OF STATIONARY PASSIVE
SAMPLERS IN INDOOR ENVIRONMENTS
1. Scope
This document covers the placement and use of passive sampling n™1™^*
atmosphere. The purpose of this document is to help ensure consistency of samplmg
a variety of indoor environments and to facilitate comparison of monito ring data This
procedure may involve hazardous materials, operations, and equipment Tlus procedure
does not purport to assess all of the safety problems assoaated with m use^ Ins the
resDonsibmtv of whoever uses this procedure to consult and establish appropnate safety and
practices^ determine the applicability of regulatory limitations prior to use.
2. Applicable Documents
2.1 ASTM Standards
D1356 Definitions of Terms Relating to Atmospheric Sampling and Analysis Practice for
Planning the Sampling of Indoor Air
3. Summary of Practice
3.1 Sample air is collected by adsorption onto a sorbent media or reacted with an
appropriate chemical in order to subsequently undergo analysis for detenmnation o
concentration. The sampled air is circulated to the adsorption media or reaction chemical
through diffusion.
3 2 Instructions are given for the handling and placement of passive monitors within an
indoor environment.
4. Terminology
For definitions and terms used in this practice refer to D1356.
5. Significance and Use
5 1 Since analysis of the indoor environment is influenced by many factors except the
method of sampling, an effort should be made to minimize interfering factors and maintain
air at normal conditions in the area of the passive monitor.
52 Passive detection provides for time-integrated measurements. Passive monitors are
usually placed in an indoor environment over a sampling period ranging from 3 days to . 1
year. Due to the length of time involved with sampling, interfering factors should be
anticipated and eliminated where possible.
5.3 Placement and recovery of the monitors can be performed by unskilled personnel with
suitable instruction (even an occupant).
Revised 9/30/89 Page U
-------
Appendix C-2 Passive Sampler Placement
6. General Principles
61 Passive monitors rely on normal convection of air currents within an indoor
environment for circulation of a representative sample atmosphere to the vicinity_ot the
monitor. Subsequent collection of the sample component is performed through diffusion.
Sampling adequacy is directly influenced by the ability of the monitor to be exposed to the
representative sample atmosphere.
62 Variability of the results will decrease with consistency in sampling protocol as well
as with increased sample component concentration.
7. Procedure
7.1 Predeployment Considerations
7.1.1 The occupants, if any, in the indoor environment to be sampled should not alter
normal activities within the measurement period.
7.12 Deployment during remodeling or redecorating is not recommended. Changes
in major furnishings such as stoves, HVAC systems, etc., should be avoided.
7.1.3 Deployment when seasonal alterations in insulation or building tightness are
occurring or will occur during the measurement period should be avoided. (When long-
term measurements on the order of months are being taken, this consideration is minimal.)
7.2 Measurement Conditions
72.1 Doors should be operated (opening/closing) in a manner consistent with normal
occupancy. Windows should be kept closed when possible. Over an extended sampling
period the effect of a few days of open windows should be minimal on results.
722 The ventilation system should be operated in a manner consistent with normal
occupancy. , .. . , ~~
723 The method of heating should not be altered during the sampling penod. Ine
normal occupancy heating method should be maintained.
7.2.4 The use of humidifiers/dehumidifiers is not recommended.
72.5 Normal occupancy activities should continue.
72.6 No effort should be made to additionally tighten the indoor environment or to
provide additional ventilation. . .
72.7 The placement of the monitor should not prevent normal occupancy activity trom
occurring.
73 Deployment
The monitor should be deployed as soon as possible after receipt and within the limitations
of the indicated storage life. A blank exposure should be retained for completeness
utilizing an unexposed monitor of the same manufactured lot.
Revised 9/30/89 Pa8e
-------
Appendix C.2 Passive Sampler Placement
7.4 Placement
7.4.1 Indoor Atmosphere Considerations
7.4.1.1 The monitor should be situated in a location such that the monitor is
exposed to representative sample air at normal conditions.
7 412 Humidity - Locations near sinks, tubs, showers, stoves, washers, dners, or
^
meteorologic variations should be avoided (e.g., drafty windows or doors). p
7.4.1.5 Airflow - Location in direct airflow such as near furnace vents, apphance
fan vents, computer cooling fans, and HVAC intake/exhaust should be avoided. Areas
where a known draft or pressure differential between areas of a building should also be
avoided.
7.42 Spatial Considerations
7.42.1 The monitor should be placed in an open and unobstructed area where
normal air convection will be encountered. The monitor should be placed iat least 20 cm
(8 in) below the ceiling, 50 cm (20 in) above the floor and 15 cm (6 in) from a wall
Outside walls should not be used if possible. Suspending monitors from the ceiling may be
SUltablC 7.422 The monitor should be placed in a position where disturbance will not occur
during the measurement period.
7.4.3 Occupant Considerations
7.4.3.1 The monitor should be placed out of the reach of small children and pets.
7.4.32 The placement of the monitor, if not deployed by the occupant, should be
agreeable and approved by the occupant.
7.5 Sampling
7 51 The sampling period begins when the lid or container of the monitor is removed
at which time the time and date should be transcribed into a log book. A means of either
resealing the monitor in the container or replacing the lid should be assured prior to the
Cn £52 eSincePdamage could occur during shipping and handling of the monitor, inspect
the monitor and package carefully. . .
7.5 J The monitor should have a permanently attached identification code or serial
number which should be transcribed into a log book. The log book should include
information describing the location of the monitor and pertinent information regarding the
building such as construction type, heating system, insulation, occupancy number and
patterns, and major appliance location. Include a diagram of the sampling location and
building depicting the information listed in this subsection. If the occupant deploys the
Revised 9/30/89 Page 13
-------
Appendix C-2 Passive Sampler Placement
monitor, sufficient instructions should be included regarding proper location and sampling
conditions. A form should be included for easy collection of information necessary for log
book entries.
7.5.4 If the monitor is deployed for other than a screening measurement, the monitor
should be placed by a reliable professional familiar with the monitor used. For specific
measurements, a deviation from the guidelines in Sections 7.2.1 through 7.4.22 is
permissible.
7.6 Passive Monitor Recovery
7.6.1 Hie sampling period is terminated when the monitor is removed and sealed from
the sample environment
1.62 Record the time and date for measurement termination. Any damage or variance
in the monitor since deployment should be noted in the log book.
7.6.3 Adequate information should be entered in the log book to permit interpretation
of results and comparison to similar measurements. Any variation in the sampling location
or building structure should be noted.
7.6.4 The monitor should be analyzed as soon as possible.
Revised 9/30/89 Page 14
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TECHNICAL REPORT DATA
(Heat read Jiutniclions on the reverie before completing)
1. REPORT NO
EPA/600/4-90/010
. mt*b' VWO I I I
Compendium of Methods for the Determination of Air
Pollutants in Indoor Air
£890 2 002 88/AS
April 1990
t-cnruniwiw
MINU ORGANIZATION CODE
AUTHORCS)—— ~ -
W. T. Winberry, Or., Linda Forehand, N. T. Murphy,
Angela Ceroli, Barbara Phinney, and Ann Evans
STELE!
PERFORMING ORGANIZATION NAME AND ADDRESS
Engineering-Science
One Harrison Park, Suite 305
401 Harrison Oaks Boulevard
Gary, NC 27513
10. T
11. CbNTRACtteRANt Ng
68-04-4467 (WA 13)
68-02-4398 (WA 9, 32)
2. SPONSORING AGENCY NAME AND ADDRESS
Atmospheric Research and Exposure Assessment
Laboratory, Office of Research and Development
U. S. Environmental Protection Agency
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVI
14. SPONSORING AGENCY CODE
E*V600/09
5. SUPPLEMENTARY NOTES
6. ABSTRACT
Determination of pollutants in indoor air is a complex task because of the
wide variety of compounds of interest and the lack of standardized sampling and
analysis procedures. To assist agencies and persons responsible for .sampling
and analysis of indoor pollutants, this methods compendium provides current,
technically-reviewed sampling and analysis procedures in a standardized format
for determination of selected pollutants of primary importance in indoor air.
Each chapter contains one or more active or passive sampling procedures along
with one or more appropriate analytical procedures. The ten chapters of the
compendium cover determination of volatile organic compounds (VOCs), nicotine,
carbon monoxide (CO) and carbon dioxide (CO,), air exchange rate, nitrogen
dioxide (NO,), formaldehyde (CHjO), benzo(a)pyrene and other polynuclear aromatic
hydrocarbons, acid gases and aerosols, particulate matter, and pesticides. As
further advancements are made, the procedures may be modified or updated, or
additional methods may be added as appropriate.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATl Field/Group
Indoor air quality
Indoor air pollutants
Monitoring methods
18. DISTRIBUTION STATEMENT
Release unlimited
19. SECURITY CLASS (This Report I
Unclassified
2O. SECURITY CLASS (This page/
Unclassified
EPA F«rm 2220-1 (••». 4-77)
PREVIOUS COITION I* O»»OUETE
i
-------
-------
Disclaimer
The information in this document has been funded wholly orjn part by thf IJ.S
Environmental Protection Agency under contract numbers 68-04-4467 and 68-02-4398. it
has been subjected to the Agency's peer and administrative review, and it has been
approved for publication as an EPA document. Mention of trade names or commercial
products does not constitute endorsement or recommendation for use.
Acknowledgement
This project is supported through the USEPA Indoor Air Program at Research Triangle
Park, NC Comments or recommendations for improvements may be directed to Frank
McElroy (MD-77), Atmospheric Research and Exposure Assessment Laboratory, Research
Triangle Park, NC 27711.
ii
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-------
CONTENTS
FOREWORD
INTRODUCTION
TABLE 1. Brief Method Description and Applicability
TABLE 2. Compounds of Primary Interest
CHAPTER IP-1 Determination of Volatile Organic Compounds (VOCs) in
Indoor Air
. Method IP-1A Stainless Steel Canister
. Method IP- IB Solid Adsorbent Tubes
CHAPTER IP-2 Determination of Nicotine hi Indoor Air
. Method IP-2A XAD-4 Sorbent Tubes
. Method IP-2B Treated Filter Cassette
CHAPTER IP-3 Detennination of Carbon Monoxide (CO) or Carbon
Dioxide (CO2) in Indoor Air
• Method IP-3A Nondispersive Infrared (NDIR)
• Method IP-3B Gas Filter Correlation (GFC)
• Method EP-3C Electrochemical Oxidation
CHAPTER IP-4 Detennination of Air Exchange Rate hi Indoor Air
. Method BP-4A Perfluorocarbon Tracer (PFT)
• Method BP-4B Tracer Gas
CHAPTER IP-5 Detennination of Nitrogen Dioxide hi Indoor Air
• Method IP-5A Continuous Luminox Monitor
• Method IP-SB Palmes Diffusion Tube
• Method BP-5C Passive Sampling Device
CHAPTER IP-6 Detennination of Formaldehyde and Other Aldehydes hi
Indoor Air
• Method IP-6A Solid Adsorbent Cartridge
. Method IP-6B Continuous Colorimetnc Analyzer
• Method IP-6C Passive Sampling Device
CHAPTER IP-7 Detennination of Benzo(a)Pyrene [B(a)P] and Other
Polynuclear Aromatic Hydrocarbons (PAHs) in Indoor Air
CHAPTER IP-8 Determination of Organochlorine Pesticides in Indoor Air
V1U
iii
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CHAPTER IP-9 Determination of Reactive Acidic and Basic Gases and
Particulate Matter in Indoor Air
CHAPTER IP-10 Determination of Respirable Particulate Matter in Indoor
Air
• Method IP-10A Size Specific Impaction
• Method IP-10B Continuous Particulate Monitor
APPENDIX
Abbreviations and Symbols
Definition of Terms
Placement of Active/Passive Monitors .
iv
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FOREWORD
The Atmospheric Research and Exposure Assessment Laboratory (AREAL) in
Research Triangle Park is a research laboratory of the Environmental Protection Agency
(EPA). It has an ongoing responsibility to assess environmental monitoring technologies
and systems, to implement Agency-wide quality assurance programs for air pollution
measurement systems, and to provide technical support to program offices in EPA and to
other groups.
The recent emergence of indoor air pollution as a major environmental and public
health concern has created the need for standardized monitoring and measurement methods
of important indoor air contaminants. Such methods are useful in the conduct of research,
in the development and implementation of policies and programs, and in the investigation
of specific indoor air quality problems which can occur in all types of building
environments.
AREAL has developed this compendium to assist federal, state and local agencies, and
private sector organizations in the conduct of their indoor air pollution monitoring activities,
and to promote the accurate determination and assessment of human exposure to indoor
air pollution.
Gary J. Foley
Director
Atmospheric Research and Exposure Assessment Laboratory
Research Triangle Park, North Carolina 27711
-------
-------
INTRODUCTION
In recent years, greatly increased attention has been focused on the quality of indoor
air. Most people spend a major portion of their time indoors, in living areas, offices or
other workplaces, stores, restaurants, waiting rooms, public buildings, public or private
transportation vehicles, etc. Obviously, then, exposure to indoor air pollutants can
constitute an important fraction of a person's total exposure to air pollution.
In addition to penetration of outdoor pollutants into the indoor environment, indoor
air pollutants may originate from many sources, including various indoor activities, use of
many different types of appliances, tools, and substances, and outgassing of various types
of construction and decoration materials. Indoor air pollutants include a wide variety of
compounds and typically occur in concentrations and mixtures that generally vary greatly
over time and from one area to another and are often episodic in nature. Consequently,
human exposures are difficult to assess for both individuals and groups. This difficulty is
further complicated by restrictions in the sampling and measurement techniques that can
be used indoors due to limitations in the physical size, noise, air flow rates, power
consumption, installation, etc. of the apparatus used. Not surprisingly, there has been a lack
of standardized procedures for sampling and analysis of indoor air pollutants, particularly
for very low concentrations of indoor air contaminants.
To date, little guidance has been available to state and local agencies or to other
organizations concerned with the determination of indoor air pollutants. As a result, state
and local agencies and others responding to indoor air pollution problems have had to
develop their own monitoring strategies, including selection of monitoring methods,
sampling plan design, and specific procedures for sampling, analysis, logistics, calibration,
and quality control. For the most part, these procedures were based on professional
judgments rather than adherence to any documented uniform guidelines. Many
governmental agencies and professional or research organizations have developed indoor
air monitoring methods and procedures, mostly to respond to specialized needs. But these
methods and procedures have generally been neither standardized nor readily available to
other agencies involved with indoor air monitoring.
This Compendium has been prepared to provide regional, state and local
environmental regulatory agencies, as well as other interested parties, with specific guidance
on the determination of selected air pollutants in indoor air. The ten chapters of the
Compendium cover those contaminants (as well as ventilation rate) that are considered to
be of primary interest in indoor air monitoring efforts. These ten chapters address:
Volatile organic compounds (VOCs)
Nicotine
Carbon monoxide (CO) and Carbon dioxide (CO2)
Air exchange rate
Nitrogen dioxide (NO2)
Formaldehyde (CH2O)
Benzo(a)pyrene and other polynuclear aromatic hydrocarbons
vi
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-------
. Acid gases and aerosols (NOX, SOX, and NH3)
• Particulate matter
• Pesticides
Each chapter contains one or more methods for measuring the parameter, including
sampling and/or analysis techniques, calibration, quality assurance, and other pertinent
topics These methods have been compiled from the best elements of methods developed
or used by various research or monitoring organizations. They are presented m a
standardized format, and each has been extensively reviewed by several technical experts
having expertise in the methodology used. However, the methods are not certified and
should not be regarded as officially recommended or endorsed by EPA. As advancements
are made in the methodology, the current methods for other contaminants may be added
as such methods become available.
Each of the methods is self-contained (including pertinent literature citations) and
can be used without the other portions of the Compendium. To the extent possible, the
American Society for Testing and Materials (ASTM) standardized format has been used,
since many potential users of these methods are familiar with that format. Each method
has been identified with a revision date so that future modifications or updates to the
methods can be identified.
4
Nearly all of the methods have some degree of flexibility in the procedure.
Consequently, it is the user's responsibility to prepare certain standard operating procedures
(SOPs) to be employed for the particular laboratory or organization using the method.
Each method description indicates those operations for which SOPs are required. Some
methods may present analytical options that can be used instead of, or in addition to, those
specifically described. In such cases, the user is referred to other methods within the
Compendium that contain the pertinent detailed analytical protocol.
Table 1 summarizes the methods currently contained in the Compendium and briefly
indicates the application of each. Table 2 presents a listing of many of the indoor air
pollutants that can be determined with one or more of the Compendium methods and
identifies which method (or methods) are applicable. Some methods may be used to
determine additional compounds, but the user must carefully evaluate the applicability of
the method to such compounds before use.
As advancements are made, the current methods may be modified from time
to time In addition, new methods addressing new pollutants of concern will be added as
methodology becomes available. Future consideration may include methodology for:
• Synthetic fibers • Asbestos
• Ethylene oxides • Radon
. Biological particles • Metals
vii
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Table 1. List of Methods in the Compendium
Method
Number
Description
IP-1A Stainless Steel Canister
IP-IB Solid Adsorbent Tubes
IP-2A XAD-4 Sorbent Tube
IP-2B Treated Filter Cassette
Types of
Compounds Determined
Volatile organic compounds (VOCs) (e.g.
aromatic hydrocarbons, chlorinated
hydrocarbons) having boiling points in the
range of 80" to 2(Xf C
Nicotine (gaseous and particulate)
IP-3A Nondispersive Infrared (NDER) Carbon monoxide and/or carbon dioxide
IP-3B Gas Filter Correlation (GFC)
IP-3C Electrochemical Oxidation
DMA Perfluorocarbon Tracer (PTF)
IP-4B Tracer Gas
IP-5A Continuous Luminox Monitor
IP-SB Palmes Diffusion Tube
IP-5C Passive Sampling Device
IP-6A Solid Adsorbent Cartridge
Carbon monoxide
Air exchange rate
Nitrogen oxides
Formaldehyde (CH2O) and other
IP-6B Continuous Colorimetric Analyzer aldehydes/ketones
IP-6C Passive Sampling Device
IP-7 Medium Volume PUF/XAD
Sampler
Polynuclear aromatic hydrocarbons
IP-8 Low Volume PUF with GC/ECD Pesticides (e.g. Organochlorine,
Organophosphorus, Urea, Pyrethrin,
Carbamate, and Triazine)
IP-9 Annular Denuder System
IP-10A Size Specific Impaction
EP-10B Continuous Particulate Monitor
Acid Gases/Aerosols/Particles
(e.g. nitrates, sulfates, and ammonia)
Particulate matter
viii
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Table 2. List of Compounds of Primary Interest
Volatile Organic Compounds
(Methods IP-1A, IP-IB)
Freon 12 (Dichlorodifluoromethane)
Methyl chloride (Chloromethane)
Freon 114 (l,2-Dich!oro-l,l,2,2-
tetrafluoroethane)
Vinyl Chloride (Chloroethylene)
Methyl bromide (Bromomethane)
(Perchloroethylene)
Ethyl chloride (Chloroethane)
Freon 11 (Trichlorofluoromethane)
Vinylidene chloride (1,1-Dichloroethane)
Dichloromethane (Methylene chloride)
Freon 113 (l,l,2-Trichloro-l,2,
2-trifluoroethane)
Tribromomethane
cis-l,2-Dichloroethylene
Chloroform (Trichloromethane)
1,2-Dichloroethane (Ethylene dichloride)
Methyl chloroform (1,1,1-Trichloro-
ethane)
Benzene (Cyclohexatriene)
Carbon tetrachloride
(Tetrachloromethane)
1,2-Dichloropropane (Propylene
dichloride)
Trichloroethylene (Trichloroethane)
cis-l,3-Dichloropropene
1,2-Dichloropropane
1,3-DichIoropropane
1,2,3-Trichloropropane
l-Bromo-3-chloropropane
3-Chloro-l-propene
1,2-Dibromopropane
2-Chlorobutane
1,3-Dichlorobutane
1,4-Dichlorobutane
Dichloropropylene
1,1,2-Trichloroethane (Vinyl trichloride)
1,1,2-Trichloroethane
Trichloroethene
2-Chloroethoxyethene
1,1,1,2-tetrachloroethane
1,1,2,2-tetrachloroethane
Toluene (Methyl benzene)
1,2-Dibromomethane (Ethylene dibromide)
Tetrachloroethylene
Chlorobenzene (Phenyl chloride)
Ethylbenzene
m-Xylene (1,3-Dimethylbenzene)
p-Xylene (1,4-Dimethylbenzene)
Styrene (Vinyl benzene)
1,1,2,2-Tetrachloroethane
o-Xylene (1,2-Dimethylbenzene)
4-EthyltoIuene
1,3,5-Trimethylbenzene (Mesitylene)
1,2,4-Trimethylbenzene (Pseudocumene)
m-Dichlorobenzene (1^-Dichlorobenzene)
Benzyl chloride (a-Chlorotoluene)
o-Dichlorobezene (1,2-Dichlorobenzene)
p-Dichlorobenzene (1,4-Dichlorobenzene)
1,2,4-Trichlorobenzene
Hexachlorobutadiene (1,1,2,3,4,4-
Hexachloro-l,3-butadiene)
(1-Methylethyl) benzene
Butylbenzene
l-Methyl-4-(l-methylethyl) Benzene
Bromobenzene
l-Ethyl-4-chlorobenzene
Bromochloromethane
Bromotrichloromethane
1-Chloropropane
2-Chloropropane
2,3-Dichlorobutane
l,4-Dichloro-2-Butane (cis)
3,4-Dichloro-l-Butane
Tetrahydrofuran
1,4-Dioxane
l-Chloro-2,3-Epo^rpropane
Benzaldehyde
Benzonitrile
Pentachloroethane
Bromoethane
1-Phenylethanone
1,1-Dichloroethane (Ethyh'dene dichloride)
IX
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Table 2. list of Compounds of Primary Interest (Cont'd)
Pesticides
(Method IP-8)
Organochlorine
Aldrin
p,p,-DDT
p,p,-DDE
Dieldrin
Dicofol
2,4,5-Tricblorophenol
Pentachlorophenol
BHC (a- and fi-Hexachlorocyclohaxanes)
Captan
Chlordane, technical
Chliorothalonil
2,4,-D esters
Organophosphorus
Chlorpyrifos
Diazinon
Dichlorvos (DDVP)
Ethylparathion
Malathion
Methyl parathion
Ronnel
Carbamates
Propuxur
Carbofuran
Bendicarb
Mexacarbate
Carbaryl
Triazine
Simazine
Atrazine
Propazine
Inorganics
(Methods IP-3A, IP-SB, IP-3C, IP-5A, IP-SB, EP-5C, IP-9, IP-10A, IP-10B)
Qrganochlorine
Methoxychlor
Mexacarbate
Mirex
trans-Nonachlor
Oxychlordane
Pentachlorobenzene
Folpet
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Lindane (and 7-BHC)
Ureas
Monuron
Diuron
Liuron
Terbuthiuron
Fluometuron
Chlortoluron
Pyrethrin
Pyrethrin I
Pyrethrin n
AUethrin
d-trans-Allethrin
Diocrotophos
Resmethrin
Fenvalerate
Ammonia (Ammonium)
Nitrogen dioxide
Nitric acid
Nitrous acid
Sulfuric acid
Sulfite
Sulfur dioxide
Carbon monoxide
Carbon dioxide
Paniculate matter
-------
Table 2. List of Compounds of Primary Interest (Cont'd)
Pnlyrmclear Aromatic Hydrocarbons (PAHs)
(Method IP-7)
Acenaphthene Benzo(k)fluoranthene
Acenaphthylene Chrysene
Anthracene Dibenzo(a,h)anthracene
Benzo(a)anthracene Fluoranthene
Benzo(a)pyrene Fluorene
Benzo(b)fluoranthene Indeno(l,2,3-cd)pyrene
Benzo(e)pyrene Naphthalene
Benzo(g,h,i)perylene Phenanthrene
Pyrene
Environmental Tobacco Smoke
(Methods IP-2A, IP-2B)
Nicotine (particle and gaseous)
Aldehydes and Ketones
(Methods IP-6A, IP-6B, IP-6C)
Formaldehyde Acetaldehyde
Acrolein Acetone
Propionaldehyde Crotonaldehyde
Butyraldehyde Benzaldehyde
Isovaleraldehyde Valeraldehyde
o-Tolualdehyde m-Tolualdehyde
p-Tolualdehyde Hexanaldehyde
2,5-Dimethylbenzaldehyde
xi
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Chapter IP-1
DETERMINATION OF VOLATILE ORGANIC
COMPOUNDS (VOCs) IN INDOOR AIR
• Method IP-IA - Stainless Steel Canisters
• Method IP-IB - Solid Adsorbent Tubes
1. Scope
1.1 This document describes procedures for sampling and analysis of volatile organic
compounds (VOCs) in indoor air. The methods are based on either collection of whole air
samples in SUMMA* passivated stainless steel canisters or collection on solid adsorbent
tubes. The VOCs are subsequently separated by gas chromatography and measured by
mass-selective detector or multidetector techniques. Method IP-IA presents procedures for
sampling VOCs into canisters to final pressure both above and below atmospheric pressure
(respectively referred to as pressurized and subatmospheric pressure sampling), while
Method IP-IB presents procedures for sampling VOCs using a solid adsorbent bod.
2. Significance
2.1 VOCs are emitted into the indoor atmosphere from a variety of sources including
diffusion from outdoor sources, manufacturing processes, and use of various products,
appliances, and building materials. Many of these VOC emissions are acutely toxic;
therefore, their determination in indoor air is necessary to assess human health impacts.
22 Conventional methods for VOC determination use solid sorbent sampling techniques.
The most widely used solid sorbent is Tenax*. An air sample is drawn through a Tenax® -
filled cartridge where certain VOCs are trapped on the polymer. The sample cartridge is
transferred to a laboratory and analyzed by GC-MS.
23 VOCs can also be successfully collected in stainless steel canisters. Collection of
indoor air samples in canisters provides 1) convenient integration of indoor samples over
a specific time period, (e.g., 24 hours), 2) remote sampling and central analysis, 3) ease of
storing and shipping samples, 4) unattended sample collection, 5) analysis of samples from
multiple sites with one analytical system, and 6) collection of sufficient sample volume to
allow assessment of measurement precision and/or analysis of samples by several analytical
systems. However, care must be exercised in selecting, cleaning, and handling sample
canisters and sampling apparatus to avoid losses or contamination of the samples.
Contamination is a critical issue with canister-based sampling because the canister is the
last element in the sampling train.
Revised 9/30/89 Pa8e
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Method IP-1A
DETERMINATION OF VOLATILE ORGANIC COMPOUNDS (VOCs)
IN INDOOR AIR USING STAINLESS STEEL CANISTERS
1. Scope
2. Applicable Documents
3. Summary of Method
4. Significance
5. Definitions
6. Interferences and Limitations
7. Apparatus
7.1 Sample Collection
7.1.1 Subatmospheric Pressure
7.12 Pressurized
12 Sample Analysis
72.1 GC-MS-SCAN Analytical System
122 GC-MS-SIM Analytical System
7.2.3 GC-Multidetector Analytical System
73 Canister Cleaning System
7.4 Calibration System and Manifold
8. Reagents and Materials
9. Sampling System
9.1 System Description
9.1.1 Subatmospheric Pressure Sampling
9.1.2 Pressurized Sampling
9.1.3 All Samplers
92 Sampling Procedure
10. Analytical System
10.1 System Description
10.1.1 GC-MS-SCAN System
10.12 GC-MS-SIM System
10.13 GC-Multidetector (GC-FID-ECD-PID)
System
10.2 GC-MS-SCAN-SIM System Performance Criteria
10.2.1 GC-MS System Operation
10.2.2 Daily GC-MS Tuning
1023 GC-MS Calibration
102.3.1 Initial Calibration
10.232 Routine Calibration
103 GC-FID-ECD System Performance Criteria (With
Optional PID)
103.1 Humid Zero Air Certification
1032 GC Retention Time Windows
Determination
Revised 9/30/89 PaSe
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10.33 GC Calibration
10.3.3.1 Initial Calibration
10.3.32 Routine Calibration
10.3.4 GC-FID-ECD-PID System Performance
Criteria
10.4 Analytical Procedures
10.4.1 Canister Receipt
10.4.2 GC-MS-SCAN Analysis (With Optional FID
System)
10.4.3 GC-MS-SIM Analysis (With Optional FID
System)
10.4.4 GC-FID-ECD Analysis (With Optional PID
System)
11. Cleaning and Certification Program
11.1 Canister Cleaning and Certification
11.2 Sampling System Cleaning and Certification
11.2.1 Cleaning Sampling System Components
11.22 Humid Zero Air Certification
11.23 Sampler System Certification With Humid
Calibration Gas Standards
12. Performance Criteria and Quality Assurance
12.1 Standard Operating Procedures (SOPs)
122 Method Relative Accuracy and Linearity
123 Method Modification
123.1 Sampling
1232 Analysis
12.4 Method Safety
12.5 Quality Assurance
12.5.1 Sampling System
12^2 GC-MS-SCAN-SIM System Performance
Criteria
12.5.3 GC-Multidetector System Performance
Criteria
13. Acknowledgements
14. References
Appendix A - Availability of Audit Cylinders from U.S.
Environmental Protection Agency (USEPA) to USEPA
Program/Regional Offices, State/Local Agencies and Their
Contractors
Appendix B - Operating Procedures for a Portable Gas
Chromatograph Equipped with a Photoionization Detector
Appendix C - Installation and Operating Procedures for U.S.
Environmental Protection Agency's Urban Air Toxic Pollutant
Program Sampler
Revised 9/30/89 Page 2
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Method IP-1A
DETERMINATION OF VOIATILE ORGANIC COMPOUNDS (VOCs)
IN INDOOR AIR USING STAINLESS STEEL CANISTERS
1. Scope
1.1 This document describes a procedure for sampling and analysis of volatile organic
compounds (VOCs) in indoor air. The method is based on collection of whole air samples
in SUMMA* passivated stainless steel canisters. The VOCs are subsequently separated by
gas chromatography and measured by mass-selective detector or multidetector techniques.
This method presents procedures for sampling into canisters to final pressures both above
and below atmospheric pressure (respectively referred to as pressurized and subatmosphenc
pressure sampling).
12 This method is applicable to specific VOCs that have been tested and determined to
be stable when stored in pressurized and subatmospheric pressure canisters. Numerous
compounds, many of which are chlorinated VOCs, have been successfully tested for storage
stability in pressurized canisters (1,2); however, minimal documentation is currently
available demonstrating stability of VOCs in subatmospheric pressure canisters.
1.3 The organic compounds that have been successfully collected in pressurized canisters
by this method are listed in Table 1. These compounds have been successfully measured
at the parts per billion by volume (ppbv) level.
2. Applicable Documents
2.1 ASTM Standards
D1356 Definition of Terms Related to Atmospheric Sampling and Analysis
E260 Recommended Practice for General Gas Chromatography Procedures
E355 Practice for Gas Chromatography Terms and Relationships
22 Other Documents
U.S. Environmental Protection Agency Technical Assistance Document (3)
Laboratory and Ambient Air Studies (4-17)
3. Summary of Method
3.1 Both subatmospheric pressure and pressurized sampling modes use an initially
evacuated canister and a pump-ventilated sample line during sample collection. Pressurized
sampling requires an additional pump to provide positive pressure to the sample canister.
A sample of indoor air is drawn through a sampling train comprised of components that
regulate the rate and duration of sampling into a pre-evacuated SUMMA* passivated
canister.
32 After the air sample is collected, the canister valve is closed, an identification tag is
attached to the canister, and the canister is transported to a predetermined laboratory for
analysis.
Revised 9/30/89 Pa8e 3
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Method IP-1A
3.3 Upon receipt at the laboratory, the canister tag data is recorded and the canister is
attached to the analytical system. During analysis, water vapor is reduced in the gas stream
by a Nafion* dryer (if applicable), and the VOCs are then concentrated by collection in a
cryogenically-cooled trap. The cryogen is then removed and the temperature of the trap
is raised. The VOCs originally collected in the trap are revolatilized, separated on a GC
column, then detected by one or more detectors for identification and quantitation.
3.4 The analytical strategy for Method IP-1A involves using a high resolution gas
chromatograph (GC) coupled to one or more appropriate GC detectors. Historically,
detectors for a GC have been divided into two groups: non-specific detectors and specific
detectors. The non-specific detectors include, but are not limited to, the nitrogen-
phosphorus detector (NPD), the flame ionization detector (FID), the electron capture
detector (BCD) and the photoionization detector (PID). The specific detectors include the
mass spectrometer (MS) operating in either the selected ion monitoring (SIM) mode or the
SCAN mode, or the ion trap detector. The use of these detectors or a combination of these
detectors as part of an analytical scheme is determined by the required specificity and
sensitivity of the application. While the nonspecific detectors are less expensive per analysis
and in some cases more sensitive than the specific detector, they vary in specificity and
sensitivity for a specific class of compounds. For instance, if multiple halogenated
compounds are targeted, an BCD is usually chosen; if only compounds containing nitrogen
or phosphorus are of interest, a NPD can be used; or, if a variety of hydrocarbon
compounds are sought, the broad response of the FID or PID is appropriate. In each of
these cases, however, the specific identification of the compound within the class is
determined only by its retention time, which can be subject to shifts or to interference from
other nontargeted compounds. When misidentification occurs, the error is generally a result
of a cluttered chromatogram, making peak assignment difficult. In particular, the more
volatile organics (chloroethanes, ethyltoluenes, dichlorobenzenes, and various freons) exhibit
less well defined chromatographic peaks, leading to misidentification using non-specific
detectors. Quantitative comparisons indicate that the FID is more subject to error than the
BCD because the BCD is a much more selective detector for a smaller class of compounds
which exhibits a stronger response. Identification errors, however, can be reduced by
employing simultaneous detection by different detectors or correlating retention times from
different GC columns for confirmation. In either case, interferences on the non-specific
detectors can still cause error in identifying a complex sample. The non-specific detector
system (GC-NPD-FBD-ECD-PID), however, has been used for approximate quantitation of
relatively clean samples. The non-specific detector system can provide a "snapshot" of the
constituents in the sample, allowing determination of:
• Extent of misidentification due to overlapping peaks,
• Position of the VOCs within or not within the concentration range of anticipated
further analysis by specific detectors (GC-MS-SCAN-SIM) (if not, the sample is further
diluted), and
• Existence of unexpected peaks which need further identification by specific detectors.
On the other hand, the use of specific detectors (MS coupled to a GC) allows positive
compound identification, thus lending itself to more specificity than the multidetector GC.
Revised 9/30/89 Page 4
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Method IP-1A
VOCs
Operating in the SIM mode, the MS can readily approach the same sensitivity as the
multidetector system, but its flexibility is limited. For SIM operation, the MS is
programmed to acquire data for a limited number of targeted compounds while disregarding
othe'r acquired information. In the SCAN mode, however, the MS becomes a universal
detector often detecting compounds which are not detected by the multidetector approach.
The GC-MS-SCAN will provide positive identification, while the GC-MS-SIM procedure
provides quantitation of a restricted "target compound" list of VOCs. The analyst often
must decide whether to use specific or nonspecific detectors by considering such factors as
project objectives, desired detection limits, equipment availability, cost and personnel
capability in developing an analytical strategy. A list of some of the advantages and
disadvantages associated with non-specific and specific detectors may assist the analyst in
the decision-making process.
Non-Specific Multidetector Analytical System
Advantages
Somewhat lower equipment
cost than GC-MS
Less sample volume required
for analysis
More sensitive (BCD may
be 1000 times more sensitive
than GC-MS
Disadvantages
• Multiple detectors cost to calibrate
• Compound identification not positive
• Lengthy data interpretation (one hour
each for analysis data reduction)
• Interference(s) from co-eluting
compounds(s)
• Cannot identify unknown compounds outside
range of calibration and without standards
• Does not differentiate targeted compounds from
interfering compounds
Revised 9/30/89
PageS
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Method IP-1A VOCs
Specific Detector Analytical System
GC-MS-SIM
Advantages Disadvantages
• positive compound identification • can't identify non-specified
(ions) compounds
• greater sensitivity than • somewhat greater equipment cost
GC-MS-SCAN than multidetector GC
• less operator interpretation than • greater sample volume required than
for multidetector GC for multidetector GC
• resolve co-eluting peaks • universality of detector sacrificed
to achieve enhancement in
sensitivity
• more specific than the
multidetector GC
GC-MS-SCAN
Advantages Disadvantages
• positive compound identification • lower sensitivity than GC-MS-SIM
• can identify all compounds • greater sample volume required than
for multidetector GC
• less operator interpretation • somewhat greater equipment cost
than multidetector GC
can resolve co-eluting peaks
c
The analytical finish for the measurement chosen by the analyst should provide a definitive
identification and a precise quantitation of volatile organics. In a large part, the actual
approach to these two objectives is subject to equipment availability. Figure 1 indicates
some of the favorite options that are used as an analytical finish. The GC-MS-SCAN
option uses a capillary column GC coupled to a MS operated in a scanning mode and
supported by spectral library search routines. This option offers the nearest approximation
to unambiguous identification and covers a wide range of compounds as defined by the
completeness of the spectral library. GC-MS-SIM mode is limited to a set of target
compounds which are user defined and is more sensitive than GC-MS-SCAN by virtue of
the longer dwell times at the restricted number of m/z values. Both these techniques, but
especially the GC-MS-SIM option, can use a supplemental general non-specific detector
to verify/identify the presence of VOCs. Finally, the option labelled GC-multidetector
system uses a combination of retention time and multiple general detector verification to
Revised 9/30/89 Page 6
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Method IP-1A . VOCs
identify compounds. However, interference due to nearly identical retention times can
affect system quantitation when using this option.
For the low concentration VOCs in indoor air, typically less than 4 parts per billion by
volume (ppbv), along with their complicated chromatograms, Method HM strongly
recommends the specific detectors (GC-MS-SCAN-SIM) for positive identification and for
primary quantitation to ensure that high-quality indoor data is acquired. For the
experienced analyst whose analytical system is limited to the non-specific detectors, Section
10.3 does provide guidelines and example chromatograms showing ^^/etenUon times
and calibration response factors, and utilizing the non-specific detectors (GC-FID-ECD-
PDD) analytical system as the primary quantitative technique.
4. Significance
41 VOCs are emitted into the indoor atmosphere from a variety of sources including
diffusion from outdoor sources, manufacturing processes, and use of various products,
appliances, and building materials. Many of these VOC emissions are acutely toxic;
therefore, their determination in indoor air is necessary to assess human health impacts.
42 Conventional methods for VOC determination use solid sorbent sampling techniques.
The most widely used solid sorbent is Tenax*. An air sample is drawn through a Tenax -
filled cartridge where certain VOCs are trapped on the polymer. The sample cartridge is
transferred to a laboratory and analyzed by GC-MS.
43 VOCs can also be successfully collected in stainless steel canisters. Collection of
indoor air samples in canisters provides: 1) convenient integration of indoor samples over
a specific time period, (e.g., 24 hours), 2) remote sampling and central analysis, 3) ease ot
storing and shipping samples, 4) unattended sample collection, 5) analysis of samples from
multiple sites with one analytical system, and 6) collection of sufficient sample volume to
allow assessment of measurement precision and/or analysis of samples by several analytical
systems. However, care must be exercised in selecting, cleaning, and handling sample
canisters and sampling apparatus to avoid losses or contamination of the samples.
Contamination is a critical issue with canister-based sampling because the canister is the
last element in the sampling train.
4.4 Interior surfaces of the canisters are treated by the SUMMA® passivation process, in
which a pure chrome-nickel oxide is formed on the surface. This type of vessel has been
used in the past for sample collection and has demonstrated sample storage stability ot
many specific organic compounds.
4 5 This method can be applied to sampling and analysis of not only VOCs, but also some
selected semivolatile organic compounds (SVOCs). The term "semivolatile organic
compounds" is used to broadly describe organic compounds that are too volatile to be
collected by filtration air sampling but not volatile enough for thermal desorption from solid
sorbents SVOCs can generally be classified as those with saturation vapor pressures at
25°C between 10'1 and 10'7 mm Hg. VOCs are generally classified as those orgamcs having
saturated vapor pressures at 25°C greater than 10" mm Hg.
Revised 9/30/89 PaSe 7
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Method IP-1A VOCs
5. Definitions
Note: Definitions used in this document and any user-prepared standard operating
procedures (SOPs) should be consistent with ASTM Methods D1356, E260, and E355. All
pertinent abbreviations and symbols are defined within this document at point of use.
Additional definitions, abbreviations, and symbols are located in Appendix A-I and B-2 of
this Compendium.
5.1 Absolute canister pressure = Pg + Pa, where Pg = gauge pressure in the canister (kPa,
psi) and Pa = barometric pressure (see Section 5.2).
52 Absolute pressure - Pressure measured with reference to absolute zero pressure (as
opposed to atmospheric pressure), usually expressed as kPa, mm Hg or psia.
5.3 Cryogen - A refrigerant used to obtain very low temperatures in the cryogenic trap of
the analytical system. A typical cryogen is liquid oxygen (bp -183.0°C) or liquid argon
(bp -185.rC).
5.4 Dynamic calibration - Calibration of an analytical system using calibration gas standard
concentrations in a form identical or very similar to the samples to be analyzed and by
introducing such standards into the inlet of the sampling or analytical system in a manner
very similar to the normal sampling or analytical process.
5.5 Gauge pressure - Pressure measured above ambient atmospheric pressure (as opposed
to absolute pressure). Zero gauge pressure is equal to ambient atmospheric (barometric)
pressure.
5.6 MS-SCAN - The GC is coupled to a MS programmed in the SCAN mode to scan all
ions repeatedly during the GC run. As used in the current context, this procedure serves
as a qualitative identification and characterization of the sample.
5.7 MS-SIM - The GC is coupled to a MS programmed to acquire data for only specified
ions and to disregard all others. This is performed using SIM coupled to retention time
discriminators. The GC-SIM analysis provides quantitative results for selected constituents
of the sample gas as programmed by the user.
5.8 Megabore* column - Chromatographic column having an internal diameter (I.D.)
greater than 0.50 mm. The Megabore* column is a trademark of the J&W Scientific Co.
For purposes of this method, Megabore* refers to chromatographic columns with 0.53 mm
I.D.
5.9 Pressurized sampling - Collection of an air sample in a canister with a (final) canister
pressure above atmospheric pressure, using a sample pump.
5.10 Qualitative accuracy - The ability of an analytical system to correctly identify
compounds.
5.11 Quantitative accuracy - The ability of an analytical system to correctly measure the
concentration of an identified compound.
Revised 9/30/89 PaSe 8
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Method IP-1A . VOCs
5.12 Static calibration - Calibration of an analytical system using standards in a form
different than the samples to be analyzed. An example of a static calibration would be
injecting a small volume of a high concentration standard directly onto a GC column,
bypassing the sample extraction and preconcentration portion of the analytical system.
5.13 Subatmospheric sampling - Collection of an air sample in an evacuated canister at a
(final) canister pressure below atmospheric pressure, without the assistance of a sampling
pump. The canister is filled as the internal canister pressure increases to ambient or near
ambient pressure. An auxiliary vacuum pump may be used as part of the sampling system
to flush the inlet tubing prior to or during sample collection.
6. Interferences and Limitations
6.1 Interferences can occur in sample analysis if moisture accumulates in the dryer (see
Section 10.1.1.2). An automated cleanup procedure that periodically heats the dryer to
about 100°C while purging with zero air eliminates any moisture buildup. This procedure
does not degrade sample integrity.
62 Contamination may occur in the sampling system if canisters are not properly cleaned
before use. Additionally, all other sampling equipment (e.g., pump and flow controllers)
should be thoroughly cleaned to ensure that the filling apparatus will not contaminate
samples. Instructions for cleaning the canisters and certifying the field sampling system are
described in Sections 12.1 and 12.2, respectively.
6.3 Because the GC-MS analytical system employs a Nafion* permeable membrane dryer
to remove water vapor selectively from the sample stream, polar organic compounds may
permeate concurrent with the moisture molecule. Consequently, the analyst should
quantitate his or her system with the specific organic constituents under examination.
7. Apparatus
7.1 Sample Collection
Note: Subatmospheric pressure and pressurized canister sampling systems are commercially
available and have been used as part of U.S. Environmental Protection Agency's Toxics Air
Monitoring Stations (TAMS), Urban Air Toxic Pollutant Program (UATP), and the non-
methane organic compound (NMOC) sampling and analysis program.
7.1.1 Subatmospheric Pressure (see Figure 2 Without Metal Bellows Type Pump)
7.1.1.1 Sampling inlet line - stainless steel tubing to connect the sampler to the
sample inlet.
7.1.1.2 Sample canister - leak-free stainless steel pressure vessels of desired volume
(e.g., 6 L), with valve and SUMMA* passivated interior surfaces (Scientific Instrumentation
Specialists, Inc., P.O. Box 8941, Moscow, ID 83843, or Anderson Samplers, Inc., 4215-C
Wendell Dr., Atlanta, GA, 30336, or equivalent).
7.1.13 Stainless steel vacuum/pressure gauge - capable of measuring vacuum (-100
to 0 kPa or 0 to 30 in Hg) and pressure (0-206 kPa or 0-30 psig) in the sampling system
Revised 9/30/89 Page?
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Method IP-1A VOCs
(Matheson, P.O. Box 136, Morrow, GA 30200, Model 63-3704, or equivalent). Gauges
should be tested clean and leak tight.
7.1.1.4 Electronic mass flow controller - capable of maintaining a constant flow rate
(•*• 10%) over a sampling period of up to 24 hours and under conditions of changing
temperature (20-40°C) and humidity (Tylan Corp., 19220 S. Normandie Ave., Torrance,
CA 90502, Model FC-260, or equivalent).
7.1.1.5 Paniculate matter filter - 2 /«n sintered stainless steel in-line filter (Nupro Co.,
4800 E. 345th St, Willoughby, OH 44094, Model SS-2F-K4-2, or equivalent).
7.1.1.6 Electronic timer - for unattended sample collection (Paragon Elect. Co., 606
Parkway Blvd., P.O. Box 28, Twin Rivers, WI 54201, Model 7008-00, or equivalent).
7.1.1.7 Solenoid valve - electrically-operated, bi-stable solenoid valve (Skinner
Magnelatch Valve, New Britain, CT, Model V5RAM49710, or equivalent) with Viton* seat
and o-rings.
7.1.1.8 Chromatographic grade stainless steel tubing and fittings - for interconnections
(Alltech Associates, 2051 Waukegan Rd., Deerfield, IL 60015, Cat. #8125, or equivalent).
All such materials in contact with sample, analyte, and support gases prior to analysis
should be chromatographic grade stainless steel.
7.1.1.9 Thermostatically controlled heater - to maintain temperature inside insulated
sampler enclosure above ambient temperature (Watlow Co., Pfafftown, NC, Part 04010080,
or equivalent).
7.1.1.10 Heater thermostat - automatically regulates heater temperature (Elmwood
Sensors, Inc., 500 Narragansett Park Dr., Pawtucket RI 02861, Model 3455-RC-01000222,
or equivalent).
7.1.1.11 Fan - for cooling sampling system (EG&G Rotron, Woodstock, NY, Model
SUZAI, or equivalent). .
7.1.1.12 Fan thermostat - automatically regulates fan operation (Elmwood Sensors,
Inc., Pawtucket, RI, Model 3455-RC-0100-0244, or equivalent).
7.1.1.13 Maxmum-minimum thermometer - records highest and lowest temperatures
during sampling period (Thomas Scientific, Brooklyn Thermometer Co., Inc., P/N 9327H30,
or equivalent).
7.1.1.14 Nupro stainless steel shut-off valve - leak free, for vacuum/pressure gauge.
7.1.1.15 Auxiliary vacuum pump - continuously draws air to be sampled through the
inlet manifold at 10 L/min. or higher flow rate. Sample is extracted from the manifold at
a lower rate, and excess air is exhausted. . , • i
Note: The use of higher inlet flow rates dilutes any contamination present in the inlet and
reduces the possibility of sample contamination as a result of contact with active adsorption
sites on inlet walls.
7.1.1.16 Elapsed time meter - measures duration of sampling (Conrac, Cramer L>iv.,
Old Saybrook, CT, Type 6364, P/N 10082, or equivalent).
7.1.1.17 Optional fixed orifice, capillary, or adjustable micrometenng valve - may be
used in lieu of the electronic flow controller for grab samples or short duration time-
integrated samples. Usually appropriate only in situations where screening samples are
taken to assess future sampling activity.
Revised 9/30/89 ~ Pagelo
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Method IP-1A VOCs
7.12 Pressurized (see Figure 2 With Metal Bellows Type Pump and Figure 3)
1.12.1 Sample pump - stainless steel, metal bellows type (Metal Bellows Corp., 1075
Providence Highway, Sharon, MA 02067, Model MB-151, or equivalent), capable of 2
atmospheres output pressure. Pump must be free of leaks, clean, and uncontaminated by
oil or organic compounds.
Note: An alternative sampling system has been developed by Dr. R. Rasmussen, The
Oregon Graduate Center (18,19) and is illustrated in Figure 3. This flow system uses, in
order, a pump, a mechanical flow regulator, and a mechanical compensating flow restrictive
device. In this configuration the pump is purged with a large sample flow, thereby
eliminating the need for an auxiliary vacuum pump to flush the sample inlet Interferences
using this configuration have been minunal.
7.122 Other supporting materials - all other components of the pressurized sampling
system [Figure 2 (with metal bellows type pump) and Figure 3] are similar to components
discussed in Sections 7.1.1.1 through 7.1.1.16.
12 Sample Analysis
7.2.1 GC-MS-SCAN Analytical System (see Figure 4)
12.1.1 The GC-MS-SCAN analytical system must be capable of acquiring and
processing data in the MS-SCAN mode.
7.2.1.2 Gas chromatograph - capable of sub-ambient temperature programming for
the oven, with other generally standard features such as gas flow regulators, automatic
control of valves and integrator, etc. Flame ionization detector optional. (Hewlett Packard,
Rt. 41, Avondale, PA 19311, Model 5880A, with oven temperature control and Level 4
BASIC programming, or equivalent.)
12.13 Chromatographic detector - mass-selective detector (Hewlett Packard,
3000-T Hanover St., 9B, Palo Alto, CA 94304, Model HP-5970 MS, or equivalent),
equipped with computer and appropriate software (Hewlett Packard, 3000-T Hanover St.,
9B, Palo Alto, CA 94304, HP-216 Computer, Quicksilver MS software, Pascal 3.0, mass
storage 9133 HP Winchester with 3.5 inch floppy disk, or equivalent). The GC-MS is set
in the SCAN mode, where the MS screens the sample for identification and quantitation
of VOC species.
7.2.1.4 Cryogenic trap with temperature control assembly; refer to Section 10.1.1.3
for complete description of trap and temperature control assembly (Nutech Corporation,
2142 Geer St., Durham, NC, 27704, Model 320-01, or equivalent).
7.2.1.5 Electronic mass flow controllers (3) - maintain constant flow for earner gas
and sample gas) and to provide analog output to monitor flow anomalies (Tylan Model 260,
0-100 cm3/min, or equivalent).
7.2.1.6 Vacuum pump - general purpose laboratory pump, capable of drawing the
desired sample volume through the cryogenic trap (Thomas Industries, Inc., Sheboygan, WI,
Model 107A20, or equivalent).
7.2.1.7 Chromatographic grade stainless steel tubing and stainless steel plumbing
fittings - refer to Section 7.1.1.8 for description.
Revised 9/30/89 ~~ PageTl
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Method IP-1A VOCs
7.2.1.8 Chromatographic column - to provide compound separation such as shown in
Table 5 (Hewlett Packard, Rt. 41, Avondale, PA 19311, OV-I capillary column, 0.32 mm
x 50 m with 0.88 /tm crosslinked methyl silicone coating, or equivalent).
72.1.9 Stainless steel vacuum/pressure gauge (optional) capable of measuring vacuum
(-101.3 to 0 kPa) and pressure (0-206 kPa) in the sampling system (Matheson, P.O. Box 136,
Morrow, GA 30200, Model 63-3704, or equivalent). Gauges should be tested clean and
leak tight.
7.2.1.10 Stainless steel cylinder pressure regulators - standard, two-stage cylinder
regulators with pressure gauges for helium, zero air and hydrogen gas cylinders.
7.2.1.11 Gas purifiers (3) - used to remove organic impurities and moisture from gas
streams (Hewlett Packard, Rt. 41, Avondale, PA, 19311, P/N 19362 -60500, or equivalent).
7.2.1.12 Low dead-volume tee (optional) - used to split the exit flow from the GC
column (Alltech Associates, 2051 Waukegan Rd., Deerfield, IL 60015, Cat. #5839, or
equivalent).
7.2.1.13 Nafion* dryer - consisting of Nafion* tubing coaxially mounted within larger
tubing (Perma Pure Products, 8 Executive Drive, Toms River, NJ, 08753, Model MD-125-
48, or equivalent). Refer to Section 10.1.1.2 for description.
7.2.1.14 Six-port gas chromatographic valve - (Seismograph Service Corp, Tulsa, OK,
Seiscor Model VIE, or equivalent).
7.2.1.15 Chart recorder (optional) - compatible with the detector output signals to
record optional FED detector response to the sample.
7.2.1.16 Electronic integrator (optional) - compatible with the detector output signal
of the FID and capable of integrating the area of one or more response peaks and
calculating peak areas corrected for baseline drift
122 GC-MS-SIM Analytical System (see Figure 4)
7.2.2.1 The GC-MS-SIM analytical system must be capable of acquiring and
processing data in the MS-SIM mode.
1222 All components of the GC-MS-SIM system are identical to Sections 7.2.1.2
through 7.2.1.16.
723 GC-Multidetector Analytical System (see Figure 5 and Figure 6)
7.2.3.1 Gas chromatograph with flame ionization and electron capture detectors
(photoionization detector optional) -capable of sub-ambient temperature programming for
the oven and simultaneous operation of all detectors, and with other generally standard
features such as gas flow regulators, automatic control of valves and integrator, etc.
(Hewlett Packard, Rt. 41, Avondale, PA 19311, Model 5880A, with oven temperature
control and Level 4 BASIC programming, or equivalent).
1232 Chart recorders - compatible with the detector output signals to record
detector response to the sample.
12.3.3 Electronic integrator - compatible with the detector output signals and capable
of integrating the area of one or more response peaks and calculating peak areas corrected
for baseline drift
Revised 9/30/89 Page 12
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Method IP-1A VOCs
733.4 Six-port gas chromatographic valve - (Seismograph Service Corp, Tulsa, OK,
Seiscor Model VIII, or equivalent). . ,_,,,,
1233 Cryogenic trap with temperature control assembly refer to Section 1U.1.1.J tor
complete description of trap and temperature control assembly (Nutech Corporation, 2142
Geer St., Durham, NC 27704, Model 320-01, or equivalent).
723.6 Electronic mass flow controllers (3) - maintain constant flow (for earner gas,
nitrogen make-up gas and sample gas) and to provide analog output to monitor flow
anomalies (Tylan Model 260, 0-100 cnr/min, or equivalent).
72.3.7 Vacuum pump - general purpose laboratory pump, capable of drawing the
desired sample volume through the cryogenic trap (see 72.1.6 for source and description).
7.2.3.8 Chromatographic grade stainless steel tubing and stainless steel plumbing
fittings - refer to Section 7.1.1.8 for description.
7.23.9 Chromatographic column - to provide compound separation such as shown in
Table 7. (Hewlett Packard, Rt. 41, Avondale, PA 19311, OV-I capillary column, 0.32 mm
x 50 m with 0.88 /im crosslinked methyl silicone coating, or equivalent).
Note: Other columns (e.g., DB-624) can be used as long as the system meets user needs.
The wider Megabore* column (i.e., 0.53 mm I.D.) is less susceptible to plugging as a result
of trapped water, thus eliminating the need for a Nafion* dryer in the analytical system.
The Megabore* column has sample capacity approaching that of a packed column, while
retaining much of the peak resolution traits of narrower columns (i.e., 0.32 mm I.D.).
7.2.3.10 Vacuum/pressure gauges (3) - refer to Section 7.2.1.9 for description.
7.23.11 Cylinder pressure stainless steel regulators standard, two-stage cylinder
regulators with pressure gauges for helium, zero air, nitrogen, and hydrogen gas cylinders.
733.12 Gas purifiers (4) - used to remove organic impurities and moisture from gas
streams (Hewlett-Packard, Rt. 41, Avondale, PA, 19311, P/N 19362 60500, or equivalent).
733.13 Low dead-volume tee - used to split (50/50) the exit flow from the GC
column (Alltech Associates, 2051 Waukegan Rd., Deerfield, BL 60015, Cat. #5839, or
equivalent).
73 Canister Cleaning System (see Figure 7)
73.1 Vacuum pump - capable of evacuating sample canister(s) to an absolute pressure
of <0.05 mm Hg.
733 Manifold - stainless steel manifold with connections for simultaneously cleaning
several canisters.
733 Shut-off valve(s) - seven (7) on-off toggle valves.
73.4 Stainless steel vacuum gauge - capable of measuring vacuum in the manifold to an
absolute pressure of 0.05 mm Hg or less.
73.5 Cryogenic trap (2 required) - stainless steel U-shaped open tubular trap cooled
with liquid oxygen or argon to prevent contamination from back diffusion of oil from
vacuum pump and to provide clean, zero air to sample canister(s).
73.6 Stainless steel pressure gauges (2) - 0-345 kPa (0-50 psig) to monitor zero air
pressure.
7.3.7 Stainless steel flow control valve - to regulate flow of zero air into camster(s).
Revised 9/30/89 Pa8e 13
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Method IP-1A
VOCs
7.3.8 Humidifier - pressurizable water bubbler containing high performance liquid
chromatography (HPLC) grade deionized water or other system capable of providing
moisture to the zero air supply.
73.9 Isothermal oven (optional) for heating canisters (Fisher Scientific, Pittsburgh, PA,
Model 349, or equivalent).
7.4 Calibration System and Manifold (See Figure 8)
7.4.1 Calibration manifold - glass manifold, (1.25 cm I.D. x 66 cm) with sampling ports
and internal baffles for flow disturbance to ensure proper mixing.
7.4.2 Humidifier - 500 mL impinger flask containing HPLC grade deionized water.
7.43 Electronic mass flow controllers - one 0 to 5 L/min and one 0 to 50 cm3/min
(Tylan Corporation, 23301-TS Wilmington Ave., Carson, CA, 90745, Model 2160, or
equivalent).
7.4.4 Teflon* filter(s) - 47 mm Teflon* filter for particulate control, best source.
8. Reagents and Materials
8.1 Gas cylinders of helium, hydrogen, nitrogen, and zero air ultrahigh purity grade, best
source.
8.2 Gas calibration standards - cylinder(s) containing approximately 10 ppmv of each of the
following compounds of interest:
vinyl chloride
vinylidene chloride
l,l,2-trichloro-l,2,2-trifluoroethane
p-dichlorobenzene
chloroform
1,2-dichloroethane
benzenecarbon
toluene
Freon 12
methyl chloride
ethylbenzene
1,2,4-trichlorobenzene
methyl bromide
ethyl chloride
Freon 11
dichloromethane
1,1-dichloroethane
cis-l,2-dichloroethylene
1,2-dichloropropane
1,1,2-trichloroethane
1,2-dibromoethane
tetrachloroethylene
chlorobenzene
benzyl chloride
hexachloro-l,3-butadiene
methyl chloroform
tetrachloride
trichloroethylene
cis-l,3-dichloropropene
trans-13-dichloropropene
l,2-dichloro-l,l,2,2-tetrafluoroethane
o-dichlorobenzene
o-xylene
m-xylene
p-xylene
styrene
1,1,2,2-tetrachloroethane
1,3,5-trimethylbenzene
1,2,4-trimethylbenzene
m-dichlorobenzene
Revised 9/30/89
Page 14
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Method IP-1A VOCs
The cylinder(s) should be traceable to a National Bureau of Standards (NBS) Standard
Reference Material (SRM) or to a NBS/EPA approved Certified Reference Material
(CRM). The components may be purchased in one cylinder or may be separated into
different cylinders. Refer to manufacturer's specification for guidance on purchasing and
mixing VOCs in gas cylinders. Those compounds purchased should match one's own target
list.
8.3 Cryogen - liquid oxygen (bp -183.0°C), or liquid argon (bp -185.7°C), best source.
8.4 Gas purifiers - connected in-line between hydrogen, nitrogen, and zero air gas cylinders
and system inlet line, to remove moisture and organic impurities from gas streams (Alltech
Associates, 2051 Waukegan Road, Deerfield, JL, 60015, or equivalent).
8.5 Deionized water - high performance liquid chromatography (HPLC) grade, ultrahigh
purity (for humidifier), best source.
8.6 4-bromofluorobenzene - used for tuning GC-MS, best source.
8.7 Hexane - for cleaning sampling system components, reagent grade, best source.
8.8 Methanol - for cleaning sampling system components, reagent grade, best source.
9. Sampling System
9.1 System Description
9.1.1 Subatmospheric Pressure Sampling (see Figure 2 Without Metal Bellows Type
Pump)
9.1.1.1 In preparation for subatmospheric sample collection in a canister, the canister
is evacuated to 0.05 mm Hg. When opened to the atmosphere containing the VOCs to be
sampled, the differential pressure causes the sample to flow into the canister. This
technique may be used to collect grab samples (duration of 10 to 30 seconds) or time-
integrated samples (duration of 12 to 24 hours) taken through a flow-restrictive inlet (e.g.,
mass flow controller, critical orifice).
9.1.L2 With a critical orifice flow restrictor, there will be a decrease in the flow rate
as the pressure approaches atmospheric. However, with a mass flow controller, the
subatmospheric sampling system can maintain a constant flow rate from full vacuum to
within about 7 kPa (1.0 psi) or less below ambient pressure.
9.12 Pressurized Sampling (see Figure 2 With Metal Bellows Type Pump)
9.1.2.1 Pressurized sampling is used when longer-term integrated samples or higher
volume samples are required. The sample is collected in a canister using a pump and flow
control arrangement to achieve a typical 103-206 kPa (15-30 psig) final canister pressure.
For example, a 6-liter evacuated canister can be filled at 10 cm3/min for 24 hours to
achieve a final pressure of about 144 kPa (21 psig).
Revised 9/30/89 Pflge 15
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Method IP-1A VOCs
9.122 In pressurized canister sampling, a metal bellows type pump draws in air from
the sampling manifold to fill and pressurize the sample canister.
9.13 All Samplers
9.13.1 A flow control device is chosen to maintain a constant flow into the canister
over the desired sample period. This flow rate is determined so the canister is filled (to
about 88.1 kPa for subatmospheric pressure sampling or to about one atmosphere above
ambient pressure for pressurized sampling) over the desired sample period. The flow rate
can be calculated by:
F = (P x V)/(T x 60)
where:
F = flow rate, cm3/min
P = final canister pressure, atmospheres absolute. P is approximately equal to:
[(kPa gauge)/101.2] + 1
V = volume of the canister, cm3
T = sample period, hours
For example, if a 6 L canister is to be rilled to 202 kPa (2 atmospheres) absolute pressure
in 24 hours, the flow rate can be calculated by:
F = (2 x 6000)/(24 x 60) = 83 cm3/min
9.13.2 For automatic operation, the timer is wired to start and stop the pump at
appropriate times for the desired sample period. The timer must also control the solenoid
valve, to open the valve when starting the pump and close the valve when stopping the
pump.
9.133 The use of the Skinner Magnelatch valve avoids any substantial temperature
rise that would occur with a conventional, normally closed solenoid valve that would have
to be energized during the entire sample period. The temperature rise in the valve could
cause outgassing of organic compounds from the Viton valve seat material. The Skinner
Magnelatch valve requires only a brief electrical pulse to open or close at the appropriate
start and stop times and therefore experiences no temperature increase. The pulses may
be obtained either with an electronic timer that can be programmed for short (5 to 60
seconds) ON periods, or with a conventional mechanical timer and a special pulse circuit.
A simple electrical pulse circuit for operating the Skinner Magnelatch solenoid valve with
a conventional mechanical timer is illustrated in Figure 9(a). However, with this simple
circuit, the valve may operate unreliably during brief power interruptions or if the tinier is
manually switched on and off too fast. A better circuit incorporating a time-delay relay to
provide more reliable valve operation is shown in Figure 9(b).
9.13.4 The connecting lines between the sample inlet and the canister should be as
short as possible to minimize their volume. The flow rate into the canister should remain
relatively constant over the entire sampling period. If a critical orifice is used, some drop
Revised 9/30/89 Page 16
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Method IP-1A VOCs
in the flow rate may occur near the end of the sample period as the canister pressure
approaches the final calculated pressure.
9.1.3.5 As an option, a second electronic timer (see Section 7.1.1.6) may be used to
start the auxiliary pump several hours prior to the sampling period to flush and condition
the inlet line.
9.1.3.6 Prior to use, each sampling system must pass a humid zero air certification
(see Section 12.2.2). All plumbing should be checked carefully for leaks. The canisters must
also pass a humid zero air certification before us (see Section 12.1).
92 Sampling Procedure
9.2.1 The sample canister should be cleaned and tested according to the procedure in
Section 12.1.
93.2. A sample collection system is assembled as shown hi Figure 2 (and Figure 3) and
must meet certification requirements as outlined in Section 12.23.
Note: The sampling system should be contained in an appropriate enclosure.
923 Prior to locating the sampling system, the user may want to perform "screening
analyses" using a portable GC system, as outlined in Appendix B, to determine potential
volatile organics present and potential "hot spots." The information gathered from the
portable GC screening analysis would be used in developing a monitoring protocol, which
includes the sampling system location, based upon the "screening analysis" results.
92A After "screening analysis," the sampling system is located. Temperatures of indoor
air and sampler box interior are recorded on canister sampling data sheet (see Figure 10).
Note: The following discussion is related to Figure 2.
92.5 To verify correct sample flow, a "practice" (evacuated) canister is used in the
sampling system.
Note: For a subatmospheric sampler, the flow meter and practice canister are needed. For
the pump-driven system, the practice canister is not needed, as the flow can be measured
at the outlet of the system. A certified mass flow meter is attached to the inlet line of the
manifold, just in front of the filter. The canister is opened. The sampler is turned on and
the reading of the certified mass flow meter is compared to the sampler mass flow
controller. The values should agree within ± 10%. If not, the sampler mass flow meter
needs to be recalibrated or there is a leak in the system. This should be investigated and
corrected.
Note: Mass flow meter readings may drift. Check the zero reading carefully and add or
subtract the zero reading when reading or adjusting the sampler flow rate, to compensate
for any zero drift. After two minutes, the desired canister flow rate is adjusted to the
proper value (as indicated by the certified mass flow meter) by the sampler flow control
unit controller (e.g., 3.5 cm3/min for 24 hr, 7.0 cm3/min for 12 hr). Record final flow under
"CANISTER FLOW RATE," Figure 10.
92.6 The sampler is turned off and the elapsed time meter is reset to 000.0.
Note: Any time the sampler is turned off, wait at least 30 seconds to turn the sampler back
on.
Revised 9/30/89 Page 17
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Method IP-1A - VOCs
92.1 The "practice" canister and certified mass flow meter are disconnected and a clean
certified (see Section 12.1) canister is attached to the system.
9.2.8 The canister valve and vacuum/pressure gauge valve are opened.
92.9 Pressure/vacuum in the canister is recorded on the canister sampling field data
sheet (see Figure 10) as indicated by the sampler vacuum/pressure gauge.
9.2.10 The vacuum/pressure gauge valve is closed and the maximum/ininimum
thermometer is reset to current temperature. Time of day and elapsed time meter readings
are recorded on the canister sampling field data sheet
9.2.11 The electronic timer is set to begin and stop the sampling period at the
appropriate times. Sampling commences and stops by the programmed electronic timer.
9.2.12 After the desired sampling period, the maximum, minimum, current interior
temperature and current indoor temperature are recorded on the sampling field data sheet.
The current reading from the flow controller is recorded.
9.2.13 At the end of the sampling period, the vacuum/pressure gauge valve on the
sampler is briefly opened and closed and the pressure/vacuum is recorded on the sampling
data sheet. Pressure should be close to desired pressure.
Note: For a subatmospheric sampling system, if the canister is at atmospheric pressure
when the final pressure check is performed, the sampling period may be suspect. This
information should be noted on the sampling field data sheet Time of day and elapsed
time meter readings are also recorded.
9.2.14 The canister valve is closed. The sampling line is disconnected from the canister
and the canister is removed from the.system. For a subatmospheric system, a certified mass
flow meter is once again connected to the inlet manifold in front of the in-line filter and
a "practice" canister is attached to the Magnelatch valve of the sampling system. The final
flow rate is recorded on the canister sampling data sheet (see Figure 10).
Note: For a pressurized system, the final flow may be measured directly. The sampler is
turned off.
92.15 An identification tag is attached to the canister. Canister serial number, sample
number, location, and date are recorded on the tag.
10. Analytical System (see Figures 4, 5 and 6)
10.1 System Description
10.1.1 GC-MS-SCAN System
10.1.1.1 The analytical system is comprised of a GC equipped with a mass-selective
detector set in the SCAN mode (see Figure 4). All ions are scanned by the MS repeatedly
during the GC run. The system includes a computer and appropriate software for data
acquisition, data reduction, and data reporting. A 400 cm3 air sample is collected from the
canister into the analytical system. The sample air is first passed through a Nafion* dryer,
through the 6-port chromatographic valve, then routed into a cryogenic trap.
Note: While the GC-multidetector analytical system does not employ a Nafion® dryer for
drying the sample gas stream, it is used here because the GC-MS system utilizes a larger
sample volume and is far more sensitive to excessive moisture than the GC-multidetector
Revised 9/30/89 ~~
-------
Method IP-1A VOCs
analytical system. Moisture can adversely affect detector precision. The Nafion* dryer also
prevents freezing of moisture on the 0.32 mm internal diameter (I.D.) column, which may
cause column blockage and possible breakage. The trap is heated (-160°C to 120°C in 60
sec) and the analyte is injected onto the OV-I capillary column (0.32 mm x 50 m).
Note: Rapid heating of the trap provides efficient transfer of the sample components onto
the gas chromatographic column. Upon sample injection onto the column, the MS
computer is signaled by the GC computer to begin detection of compounds which elute
from the column. The gas stream from the GC is scanned within a preselected range of
atomic mass units (amu). For detection of compounds hi Table 1, the range should be 18
to 250 amu, resulting in a 1.5 Hz repetition rate. Six scans per eluting chromatographic
peak are provided at this rate. The 10-15 largest peaks are chosen by an automated data
reduction program, the three scans nearest the peak apex are averaged, and a background
subtraction is performed. A library search is then performed and the top ten best matches
for each peak are listed. A qualitative characterization of the sample is provided by this
procedure. A typical chromatogram of VOCs determined by GC-MS-SCAN is illustrated
in Figure ll(a).
10.1.1.2 A Nafion* permeable membrane dryer is used to remove water vapor
selectively from the sample stream. The permeable membrane consists of Nafion* tubing
(a copolymer of tetrafluoroethylene and fluorosulf onyl monomer) that is coaxially mounted
within larger tubing. The sample stream is passed through the ulterior of the Nafion*
tubing, allowing water (and other light, polar compounds) to permeate through the walls
into a dry air purge stream flowing through the annular space between the Nafion* and
outer tubing. . ,
Note: To prevent excessive moisture build-up and any memory effects in the dryer, a
cleanup procedure involving periodic heating of the dryer (100°C for 20 minutes) while
purging with dry zero air (500 cm3/min) should be implemented as part of the user's
standard operating procedure (SOP) manual. The clean-up procedure is repeated during
each analysis (see Section 14, reference 7). Recent studies have indicated no substantial
loss of targeted VOCs utilizing the above clean-up procedure (7). This cleanup procedure
is particularly useful when employing cryogenic preconcentration of VOCs with subsequent
GC analysis using a 0.32 mm I.D. column because excess accumulated water can cause trap
and column blockage and also adversely affect detector precision. In addition, the
improvement hi water removal from the sampling stream will allow analyses of much larger
volumes of sample air hi the event that greater system sensitivity is required for targeted
compounds. . , X7~~
10.1.13 The packed metal tubing used for reduced temperature trapping ot VOCs
is shown in Figure 12. The cooling unit is comprised of a 032 cm outside diameter (O.D.)
nickel tubing loop packed with 60-80 mesh Pyrex* beads (Nutech Model 320-01, or
equivalent). The nickel tubing loop is wound onto a cylindrically formed tube heater (250
watt). A cartridge heater (25 watt) is sandwiched between pieces of aluminum plate at the
trap inlet and outlet to provide additional heat to eliminate cold spots hi the transfer
tubing. During operation, the trap is inside a two-section stainless steel shell which is well
insulated. Rapid heating (-150 to + 100°C in 55 s) is accomplished by direct thermal contact
Revised 9/30/89 ~~~ ~~ Pa§e w
-------
Method IP-1A VOCs
between the heater and the trap tubing. Cooling is achieved by vaporization of the cryogen.
In the shell, efficient cooling (+120 to -150°C in 225 s) is facilitated by confining the
vaporized cryogen to the small open volume surrounding the trap assembly. The trap
assembly and chromatographic valve are mounted on a baseplate fitted into the injection
and auxiliary zones of the GC on an insulated pad directly above the column oven when
used with the Hewlett-Packard 5880 GC.
Note: Alternative trap assembly and connection to the GC may be used depending upon
user's requirements. The carrier gas line is connected to the injection end of the analytical
column with a zero-dead-volume fitting that is usually held in the heated zone above the
GC oven. A15cmxl5cmx24cm aluminum box is fitted over the sample handling
elements to complete the package. Vaporized cryogen is vented through the top of the box.
10.1.1.4 As an option, the analyst may wish to split the gas stream exiting the column
with a low dead-volume tee, passing one-third of the sample gas (1.0 mL/min) to the mass
selective detector and the remaining two-thirds (2.0 mL/min) through a flame ionization
detector, as illustrated as an option in Figure 4. The use of the specific detector (MS-
SCAN) coupled with the nonspecific detector (FED) enables enhancement of data acquired
from a single analysis. In particular, the FID provides the user:
*
• Semi-real time picture of the progress of the analytical scheme;
• Confirmation by the concurrent MS analysis of other labs that can
provide only FID results; and
• Ability to compare GC-FBD with other analytical laboratories with
only GC-FED capability.
10.12 GC-MS-SIM System
10.12.1 The analytical system is comprised of a GC equipped with an OV-I capillary
column (032 mm x 50 m) and a mass-selective detector set in the SIM mode (see Figure
4). The GC-MS is set up for automatic, repetitive analysis. The system is programmed to
acquire data for only the target compounds and to disregard all others. The-sensitivity is
0.1 ppbv for a 250 cm3 air sample with analytical precision of about 5% relative standard
deviation. Concentration of compounds based upon a previously installed calibration table
is reported by an automated data reduction program. A Nafion® dryer is also employed
by this analytical system prior to cryogenic preconcentration; therefore, many polar
compounds are not identified by this procedure.
10.122 SIM analysis is based on a combination of retention times and relative
abundances of selected ions (see Table 2). These qualifiers are stored on the hard disk of
the GC-MS computer and are applied for identification of each chromatographic peak.
The retention time qualifier is determined to be ± 0.10 minute of the library retention
time of the compound. The acceptance level for relative abundance is determined to be
± 15% of the expected abundance, except for vinyl chloride and methylene chloride, which
is determined to be ± 25%. Three ions are measured for most of the forty compounds.
When compound identification is made by the computer, any peak that fails any of the
qualifying tests is flagged (e.g., with an *). All the data should be manually examined by
the analyst to determine the reason for the flag and whether the compound should be
Revised 9/30/89 Page 20
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Method IP-1A _ VOCs
reported as found. While this adds some subjective judgment to the analysis, computer-
generated identification problems can be clarified by an experienced operator. Manual
inspection of the quantitative results should also be performed to verify concentrations
outside the expected range. A typical chromatogram of VOCs determined by GC-MS-SIM
mode is illustrated in Figure ll(b).
10.13 GC-Multidetector (GC-FID-ECD) System with Optional PID
10.1.3.1 The analytical system (see Figure 5) is comprised of a gas chromatograph
equipped with a capillary column and electron capture and flame ionization detectors (see
Figure 5). In typical operation, sample air from pressurized canisters is vented past the inlet
to the analytical system from the canister at a flow rate of 75 cm3/min. For analysis, only
35 cm3/min of sample gas is used, while excess is vented to the atmosphere. Sub-ambient
pressure canisters are connected directly to the inlet The sample gas stream is routed
through a six port chromatographic valve and into the cryogenic trap for a total sample
volume of 490 cm3.
Note: This represents a 14 minute sampling period at a rate of 35 cm /min. The trap (see
Section 10.1.1.3) is cooled to -150°C by controlled release of a cryogen. VOCs and SVOCs
are condensed on'the trap surface while N2, O2, and other sample components are passed
to the pump. After the organic compounds are concentrated, the valve is switched and the
trap is heated. The revolatilized compounds are transported by helium carrier gas at a rate
of 4 cm3/min to the head of the Megabore« OV-I capillary column (0.53 mm x 30 m).
Since the column's initial temperature is at -50°C, the VOCs and SVOCs are cryofocussed
on the head of the column. Then, the oven temperature is programmed to increase and
the VOCs/SVOCs in the carrier gas are chromatographically separated. The carrier gas
containing the separated VOCs/SVOCs is then directed to two parallel detectors at a flow
rate of 2 cm3/min each. The detectors sense the presence of the speciated VOCs/SVOCs,
and the response is recorded by either a strip chart recorder or a data processing unit.
10.1.3.2 Typical chromatograms of VOCs determined by the GC-FTD-ECD analytical
system are illustrated in Figures ll(c) and ll(d), respectively.
10.1.3.3 Helium is used as the carrier gas (4 cnr/min) to purge residual air from the
trap at the end of the sampling phase and to carry the revolatilized VOCs through the
Megabore* GC column. Moisture and organic impurities are removed from the helium gas
stream by a chemical purifier installed in the GC (see Section 72.1.11). After exiting the
OV-I Megabore* column, the carrier gas stream is split to the two detectors at rates of 2
cm3/min each.
10.13.4 Gas scrubbers containing Drierite* or silica gel and 5A molecular sieve are
used to remove moisture and organic impurities from the zero air, hydrogen, and nitrogen
gas streams.
Note: Purity of gas purifiers is checked prior to use by passing humid zero air through the
gas purifier and analyzing according to Section 12.2.2.
10.13.5 All lines should be kept as short as practical. All tubing used for the system
should be chromatographic grade stainless steel connected with stainless steel fittings. After
assembly, the system should be checked for leaks according to manufacturer's specifications.
Revised 9/30/89 ~~~ Page 21
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Method IP-1A . VOCs
10.13.6 The FID burner air, hydrogen, nitrogen (makeup), and helium (carrier) flow
rates should be set according to the manufacturer's instructions to obtain an optimal FID
response while maintaining a stable flame throughout the analysis. Typical flow rates are:
burner air, 450 cm3/min; hydrogen, 30 cm3/min; nitrogen, 30 cm3/min; helium, 2 cm /mm.
10.1.3.7 The BCD nitrogen make-up gas and helium carrier flow rates should be set
according to manufacturer's instructions to obtain an optimal ECD response. Typical flow
rates are: nitrogen, 76 cm3/min and helium, 2 cm /min.
10.13.8 The GC-FID-ECD could be modified to include a PID (see Figure 6) for
increased sensitivity (20). In the photoionization process, a molecule is ionized by
ultraviolet light as follows: R + hv --> R + e-, where R+ is the ionized species and a
photon is represented by hv, with energy less than or equal to the ionization potential of
the molecule. Generally all species with an ionization potential less than the ionization
energy of the lamp are detected. Because the ionization potential of all major components
of air (O2, N2, CO, CO2, and H2O) is greater than the ionization energy of lamps in general
use, they are not detected. The sensor is comprised of an argon-filled, ultraviolet (UV)
light source where a portion of the organic vapors is ionized in the gas stream. A pair of
electrodes is contained in a chamber adjacent to the sensor. When a positive potential is
applied to the electrodes, any ions formed by the absorption of UV light are driven by the
created electronic field to the cathode, and the current (proportional to the organic vapor
concentration) is measured. The FED is generally used for compounds having ionization
potentials less than the ratings of the ultraviolet lamps. This detector is used for
determination of most chlorinated and oxygenated hydrocarbons, aromatic compounds, and
high molecular weight aliphatic compounds. Because the FID is insensitive to methane,
ethane, carbon monoxide, carbon dioxide, and water vapor, it is an excellent detector. The
electron volt rating is applied specifically to the wavelength of the most intense emission
line of the lamp's output spectrum. Some compounds with ionization potentials above the
lamp rating can still be detected due to the presence of small quantities of more intense
light. A typical system configuration associated with the GC-FID-ECD-PID is illustrated
in Figure 6. This system is currently being used in EPA's FY-89 Urban Air Toxics
Monitoring Program.
10.2 GC-MS-SCAN-SIM System Performance Criteria
10.2.1 GC-MS System Operation
102.1.1 Prior to analysis, the GC-MS system is assembled and checked according to
manufacturer's instructions.
10.2.1.2 Table 3.0 outlines general operating conditions for the GC-MS-SCAN-SIM
system with optional FID.
102.13 The GC-MS system is first challenged with humid zero air (see Section
11.22).
10.2.1.4 The GC-MS and optional FID system is acceptable if it contains less than
02 ppbv of targeted VOCs.
10.22 Daily GC-MS Tuning (see Figure 13)
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Method IP-1A VOCs
1022.1 At the beginning of each day or prior to a calibration, the GC-MS system
must be tuned to verify that acceptable performance criteria are achieved.
10222 For tuning the GC-MS, a cylinder containing 4-bromofluorobenzene is
introduced via a sample loop valve injection system.
Note: Some systems allow auto-tuning to facilitate this process. The key ions and ion
abundance criteria that must be met are illustrated in Table 4. Analysis should not begin
until all those criteria are met.
10.2.2.3 The GC-MS tuning standard could also be used to assess GC column
performance (chromatographic check) and as an internal standard. Obtain a background
correction mass spectra of 4-bromofluorobenzene and check that all key ions criteria are
met. If the criteria are not achieved, the analyst must retune the mass spectrometer and
repeat the test until all criteria are achieved.
10.2.2.4 The performance criteria must be achieved before any samples, blanks or
standards are analyzed. If any key ion abundance observed for the daily
4-bromofluorobenzene mass tuning check differs by more than 10% absolute abundance
from that observed during the previous daily tuning, the instrument must be retuned or the
sample and/or calibration gases reanalyzed until the above condition is met.
10.2.3 GC-MS Calibration (see Figure 13)
Note: Initial and routine calibration procedures are illustrated in Figure 13.
102.3.1 Initial Calibration - Initially, a multipoint dynamic calibration (three levels
plus humid zero air) is performed on the GC-MS system, before sample analysis, with the
assistance of a calibration system (see Figure 8). The calibration system uses National
Bureau of Standards (NBS) traceable standards or NBS/EPA CRMs in pressurized
cylinders [containing a mixture of the targeted VOCs at nominal concentrations of 10 ppmv
in nitrogen (Section 8.2)] as working standards to be diluted with humid zero air. The
contents of the working standard cylinder(s) are metered (2 cm3/min) into the heated
mixing chamber where they are mixed with a 2 L/min humidified zero air gas stream to
achieve a nominal 10 ppbv per compound calibration mixture (see Figure 8). This nominal
10 ppbv standard mixture is allowed to flow and equilibrate for a minimum of 30 minutes.
After the equilibration period, the gas standard mixture is sampled and analyzed by the
real-time GC.MS system [see Figure 8(a) and Section 72.1]. The results of the analyses are
averaged, flow audits are performed on the mass flow meters and the calculated
concentration compared to generated values. After the GC-MS is calibrated at three
concentration levels, a second humid zero air sample is passed through the system and
analyzed. The second humid zero air test is used to verify that the GC.MS system is
certified clean (less than 0.2 ppbv of target compounds).
102.3.2 As an alternative, a multipoint humid static calibration (three levels plus zero
humid air) can be performed on the GC-MS system. During the humid static calibration
analyses, three (3) SUMMA* passivated canisters are filled each at a different
concentration between 1-20 ppbv from the calibration manifold using a pump and mass flow
control arrangement [see Figure 8(c)]. The canisters are then delivered to the GC-MS to
serve as calibration standards. The canisters are analyzed by the MS in the SIM mode, each
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Method IP-1A VOCs
analyzed twice. The expected retention time and ion abundance (see Table 2 and Table
5) are used to verify proper operation of the GC-MS system. A calibration response factor
is determined for each analyte, as illustrated in Table 5, and the computer calibration table
is updated with this information, as illustrated in Table 6.
10.2.3.3 Routine Calibration - The GC-MS system is calibrated daily (and before
sample analysis) with a one point calibration. The GC-MS system is calibrated either with
the dynamic calibration procedure [see Figure 8(a)] or with a 6 L SUMMA® passivated
canister filled with humid calibration standards from the calibration manifold (see Section
10.2.3.2). After the single point calibration, the GC-MS analytical system is challenged with
a humidified zero gas stream to insure the analytical system returns to specification (less
than 0.2 ppbv of selective organics).
103 GC-FID-ECD System Performance Criteria (With Optional PID System) (See
Figure 14)
103.1 Humid Zero Air Certification
103.1.1 Before system calibration and sample analysis, the GC-FID-ECD analytical
system is assembled and checked according to manufacturer's instructions.
103.12 The GC-FID-ECD system is first challenged with humid zero air (see Section
12.22) and monitored.
103.13 Analytical systems contaminated with less than 0.2 ppbv of targeted VOCs
are acceptable.
1032 GC Retention Time Windows Determination (see Table 7)
1032.1 Before analysis can be performed, the retention time windows must be
established for each analyte.
10322 Make sure the GC system is within optimum operating conditions.
10323 Make three injections of the standard containing all compounds for retention
time window determination.
Note: The retention time window must be established for each analyte every 72 hours
during continuous operation.
1032.4 Calculate the standard deviation of the three absolute retention times for
each single component standard. The retention window is defined as the mean plus or
minus three times the standard deviation of the individual retention times for each standard.
In those cases where the standard deviation for a particular standard is zero, the laboratory
must substitute the standard deviation of a closely-eluting, similar compound to develop a
valid retention time window.
1032.5 The laboratory must calculate retention time windows for each standard (see
Table 7) on each GC column, whenever a new GC column is installed or when major
components of the GC are changed. The data must be noted and retained in a notebook
by the laboratory as part of the user SOP and as a quality assurance check of the analytical
system.
1033 GC Calibration
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Method IP-1A _____ VOCs
Note: Initial and routine calibration procedures are illustrated in Figure 14.
1033.1 Initial Calibration - Initially, a multipoint dynamic calibration (three levels
plus humid zero air) is performed on the GC-FID-ECD system, before sample analysis, with
the assistance of a calibration system (see Figure 8). The calibration system uses NBS
traceable standards or NBS/EPA CRMs in pressurized cylinders [containing a mixture of
the targeted VOCs at nominal concentrations of 10 ppmv in nitrogen (Section 8.2)] as
working standards to be diluted with humid zero air. The contents of the working standard
cylinders are metered (2 cm3/min) into the heated mixing chamber where they are mixed
with a 2 L/min humidified zero air stream to achieve a nominal 10 ppbv per compound
calibration mixture (see Figure 8). This nominal 10 ppbv standard mixture is allowed to
flow and equilibrate for an appropriate amount of time. After the equilibration period, the
gas standard mixture is sampled and analyzed by the GC-MS system [see Figure 8(a)]. The
results of the analyses are averaged, flow audits are performed on the mass flow controllers
used to generate the standards and the appropriate response factors (concentration/ area
counts) are calculated for each compound, as illustrated in Table 5.
Note: GC-FIDs are linear in the 1-20 ppbv range and may not require repeated multipoint
calibrations; whereas, the GC-ECD will require frequent linearity evaluation. Table 5
outlines typical calibration response factors and retention times for 40 VOCs. After the
GC-FED-ECD is calibrated at the three concentration levels, a second humid zero air
sample is passed through the system and analyzed. The second humid zero air test is used
to verify that the GC-FID-ECD system is certified clean (less than 0.2 ppbv of target
compounds).
103.3.2 Routine Calibration - A one point calibration is performed daily on the
analytical system to verify the initial multipoint calibration (see Section 10.3.3.1). The
analyzers (GC-FID-ECD) are calibrated (before sample analysis) using the static calibration
procedures (see Section 10.23.2) involving pressurized gas cylinders containing low
concentrations of the targeted VOCs (10 ppbv) in nitrogen. After calibration, humid zero
air is once again passed through the analytical system to verify residual VOCs are not
present.
103.4 GC-FID-ECD-PID System Performance Criteria
103.4.1 As an option, the user may wish to include a photoionization detector (PID)
to assist in peak identification and increase sensitivity.
103.4.2 This analytical system is presently being used in U.S. Environmental
Protection Agency's Urban Air Toxic Pollutant Program (UATP).
103.43 Preparation of the GC-FID-ECD-PID analytical system is identical to the
GC-FID-ECD system (see Section 103).
103.4.4 Table 8 outlines typical retention times (minutes) for selected organics using
the GC-FID-ECD-PID analytical system.
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Method IP-1A VOCs
10.4 Analytical Procedures
10.4.1 Canister Receipt
10.4.1.1 The overall condition of each sample canister is observed. Each canister
should be received with an attached sample identification tag.
10.4.12 Each canister is recorded in the dedicated laboratory logbook. Also noted
on the identification tag are date received and initials of recipient.
10.4.13 The pressure of the canister is checked by attaching a pressure gauge to the
canister inlet. The canister valve is opened briefly and the pressure (kPa, psig) is recorded.
Note: K pressure is <83 kPa (< 12 psig), the user may wish to pressurize the canisters, as
an option, with zero grade nitrogen up to 137 kPa (20 psig) to ensure that enough sample
is available for analysis. However, pressurizing the canister can introduce additional error,
increase the minimum detection limit (MDL), and is time consuming. The user should
weigh these limitations as part of his program objectives before pressurizing. Final cylinder
pressure is recorded on canister sampling data sheet (see Figure 10).
10.4.1.4 If the canister pressure is increased, a dilution factor (DF) is calculated and
recorded on the sampling data sheet:
DF = Ya/Xa
where:
Xa = canister pressure absolute before dilution, kPa, psia
Ya = canister pressure absolute after dilution, kPa, psia
After sample analysis, detected VOC concentrations are multiplied by the dilution factor
to determine concentration in the sampled air.
10.42 GC-MS-SCAN Analysis (With Optional FID System)
10.42.1 The analytical system should be properly assembled, humid zero air certified
(see Section 123), operated (see Table 3), and calibrated for accurate VOC determination.
10.422 The mass flow controllers are checked and adjusted to provide correct flow
rates for the system.
10.423 The sample canister is connected to the inlet of the GC-MS-SCAN (with
optional FID) analytical system. For pressurized samples, a mass flow controller is placed
on the canister, the canister valve is opened and the canister flow is vented past a tee inlet
to the analytical system at a flow of 75 cm3/min so that 40 cm3/min is pulled through the
Nafion® dryer to the six-port chromatographic valve.
Note: Flow rate is not as important as acquiring sufficient sample volume. Sub-ambient
pressure samples are connected directly to the inlet.
10.42.4 The GC oven and cryogenic trap (inject position) are cooled to their set
points of -50°C and -160°C, respectively.
10.42.5 As soon as the cryogenic trap reaches its lower set point of -160.C, the six-
port chromatographic valve is turned to its fill position to initiate sample collection.
10.42.6 A ten minute collection period of canister sample is utilized.
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Method IP-1A __ VOCs
Note: 40 cm3/min x 10 min = 400 cm3 sampled canister contents.
10.42.7 After the sample is preconcentrated in the cryogenic trap, the GC sampling
valve is cycled to the inject position and the cryogenic trap is heated. The trapped analytes
are thermally desorbed onto the head of the OV-I capillary column (0.31 mm LD. x 50 m
length). The GC oven is programmed to start at -50°C and after 2 min to heat to 150°C
at a rate of 8°C per minute.
10.42.8 Upon sample injection onto the column, the MS is signaled by the computer
to scan the eluting carrier gas from 18 to 250 amu, resulting in a 1.5 Hz repetition rate.
This corresponds to about 6 scans per eluting chromatographic peak.
10.4.2.9 Primary identification is based upon retention time and relative abundance
of eluting ions as compared to the spectral library stored on the hard disk of the GC-MS
data computer.
10.42.10 The concentration (ppbv) is calculated using the previously established
response factors (see Section 10.2.3.2), as illustrated in Table 5.
Note: If the canister is diluted before analysis, an appropriate multiplier is applied to
correct for the volume dilution of the canister (Section 10.4.1.4).
10.42.11 The optional FID trace allows the analyst to record the progress of the
analysis.
10.4.3 GC-MS-SIM Analysis (With Optional FID System)
10.43.1 When the MS is placed in the SIM mode of operation, the MS monitors only
preselected ions, rather than scanning all masses continuously between two mass limits.
10.4.3.2 As a result, increased sensitivity and improved quantitative analysis can be
achieved.
10.4.3.3 Similar to the GC-MS-SCAN configuration, the GC-MS-SIM analysis is based
on a combination of retention times and relative abundances of selected ions (see Table
2 and Table 5). These qualifiers are stored on the hard disk of the GC-MS computer and
are applied for identification of each chromatographic peak. Once the GC-MS-SIM has
identified the peak, a calibration response factor is used to determine the analyte's
concentration.
10.4.3.4 The individual analyses are handled in three phases: data acquisition, data
reduction, and data reporting. The data acquisition software is set in the SIM mode, where
specific compound fragments are monitored by the MS at specific times in the analytical
run. Data reduction is coordinated by the postprocessing macro program that is
automatically accessed after data acquisition is completed at the end of the GC run.
Resulting ion profiles are extracted, peaks are identified and integrated, and an internal
integration report is generated by the program. A reconstructed ion chrpmatogram for
hardcopy reference is prepared by the program and various parameters of interest such as
time, date, and integration constants are printed. At the completion of the macro program,
the data reporting software is accessed. The appropriate calibration table (see Table 9) is
retrieved by the data reporting program from the computer's hard disk storage and the
proper retention time and response factor parameters are applied to the macro program's
integration file. With reference to certain pre-set acceptance criteria, peaks are
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I
Method IP-1A VOCs
automaticaUy identified and quantified and a final summary report is prepared, as illustrated
in Table 10.
10.4.4 GC-FID-ECD Analysis (With Optional PID System)
10.4.4.1 The analytical system should be properly assembled, humid zero air certified
(see Section 12.2) and calibrated through a dynamic standard calibration procedure (see
Section 10.3.2). The FID detector is lit and allowed to stabilize.
10.4.42 Sixty-four minutes are required for each sample analysis, 15 for system
initialization, 14 for sample collection, 30 for analysis, and 5 for post-time, during which a
report is printed.
Note: This may vary depending upon system configuration and programming.
10.4.43 The helium and sample mass flow controllers are checked and adjusted to
provide correct flow rates for the system. Helium is used to purge residual air from the
trap at the end of the sampling phase and to carry the revolatilized VOCs from the trap
onto the GC column and into the FID-ECD. The hydrogen, burner air, and nitrogen flow
rates should also be checked. The cryogenic trap is connected and verified to be operating
properly while flowing cryogen through the system. ^^ .
10.4.4.4 The sample canister is connected to the inlet of the GC-FID-ECD analytical
system. The canister valve is opened and the canister flow is vented past a tee inlet to the
analytical system at 75 cm3/min using a 0-500 cm3/min Tylan mass flow controller. During
analysis, 40 cm3/rnin of sample gas is pulled through the six-port chromatographic valve arid
routed through the trap at the appropriate time while the extra sample is vented. The
VOCs are condensed in the trap while the excess flow is exhausted through an exhaust vent,
which assures that the sample air flowing through the trap is at atmospheric pressure.
10.4.4.5 The six-port valve is switched to the inject position and the canister valve is
closed.
10.4.4.6 The electronic integrator is started.
10.4.4.7 After the sample is preconcentrated on the trap, the trap is heated and the
VOCs are thermally desorbed onto the head of the capillary column. Since the column is
at -50°C, the VOCs are cryofocussed on the column. Then, the oven temperature
(programmed) increases and the VOCs elute from the column to the parallel FID-ECD
assembly.
10.4.4.8 The peaks eluting from the detectors are identified by retention tune (see
Table 7 and Table 8), while peak areas are recorded in area counts. Figures 15 and 16
illustrate typical response of the FID and ECD, respectively, for the forty (40) targeted
VOCs.
Note* Refer to Table 7 for peak number and identification.
10.4.4.9 The response factors (see Section 103.3.1) are multiplied by the area counts
for each peak to calculate ppbv estimates for the unknown sample. If the canister is diluted
before analysis, an appropriate dilution multiplier (DF) is applied to correct for the volume
dilution of the canister (see Section 10.4.1.4).
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Method IP-1A VOCs
10.4.4.10 Depending on the number of canisters to be analyzed, each canister is
analyzed twice and the final concentrations for each analyte are the averages of the two
analyses.
10.4.4,11 However, if the GC-FID-ECD analytical system discovers unexpected peaks
which need further identification and attention or overlapping peaks are discovered,
eliminating possible quantitation, the sample should then be subjected to a GC-MS-SCAN
for positive identification and quantitation.
11. Cleaning and Certification Program
11.1 Canister Cleaning and Certification
11.1.1 All canisters must be clean and free of any contaminants before sample collection.
11.1.2 All canisters are leak tested by pressurizing them to approximately 206 kPa (30
psig) with zero air.
Note: The canister cleaning system in Figure 7 can be used for this task.
The initial pressure is measured, the canister valve is closed, and the final pressure is
checked after 24 hours. If leak tight, the pressure should not vary more than ± 13.8 kPa
(±2 psig) over the 24 hour period.
11.1.3 A canister cleaning system may be assembled as illustrated in Figure 7. Cryogen
is added to both the vacuum pump and zero air supply traps. The canister(s) are connected
to the manifold. The vent shut-off valve and the canister valve(s) are opened to release
any remaining pressure in the canister(s). The vacuum pump is started and the vent shut-
off valve is then closed and the vacuum shut-off valve is opened. The canister(s) are
evacuated to < 0.05 mm Hg (for at least one hour).
Note: On a daily basis or more often if necessary, the cryogenic traps should be purged
with zero air to remove any trapped water from previous canister cleaning cycles.
11.1.4 The vacuum and vacuum/pressure gauge shut-off valves are closed and the zero
air shut-off valve is opened to pressurize the canister(s) with humid zero air to
approximately 206 kPa (30 psig). If a zero gas generator system is used, the flow rate may
need to be limited to maintain the zero air quality.
11.1.5 The zero shut-off valve is closed and the canister(s) is allowed to vent down to
atmospheric pressure through the vent shut-off valve. The vent shut-off valve is closed.
Steps 11.13 through 11.1.5 are repeated two additional times for a total of three (3)
evacuation/pressurization cycles for each set of canisters.
11.1.6 At the end of the evacuation/pressurization cycle, the canister is pressurized to
206 kPa (30 psig) with humid zero air. The canister is then analyzed by a GC-MS or GC-
FID-ECD analytical system. Any canister that has not tested clean (compared to direct
analysis of humidified zero air of less than 0.2 ppbv of targeted VOCs) should not be used.
As a "blank" check of the canister(s) and cleanup procedure, the final humid zero air fill
of 100% of the canisters is analyzed until the cleanup system and canisters are proven
reliable (less than 02 ppbv of target VOCs). The check can then be reduced to a lower
percentage of canisters.
11.1.7 The canister is reattached to the cleaning manifold and is then reevacuated to
<0.05 mm Hg and remains in this condition until used. The canister valve is closed. The
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Method IP-1A VOCs
canister is removed from the cleaning system and the canister connection is capped with a
stainless steel fitting. The canister is now ready for collection of an air sample. An
identification tag is attached to the neck of each canister for field notes and chain-of-
custody purposes.
11.1.8 As an option to the humid zero air cleaning procedures, the canisters could be
heated in an isothermal oven to 100°C during Section 11.13 to ensure that lower molecular
weight compounds (C2-C8) are not retained on the walls of the canister.
Note: For sampling heavier, more complex VOC mixtures, the canisters should be heated
to 250°C during Section 11.13.7. Once heated, the canisters are evacuated to 0.05 mm Hg.
At the end of the heated/evacuated cycle, the canisters are pressurized with humid zero air
and analyzed by the GC-FTD-ECD system. Any canister that has not tested clean (less than
0.2 ppbv of targeted compounds) should not be used. Once tested clean, the canisters are
reevacuated to 0.05 mm Hg and remain in the evacuated state until used.
112 Sampling System Cleaning and Certification
113.1 Cleaning Sampling System Components
11.2.1.1 Sample components are disassembled and cleaned before the sampler is
assembled. Nonmetallic parts are rinsed with HPLC grade deionized water and dried in
a vacuum oven at 50°C. Typically, stainless steel parts and fittings are cleaned by placing
them in a beaker of methanol in an ultrasonic bath for 15 minutes. This procedure is
repeated with hexane as the solvent.
112.12 The parts are then rinsed with HPLC grade deionized water and dried in a
vacuum oven at 100°C for 12 to 24 hours.
113.13 Once the sampler is assembled, the entire system is purged with humid zero
air for 24 hours.
11.2.2 Humid Zero Air Certification
Note: In the following sections, "certification" is defined as evaluating the sampling system
with humid zero air and humid calibration gases that pass through all active components
of the sampling system. The system is "certified" if no significant additions or deletions (less
than 0.2 ppbv of targeted compounds) have occurred when challenged with the test gas
stream.
1122.1 The cleanliness of the sampling system is determined by testing the sampler
with humid zero air without an evacuated gas cylinder, as follows.
11222 The calibration system and manifold are assembled as illustrated in Figure
8. The sampler (without an evacuated gas cylinder) is connected to the manifold and the
zero air cylinder activated to generate a humid gas stream (2 L/min) to the calibration
manifold [see Figure 8 (b)]. •
11223 The humid zero gas stream passes through the calibration manifold, through
the sampling system (without an evacuated canister) to a GC-FID-ECD analytical system
at 75 cm3/min so that 40 cm3/min is pulled through the six port valve and routed through
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Method IP-1A VOCs
the cryogenic trap (see Section 102.2.1) at the appropriate time while the extra sample is
vented.
Note: The exit of the sampling system (without the canister) replaces the canister in
Fifiurc 4.
After the sample (400 mL) is preconcentrated on the trap, the trap is heated and the VOCs
are thermally desorbed onto the head of the capillary column. Since the column is at -50°C,
the VOCs are cryofocussed on the column. Then, the oven temperature (programmed)
increases and the VOCs begin to elute and are detected by a GC-MS (see Section 10.2)
or the GC-F1D-ECD (see Section 10.3). The analytical system should not detect greater
than 0.2 ppbv of targeted VOCs in order for the sampling system to pass the humid zero
air certification test. Chromatograms of a certified sampler and contaminated sampler are
illustrated in Figures 17(a) and (b), respectively. If the sampler passes the humid zero air
test, it is then tested with humid calibration gas standards containing selected VOCs at
concentration levels expected in field sampling (e.g., 0.5 to 2 ppbv) as outlined in Section
11.2.3.
1123 Sampler System Certification with Humid Calibration Gas Standards
11.2.3.1 Assemble the dynamic calibration system and manifold as illustrated in
Figure 8.
11232 Verify that the calibration system is clean (less than 0.2 ppbv of targeted
compounds) by sampling a humidified gas stream, without gas calibration standards, with
a previously certified clean canister (see Section 12.1).
11233 The assembled dynamic calibration system is certified clean if less than 0.2
ppbv of targeted compounds are found.
1123.4 For generating the humidified calibration standards, the calibration gas
cylinder(s) (see Section 8.2) containing nominal concentrations of 10 ppmv in nitrogen of
selected VOCs are attached to the calibration system, as outlined in Section 10.2.3.1. The
gas cylinders are opened and the gas mixtures are passed through 0 to 10 cm /min certified
mass flow controllers to generate ppb levels of calibration standards.
11.23.5 After the appropriate equilibrium period, attach the sampling system
(containing a certified evacuated canister) to the manifold, as illustrated in Figure 8(a).
1123.6 Sample the dynamic calibration gas stream with the sampling system
according to Section 92.1.
Note: To conserve generated calibration gas, bypass the canister sampling system manifold
and attach the sampling system to the calibration gas stream at the inlet of the in-line filter
of the sampling system so the flow will be less than 500 cm /min.
1123.7 Concurrent with the sampling system operation, real time monitoring of the
calibration gas stream is accomplished by the on-line GC-MS or GC-multidetector analytical
system [see Figure 8(b)] to provide reference concentrations of generated VOCs.
1123.8 At the end of the sampling period (normally same time period used for
anticipated sampling), the sampling system canister is analyzed and compared to the
reference GC-MS or GC-multidetector analytical system to determine if the concentration
of the targeted VOCs was increased or decreased by the sampling system.
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Method IP-1A _ _ VOCs
113, 3.9 A recovery of between 90% and 110% is expected for all targeted VOCs.
12. Performance Criteria and Quality Assurance
12.1 Standard Operating Procedures (SOPs)
12.1.1 SOPs should be generated in each laboratory describing and documenting the
following activities: 1) assembly, calibration, leak check, and operation of specific sampling
systems and equipment used, 2) preparation, storage, shipment, and handling of samples,
3) assembly, leak-check, calibration, and operation of the analytical system, addressing the
specific equipment used, 4) canister storage and cleaning, and 5) all aspects of data
recording and processing, including lists of computer hardware and software used.
12.1.2 Specific stepwise instructions should be provided in the SOPs and should be
readily available to and understood by the laboratory personnel conducting the work.
Method Relative Accuracy and Linearity
12 2.1 Accuracy can be determined by injecting VOC standards (see Section 8.2) from
an audit cylinder into a sampler. The contents are then analyzed for the components
contained in the audit canister. Percent relative accuracy is calculated:
% Relative Accuracy = (X-Y)/X x 100
where:
Y = Concentration of the targeted compound recovered from sampler
X = Concentration of VOC targeted compound in the NBS-SRM or EPA-CRM audit
cylinders
12 22 If the relative accuracy does not fall between 90 and 110 percent, the sampler
should be removed from use, cleaned, and recertified according to initial certification
procedures outlined in Section 112.2 and Section 11.2.3. Historically, concentrations of
carbon tetrachloride, tetrachloroethylene, and hexachlorobutadiene have sometimes been
detected at lower concentrations when using parallel ECD and FID detectors. When these
three compounds are present at concentrations close to calibration levels, both detectors
usually agree on the reported concentrations. At concentrations below 4 ppbv, there is a
problem with non-linearity of the ECD. Plots of concentration versus peak area for
calibration compounds detected by the ECD have shown that the curves are nonlinear for
carbon tetrachloride, tetrachloroethylene, and hexachlorobutadiene, as illustrated in Figures
18(a) through 18(c). Other targeted ECD and FID compounds scaled linearly for the range
0 to 8 ppbv, as shown for chloroform in Figure 18(d). For compounds that are not linear
over the calibration range, area counts generally roll off between 3 and 4 ppbv. To correct
for the nonlinearity of these compounds, an additional calibration step is performed. An
evacuated stainless steel canister is pressurized with calibration gas at a nominal
concentration of 8 ppbv. The sample is then diluted to approximately 3.5 ppbv with zero
air and analyzed. The instrument response factor (ppbv/area) of the ECD for each of the
three compounds is calculated for the 3.5 ppbv sample. Then, both the 3.5 ppbv and the
8 ppbv response factors are entered into the ECD calibration table. The software for the
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Method IP-1A VOCs
Hewlett-Packard 5880 level 4 GC is designed to accommodate multilevel calibration entries,
so the correct response factors are automatically calculated for concentrations in this range.
12.3 Method Modification
12.3.1 Sampling
12.3.1.1 The sampling system for pressurized canister sampling could be modified to
use a lighter, more compact pump. The pump currently being used weighs about 16
kilograms (35 Ibs). Commercially available pumps that could be used as alternatives to
the prescribed sampler pump are described below. Metal Bellows MB-41 pump: These
pumps are cleaned at the factory; however, some precaution should be taken with the
circular (4.8 cm diameter) Teflon* and stainless steel part directly under the flange. It is
often dirty when received and should be cleaned before use. This part is cleaned by
removing it from the pump, manually cleaning with deionized water, and placing in a
vacuum oven at 100°C for at least 12 hours. Exposed parts of the pump head are also
cleaned with swabs and allowed to air dry. These pumps have proven to be very reliable;
however, they are only useful up to an outlet pressure of about 137 kPa (20 psig).
Neuberger Pump: Viton gaskets or seals must be specified with this pump. The "factory
direct" pump is received contaminated and leaky. The pump is cleaned by disassembling
the pump head (which consists of three stainless steel parts and two gaskets), cleaning the
gaskets with deionized water and drying in a vacuum oven, and remachining (or manually
lapping) the sealing surfaces of the stainless steel parts. The stainless steel parts are then
cleaned with methanol, hexane, deionized water and heated in a vacuum oven. The cause
for most of the problems with this pump has been scratches on the metal parts of the pump
head. Once this rework procedure is performed, the pump is considered clean and can be
used up to about 240 kPa (35 psig) output pressure. This pump is utilized in the sampling
system illustrated in Figure 3.
123.12 Urban Air Toxics Sampler - The sampling system described in this method
can be modified like the sampler in EPA's FY-89 Urban Air Toxics Pollutant Program.
This particular sampler is described in Appendix C (see Figure 19).
12.3.2 Analysis
12.3.2.1 Inlet tubing from the calibration manifold could be heated to 50°C (same
temperature as the calibration manifold) to prevent condensation on the internal walls of
the system. .
12322 The analytical strategy for Method IP-1A involves positive identification and
quantitation by GC-MS-SCAN-SIM mode of operation with optional FID. This is a highly
specific and sensitive detection technique. Because a specific detector system (GC-MS-
SCAN-SIM) is more complicated and expensive than the use of non-specific detectors (GC-
FID-ECD-PID), the analyst may want to perform a screening analysis and preliminary
quantitation of VOC species in the sample, including any polar compounds, by utilizing
the GC-multidetector (GC-FID-ECD-PID) analytical system prior to GC-MS analysis. This
Revised 9/30/89 Pa8e 33
-------
Method IP-1A VOCs
system can be used for approximate quantitation. The GC-FID-ECD-PID provides a
"snapshot" of the constituents in the sample, allowing the analyst to determine:
• Extent of misidentification due to overlapping peaks,
• Whether the constituents are within the calibration range of the
anticipated GC-MS-SCAN-SIM analysis or does the sample require further
dilution, and
• Are there unexpected peaks which need further identification through
GC-MS-SCAN or are there peaks of interest needing attention?
If unusual peaks are observed from the GC-FID-ECD-PID system, the analyst then
performs a GC-MS-SCAN analysis. The GC-MS-SCAN will provide positive identification
of suspect peaks from the GC-FID-ECD-PID system. If no unusual peaks are identified
and only a select number of VOCs are of concern, the analyst can then proceed to GC-
MS-SIM. The GC-MS-SIM is used for final quantitation of selected VOCs. Polar
compounds, however, cannot be identified by the GC-MS-SIM due to the use of a Nafion®
dryer to remove water from the sample prior to analysis. The dryer removes polar
compounds along with the water. The analyst often has to make this decision incorporating
project objectives, detection limits, equipment availability, cost and personnel capability in
developing an analytical strategy. Figure 20 outlines the use of the GC-FID-ECD-PID as
a "screening" approach, with the GC-MS-SCAN-SIM for final identification and quantitation.
12.4 Method Safety
This procedure may involve hazardous materials, operations, and equipment. This method
does not purport to address all of the safety problems associated with its use. It is the
user's responsibility to establish appropriate safety and health practices and determine the
applicability of regulatory limitations prior to the implementation of this procedure. This
should be part of the user's SOP manual.
12.5 Quality Assurance (See Figure 21)
12.5.1 Sampling System
12.5.1.1 Section 9.2 suggests that a portable GC system be used as a "screening
analysis" prior to locating fixed-site samplers (pressurized or subatmospheric).
12.5.L2 Section 92 requires pre-and post-sampling measurements with a certified
mass flow controller for flow verification of sampling system.
12.5.13 Section 11.1 requires all canisters to be pressure tested to 206 kPa ± 14 kPa
(30 psig ± 2 psig) over a period of 24 hours.
12.5.1.4 Section 11.1 requires that all canisters be certified clean (containing less than
02 ppbv of targeted VOCs) through a humid zero air certification program.
12.5.1.5 Section 1122 requires all sampling systems to be certified initially clean
(containing less than 0.2 ppbv of targeted VOCs) through a humid zero air certification
program.
Revised 9/30/89 Page 34
-------
Method IP-1A ___ ___ VOCs
12.5.1.6 Section 11.2.3 requires all sampling systems to pass an initial humidified
calibration gas certification [at VOC concentration levels expected in the field (e.g., 0.5 to
2 ppbv)] with a percent recovery of greater than 90.
12.52 GC-MS-SCAN-SIM System Performance Criteria
12.5.2.1 Section 10.2.1 requires the GC-MS analytical system to be certified clean
(less than 0.2 ppbv of targeted VOCs) prior to sample analysis, through a humid zero air
certification.
12.522 Section 1022 requires the tuning of the GC-MS with 4-bromofluorobenzene
(4-BFB) and that it meet the key ions and ion abundance criteria (10%) outlined in
Table 5. ,„ .
12.5.23 Section 10.2.3 requires both an initial multipoint humid static calibration
(three levels plus humid zero air) and a daily calibration (one point) of the GC-MS
analytical system.
12.5.3 GC-Multidetector System Performance Criteria
12.53.1 Section 10.3.1 requires the GC-FID-ECD analytical system, prior to analysis,
to be certified clean (less than 0.2 ppbv of targeted VOCs) through a humid zero air
certification.
12.5.3.2 Section 1032 requires that the GC-FID-ECD analytical system establish
retention time windows for each analyte prior to sample analysis, when a new GC column
is installed, or major components of the GC system altered since the previous
determination.
12.533 Section 82 requires that all calibration gases be traceable to a National
Bureau of Standards (NBS) Standard Reference Material (CRM).
12.53.4 Section 10.3.2 requires that the retention time window be established
throughout the course of a 72-hr analytical period.
12.53.5 Section 10.3.3 requires both an initial multipoint calibration (three levels plus
humid zero air) and a daily calibration (one point) of the GC-FID-ECD analytical system
with zero gas dilution of NBS traceable or NBS/EPA CRMs gases.
Note: Gas cylinders of VOCs at the ppm and ppb level are available for audits from the
USEPA, Atmospheric Research and Exposure Assessment Laboratory, Quality Assurance
Division, MD-77B, Research Triangle Park, NC 27711, (919)541-4531. Appendix A outlines
five groups of audit gas cylinders available from USEPA.
13. Acknowledgements
The determination of volatile and some semi-volatile organic compounds in indoor air is
a complex task, primarily because of the wide variety of compounds of interest and the lack
of standardized sampling and analytical procedures. While there are numerous procedures
for sampling and analyzing VOCs/SVOCs in indoor air, this method draws upon the best
aspects of each one and combines them into a standardized methodology. To that end, the
following individuals contributed to the research, documentation and peer review of this
manuscript:
Revised 9/30/89 Pa8e 35
-------
Method IP-1A
VOCs
Topic
Contact
GC-MS- Dr. BUI McClenny
SCAN-SIM Mr. Joachim Pleil
Dr. Lou Ballard
Canister Mr. Vince Thompson
Cleaning,
Certification
and Storage
Stability
Dr. Bill McClenny
Mr. Joachim Pleil
Dave-Paul Dayton
JoAnn Rice
Dr. R.K.M. Jayanty
Cryogenic Mr. Lou Ballard
Sampling
Unit
Ajdress/Phone
U.S. Environmental Protection Agency
Atmospheric Research and Exposure
Laboratory
MD-44
Research Triangle Park, NC 27711
919-541-3158
Research Triangle Laboratories, Inc.
P.O. Box 12507
Research Triangle Park, NC 27709
919-544-5775
U.S. Environmental Protection Agency
Atmospheric Research and Exposure
Laboratory
MD-77
Research Triangle Park, NC 27711
919-541-2622
U.S. Environmental Protection Agency
Atmospheric Research and Exposure
Laboratory
MD-44
Research Triangle Park, NC 27711
919-541-3158
Radian Corporation
P.O. Box 13000
Progress Center
Research Triangle Park, NC 27709
919-481-0212
Research Triangle Institute
P.O. Box 12194
Research Triangle Park, NC 27709
919-541-6000
NuTech Corporation
2806 Cheek Road
Durham, NC 27704
919-682-0402
Revised 9/30/89
Page 36
-------
Method IP-1A
VOCs
Topic
Contact
Mr. Joachim Pleil
Sampling
System
Mr. Frank McElroy
Mr. Vince Thompson
Dr. Bill McClenny
Mr. Joachim Pleil
Mr. Tom Merrifield
Mr. Joseph P. Krasnec
GC-FED Mr. Vince Thompson
Address/Phone
U.S. Environmental Protection Agency
Atmospheric Research and Exposure
Laboratory
MD-44
Research Triangle Park, NC 27711
919-541-3158
U.S. Environmental Protection Agency
Atmospheric Research and Exposure
Laboratory
MD-77
Research Triangle Park, NC 27711
919-541-2622
U.S. Envimomental Protection Agency
Atmospheric Research and Exposure
Laboratory
MD-44
Research Triangle Park, NC 27711
919-541-3158
Anderson Samplers, Inc.
4215-C Wendell Drive
Atlanta, GA 30336
1-800-241-6898
Scientific Instrumentation Spec.
P.O. Box 8941
Moscow, Idaho 83843
202-882-3860
U.S. Environmental Protection Agency
Atmospheric Research and Exposure
Laboratory
MD-77
Research Triangle Park, NC 27711
919-541-2622
Revised 9/30/89
Page 37
-------
Method IP-1A
VOCs
Topic
GC-FJD-
ECD
GC-FID-
ECD-PID
U.S. EPA
Audit Gas
Standards
Contact
Dr. Bill Mcdenny
Mr. Joachim Pleil
Ms. Karen D. Oliver
Dave-Paul Dayton
JoAnn Rice
Mr. Bob Lampe
14. References
Address/Phone
U.S. Environmental Protection Agency
Atmospheric Research and Exposure
Laboratory
MD-44
Research Triangle Park, 27711
919-541-3158
Northrop Services, Inc.
Environmental Sciences
P.O. Box 12313
Research Triangle Park, NC 27709
919-549-0611
Radian Corporation
P.O. Box 13000
Progress Center
Research Triangle Park, NC 27709
919-481-0212
U.S. Environmental Protection Agency
Atmospheric Research and Exposure
Laboratory
MD-77B
Research Triangle Park, NC 27711
919-541-4531
1. Oliver, K. p., Pleil, J. D., and McClenny, W. A., "Sample Integrity of Trace Level
Volatile Organic Compounds in Ambient Air Stored in SUMMA® Polished Canisters,"
Atmospheric Environ., 20:1403, 1986.
2. Holdren, M. W., and Smith, D. L,, "Stability of Volatile Organic Compounds While
Stored in SUMMA* Polished Stainless Steel Canisters," Final Report, EPA Contract No.
68-02-4127, Research Triangle Park, NC, Battelle Columbus Laboratories, January, 1986.
3. Riggin, R. M., Technical Assistance Document for Sampling and Analysis of Toxic Organic
Compounds in Ambient Air, EPA-600/4-83-027, U.S. Environmental Protection Agency,
Research Triangle Park, NC, 1983.
4. Riggin, R. M., Compendium of Methods for the Determination of Toxic Organic
Compounds in Ambient Air, EPA-600/4-84-041, U.S. Environmental Protection Agency,
Research Triangle Park, NC, 1986.
Revised 9/30/89
Page 38
-------
Method IP-1A
5. Winberry, W. T., and Tilley, N. V., Supplement to EPA-600/4-84-041: Compendiurnof
Methods for the Determination of Toxic Organic Compounds in Ambient Au ^EPA-600/ 4-8 /-
006, U.S. Environmental Protection Agency, Research Triangle Park, NC, 1986.
6 McClenny, W. A., Pleil, J. D., Holdren, J. W., and Smith, R. N., "Automated Cryogenic
Preconcentration and Gas Chromatographic Determination of Volatile Organic
Compounds," AnaL Chem., 56:2947, 1984.
7 PleU J. D., and Oliver, K. D., "Evaluation of Various Configurations of Nafion Dryers:
Water Removal from Air Samples Prior to Gas Chromatographic Analysis," EPA Contract
No. 68-02-4035, Research Triangle Park, NC, Northrop Services, Inc. - Environmental
Sciences, 1985.
8 Oliver, K. D., and Pleil, J. D., "Automated Cryogenic Sampling and Gas
Chromatographic Analysis of Ambient Vapor-Phase Organic Compounds: Procedures and
Comparison Tests," EPA Contract No. 68-02-4035, Research Triangle Park, NC, Northrop
Services, Inc. - Environmental Sciences, 1985.
9 McClenny, W. A., and Pleil, J. D., "Automated Calibration and Analysis of VOCs with
a Capillary Column Gas Chromatograph Equipped for Reduced Temperature Trapping,
Proceedings of the 1984 Air Pollution Control Association Annual Meeting, San Francisco,
CA, June 24-29, 1984.
10. McClenny, W. A., PleU, J. D.,Lumpkin, T. A., and Oliver, K. D., "Update on Canister-
Based Samplers for VOCs," Proceedings of the 1987EPA/APCA Symposium onMeasurement
of Toxic and Related Air Pollutants, May, 1987 APCA Publication VIP-8, EPA 600/9-87-
010.
11 Pleil, J. D., "Automated Cryogenic Sampling and Gas Chromatographic Analysis of
Ambient Vapor-Phase Organic Compounds: System Design," EPA Contract No. 68-02-
2566, Research Triangle Park, NC, Northrop Services, Inc. - Environmental Sciences, 1982.
12 Oliver, K. D., and Pleil, J. D., "Analysis of Canister Samples Collected During the
CARB Study in August 1986," EPA Contract No. 68-02-4035, Research Triangle Park, NC,
Northrop Services, Inc. - Environmental Sciences, 1987.
13 Pleil J D., and Oliver, K. D., "Measurement of Concentration Variability of Volatile
Organic Compounds in Indoor Air: Automated Operation of a Sequential Syringe Sampler
and Subsequent GC/MS Analysis," EPA Contract No. 68-02-4444, Research Triangle Park,
NC, Northrop Services, Inc. - Environmental Sciences, 1987.
14. Walling, J. R, 'The Utility of Distributed Air Volume Sets When Sampling Ambient
Air Using Solid Adsorbents," Atmospheric Environ., 18:855-859, 1984.
15. Walling, J. F., Bumgarner, J. E., Driscoll, J. D., Morris, C. M., Riley, A. E., and Wright,
L. H., "Apparent Reaction Products Desorbed From Tenax Used to Sample Ambient Air,
Atmospheric Environ., 20:51-57, 1986.
Revised 9/30/89 Pa8e 39
-------
Method IP-1A VOCs
16 Portable Instruments User's Manual for Monitoring VOC Sources, EPA340/1-88-015, U.S.
Environmental Protection Agency, Office of Air Quality Planning and Standards,
Washington, DC, June, 1986.
17. McElroy, F. F., Thompson, V. L., and Richter, H. G., A Cryogenic Preconcentration -
Direct FID (PDFID) Method for Measurement ofNMOC in the Ambient Air, EPA-600/4-85-
063, U.S. Environmental Protection Agency, Research Triangle Park, NC, August 1985.
18. Rasmussen, R. A., and Lovelock, J. E., "Atmospheric Measurements Using Canister
Technology," /. Geophys. Res., 83:8369-8378, 1983.
19. Rasmussen, R. A., and Khalil, M. A. K., "Atmospheric Halocarbons: Measurements
and Analysis of Selected Trace Gases," Proc.. NATO ASI on Atmospheric Ozone, BO:209-
231.
20. Dayton, D. P., and Rice, J., "Development and Evaluation of a Prototype Analytical
System for Measuring Air Toxics," Final Report, Radian Corporation for the U.S.
Environmental Protection Agency, Environmental Monitoring Systems Laboratory, Research
Triangle Park, NC 27711, EPA Contract No. 68-02-3889, WA No. 120, November, 1987.
21. Pellizzari, E. D., Norwood, D., Sheldon, L., Thomas, K., Whitaker, D., Michael, L.,
and Moseley, M. A., Total Exposure Assessment Methodology (TEAM): Follow-Up Study
in California, Part 11: Protocols for Environmental and Human Sampling and Analysis,"
draft work plan for the U.S. Environmental Protection Agency and California Air Resources
Board, Research Triangle Institute, Research Triangle Park, NC, 1986.
Revised 9/30/89 Pa8e 40
-------
Method IP-1A
VOCs
Table 1. Volatile Organic Compound Data Sheet
COMPOUND (SYNONYM)
Freon 12 (Dichlorodifluoromethane)
Methyl chloride (Chloromethane)
Freon 114 (l,2-0ichloro-l,l,2.2-
tetrafluoroethane)
Vinyl chloride (Chloroethylene)
Methyl bromide (Broraomethane)
Ethyl chloride (Chloroethane)
. Freon 11 (Trichlorofluoromethane)
Vinylidene chloride (l.l-01chloroethene)
Dichloromethane (Methylene chloride)
Freon 113 (l,l,2-Tr1chloro-l,2,2-
trlfluoroethane)
1,1-Oichloroethane (Ethylidene chloride)
cis-l,2-Dichloroethylene
Chloroform (Trichlora»ethane)
1,2-Oichloroethane (Ethylene dlchloride)
Methyl chloroform (1.1.1-Trlchloroethane)
Benzene (Cyclohexatriene)
Carbon tetrachloride (Tetrachloronethane)
1,2-Oichloropropane (Propylene
di chloride)
Trlchloroethylene (Trlchloroethene)
c1s-l,3-0ichloropropene (cis-1.3-
dichloropropylene)
trans-l.3-01chloropropene (ds-1,3-
Olchloropropylene)
1.1,2-Trichloroethane (Vinyl trichloride)
Toluene (Methyl benzene)
1,2-D1brcmoethsne (Ethylene dlbromide)
Tetrachloroethylene (Perchl oroethylene)
Chlorobenzene (Phenyl chloride)
Ethyl benzene
m-Xylene (1,3-Dimethylbenzene)
p-Xylene (l,4-Dimethylxylene)
Styrene (Vinyl benzene)
-1,1,2,2-Tetrachloroethane
o-Xylene (1,2-Dimethylbenzene)
1,3,5-Trimethylbenzene (Mesitylene)
1,2,4-Trimethylbenzene (Pseudocumene)
m-Oichlorobenzene (1,3-Dichlorobenzene)
Benzyl chloride («-Chlorotoluene)
o-Oichlorobenzene (1,2-Oichlorobenzene)
p-Oichlorobenzene (1.4-Dichlorobenzene)
1,2,4-Trichlorobenzene
Hexachlorobutadiene (1,1,2,3,4,4-
Hexachloro-1,3-butadi ene)
FORMULA
C1?CF2
CHjCl2
C1CF2CC1F2
CH2-CHC1
CHjBr
CC13F
CH?Cl7
CF2C1CC12F
CH3CHC12
CHC1-CHC1
CMC 13
C1CH2CH2C1
CH3CC13
CfiHg
O D
CH3CHC1CH2C1
C1CH-CC12
CH3CC1»CHC1
C1CH2CH»CHC1
CH2C1CHC12
BrCH2CH?Br
C12C-CC12
CfiHeCjHs
1 ,3-(CH3)2CsH4
1,4-(CH3)2C6H4
CHC12CHC12
1 2-(CH3)2CfiH4
l!3,5-(CH3)3CSH6
1.2.4-(CH3)3C6H6
1,3-C12C6H4
C6HsCH2Cl
1,2-C12C6H4
1.4-C12C6H4
1.2.4-C13C6H3
IWLECULAR
WEIGHT
120.91
50.49
170.93
62.50
. 94.94
64.52
137 .38
96.95
84.94
187.38
98.96
96.94
119.38
98.96
133.41
78.12
153.82
112.99
131.29
110.97
110.97
133.41
92.15
187.88
165.83
112.56
106.17
106.17
106.17
104.16
167.85
106.17
120.20
120.20
147.01
126.59
147.01
147.01
• 181.45
BOILING
POINT (*C)
-29.8
-24.2
4.1
-13.4
3.6
12.3
23.7
31.7
39.8
47.7
57.3
60.3
61,7
83.5
74.1
80.1
76.5
96.4
87
76
112.0
113.8
110.6
131.3
121.1
132.0
136.2
139.1
138.3
145.2
146.2
144.4
164.7
169.3
173.0
179.3
180.5
174.0
213.5
MELTING
POINT CCJ
-158.0
-97.1
-94.0
-1538.0
-93.6
-136.4
-111.0
-122.5
-95.1
-36.4
-97.0
-80.5
-63.5
-35.3
' -30.4
5.5
-23.0
-100.4
-73.0
-36.5
-95.0
9.8
-19.0
-45.6
-95.0
-47.9
13.3
-30.6
-36.0
-25.2
-44.7
-43.8
-24.7
-39.0
-17.0
53.1
17.0
CAS
NUMBER
74-87-3
75-01-4
74-83-9
75-00-3
75-35-4
75-09-2
. 74-34-3
67-66-3
107-06-2
71-55-6
71-43-2
56-23-5
78-87-5
79-01-6
79-00-5
108-88-3
106-93-4
127-18-4
108-90-7
100-41-4
100-42-5
79-34-5
108-67-8
95-63-6
541-73-1
100-44-7
95-50-1
106-46-7
120-82-1
Revised 9/30/89
Page 41
-------
Method IP-1A
VOCs
Table 2. Ion/Abundance and Expected Retention Time
for Selected VOCs Analyzed by GC-MS-SIM
Ion/Abundance Expected Retention
Comoound (amn/% base oeak) Time (minutes)
jijimfci^UsJUji V
Freon 12 (Dichlorodifluoromethane)
Methyl chloride (Chloromethane)
Freon 114 (1, 2-Dichloro-l, 1,2,2-
tetrafl uoroethane)
Vinyl chloride (Chloroethene)
Methyl bromide (Bromomethane)
Ethyl chloride (Chloroethane)
Freon 11 (Trichlorofluoromethane)
Vinyl idene chloride
(1,1-Dichloroethylene)
Di chloromethane
thylene chloride)
Freon 113 (l,l,2-Trichloro-l,2,2-
trifl uoroethane)
1,1 -Di chloroethane
(Ethyl idene dichloride)
cis-l,2-Dichloroethylene
Chloroform (Tri chloromethane)
1,2-01 chloroethane
(Ethylene dichloride)
Methyl chloroform
(1,1,1-Trichloroethane)
85/100
87/ 31
50/100
52/ 34
85/100
135/ 56
87/ 33
62/100
27/125
64/ 32
94/100
96/ 85
64/100
29/140
27/140
101/100
103/ 67
61/100
96/ 55
63/ 31
49/100
84/ 65
86/ 45
151/100
101/140
103/ 90
63/100
27/ 64
65/ 33
61/100
96/ 60
98/ 44
83/100
85/ 65
47/ 35
62/100
27/ 70
64/ 31
97/100
99/ 64
61/ 61
5.01
5.69
6.55
6.71
7.83
8.43
9.97
10.93
11.21
11.60
12.50
13.40
13.75
14.39
14.62
Revised 9/30/89
Page 42
-------
VOCs
Table
f* nntnniinH
njnipuunu
Benzene (Cyclohexatriene)
Carbon tetrachloride
(Tetrachl oromethane)
1,2-Dlchloropropane
(Propylene dichloride)
Tri chroethyl ene (Tri chl oroethene)
ci s-1 ,3-Dichl oropropene
trans-l,3-Dichloropropene (1,3-
dichloro-1-propene)
1,1,2-Trichloroethane (Vinyl
trichloride)
Toluene (Methyl benzene)
1,2-Dibromoethane (Ethylene
di bromide)
Tetrachl oroethyl ene
(Perchloroethylene)
Chlorobenzene (Benzene chloride)
Ethyl benzene
m,p-Xylene(l,3/l,4-dimethylbenzene)
Styrene (Vinyl benzene)
1,1,2, 2-Tetrachl oroethane
(Tetrachl oroethane)
o-Xylene
(1,2 -Dimethyl benzene)
2. (cont.)
Ion/Abundance
famu/% base oeak)
78/100
«« / A F
77/ 25
SO/ 35
117/100
119/ 97
63/100
41/ 90
f n / T ft
62/ 70
130/100
* •* f\ i f\ n
132/ 92
95/ 87
75/100
39/ 70
77/ 30
75/100
39/ 70
77/ 30
97/100
83/ 90
61/ 82
91/100
92/ 57
107/100
109/ 96
27/115
166/100
164/ 74
•• «& « / f /\
131/ 60
112/100
77/ 62
114/ 32
91/100
106/ 28
91/100
106/ 40
104/100
78/ 60
103/ 49
83/100
85/ 64
91/100
106/ 40
Expected Retention
Time (minutes)
15.04
15.18
15.83
16.10
16.96
17.49
17.61
17.86
18.48
19.01
19.73
20.20
20.41
20.81
20.92
20.92
Revised 9/30/89
-------
Method IP-1A
VOCs
Compound
4-Ethyltoluene
1,3,5-Trimethyl benzene
(Mesitylene)
1,2,4-Trimethylbenzene
(Pseudocumene)
ra-Dichlorobenzene
(1,3-Dichlorobenzene)
Benzyl chloride (a-Chlorotoluene)
p-Dichlorobenzene
(1,4-Di chlorobenzene)
o-Dichlorobenzene
(1,2-Dichlorobenzene)
1,2,4-Trichlorobenzene
Hexachlorobutadiene (1,1,2,3,4,4-
Hexachloro-1,3-butad i ene)
Table 2. (cont.)
Ion/Abundance Expected Retention
famu/% base peak) Time (minutes)
105/100
120/ 29
105/100
120/ 42
105/100
120/ 42
146/100
148/ 65
111/ 40
91/100
126/ 26
146/100
148/ 65
111/ 40
146/100
148/ 65
111/ 40
180/100
182/ 98
184/ 30
225/100
227/ 66
223/ 60
22.53
22.65
23.18
23.31
23.32
23.41
23.88
26.71
27.68
Revised 9/30/89
Page 44
-------
Method IP-1A
VOCs
Table 3. General GC and MS Operating Conditions
Chromatociraphv
Column
Carrier Gas
Injection Volume
Injection Mode
Hewlett-Packard OV-1 cross!inked methyl silicone (50 m x
0.31-mm I.D., 17 im film thickness), or equivalent
Helium (2.0 cm3/nrin at 250'C)
Constant (1-3 pi)
Split!ess
Temperature Program
Initial Column
Temperature
Initial Hold Time
Program
Final Hold Time
-50°C
2 min
8*C/min to 150'C
15 min
Mass Spectrometer
Mass Range
Scan Time
El Condition
Mass Scan
Detector Mode
18 to 250 amu
1 sec/scan
70 eV
Follow manufacturer's
instruction for selecting
selective (MS) detector and selected ion monitoring
mode
Multiple ion detection
mass
(SIM)
FID System (Optional)
Hydrogen Flow
Carrier Flow
Burner Air
30 cm3/nrinute
30 cm3/minute
400 cm3/minute
Revised 9/30/89
Page 45
-------
Method IP-1A VOCs
Table 4. 4-Bromofluorobenzene Key Ions and Ion Abundance Criteria
Mass Ion Abundance Criteria
50 15 to 40% of mass 95
75 30 to 60% of mass 95
95 Base Peak, 100% Relative Abundance
96 5 to 9% of mass 95
173 <2% of mass 174
174 >50% of mass 95
175 5 to 9% of mass 174
176 >95% but <101% of mass 174
177 5 to 9% of mass 176
Revised 9/30/89 Page 46
-------
Method IP-1A VOCs
Table 5. Response Factors (ppbv/area count) and
Expected Retention Time for GC-MS-SIM Analytical Configuration
Response Factor Expected Retention
Time (minutes)
V*UIIIUUUIIU
Freon 12
Methyl chloride
Freon 114
Vinyl chloride
Methyl bromide
Ethyl chloride
Freon 11
Vinyl idene chloride
Dichloromethane
Trichlorotri
fluoroethane
1,1-Dichloroethane
ds-1,2-1.363
Dichloroethylene
Chloroform
1,2-Dichloroethane
Methyl chloroform
Benzene
Carbon tetrachloride
1,2-Dichloropropane
Trichloroethylene
cis-1,3-
Dichloropropene
trans-1,3-
Dichloropropene
1 , 1 , 2-Tri chl oroethane
Toluene
1,2-Dibromoethane
(EBD)
Tetrachl oroethyl ene
Chlorobenzene
Ethyl benzene
m,p-Xylene
Styrene
1,1,2,2-
Tetrachl oroethane
o-Xylene
4- Ethyl toluene
1,3,5-Trimethyl-
benzene
0,6705
4.093
0.4928
2.343
2.647
2.954
0.5145
1.037
2.255
0.9031
1.273
13.40
0.7911
1.017
0.7078
1.236
0.5880
2.400
1.383
1.877
1.338
1.891
0.9406
0.8662
0.7357
0.8558
0.6243
0.7367
1.888
1.035
*•
0.7498
0.6181
0.7088
5.01
5.64
6.55
6.71
7.83
8.43
9.87
10.93
11.21
11.60
12.50
13.75
14.39
14.62
15.04
15.18
15.83
16.10
16.96
17.49
17.61
17.86
18.48
19.01
19.73
20.20
20.41
20.80
20.92
20.92
22.53
22.65
Revised 9/30/89 Page 47
-------
Method IP-1A VOCs
Table 5. (cont.)
Response Factor Expected Retention
Compound (ppbv/area count) Time (minutes)
1,2,4-Trimethyl- 0.7536 23.18
benzene
m-Dichlorobenzene 0.9643 23.31
Benzyl chloride 1.420 23.32
p-Dichlorobenzene 0.8912 23.41
o-Dichlorobenzene 1.004 23.88
1,2,4-Trichloro- 2.150 26.71
benzene
Hexachlorobutadiene 0.4117 27.68
Revised 9/30/89 Page 48
-------
Method IP-1A
VOCs
Table 6. GC-MS-SIM Calibration Table
*»* External Standard . *»*
Operator: JDF
Sample In-fc : SYR I
Misc In-fo:
Integration File Name : DATA:SYR2A02A.I
Sequence Inde::: 1
8 Jan 87 10:CC
Bottle Number : 2
Last Update: 8 Jan 87 8:13 am
Reference Peak Window: 3.00 Absolute Minutes
Non-Re-ference Peak Window: 0.40 Absolute Minutes
Sample Amount: O.OOO Uncalibrated Peak RF: O.OOO Multiplier: 1.667
Peak Int
Num Type Type
1 1 PP
2 1 PP
3 1 BP
4 1 .PB
5 1 BP
6 1 BB
7 1 BV
S i BP
9 1 BP
f\
i
1 .i
13
14
15
16
17
IS
19
20
21
22
S3
24
25
26
27
23
2?
30
31
32
33
54
35
i
JT7
32
39
40
41
1
1
1
1
1
1
1
1
1.
1
1
1
1
1
1
1
*
' 1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
PP
BP
BP
VP
FH
BF
PB
VP
VP
BB
BB
PB
BP
BB
BV
FB
PH
PB
BP
FB
BV
BH
BP
W
VB
BB
BV
W
VB
BP
BB
BB
Ret
Time
5.02O
3.634
6.S25
6.650
7.818
3.421
9.940
10.369
11. 1B7
11.
11.
12.
13.
13.
14.
14.
1-5.
15.
IS.
16.
16.
17.
17.
17.
18.
18.
19.
20.
20.
225
578
492
394
713
378
594
OO9
154
821
067
941
475
594
844
463
989
705
168
372
20.778
20.887
20.
*">*>
22.
23.
23.
23.
892
483
609
144
273
279
23.378
23.
26.
27.
850
673
637
Signal
Description
Mass 85. OO
Mass 50.00
MASS 85.00
Mass 62.00
Mass 94 . OO
Mass 64. 00
Mass 101.00
Miss . 61. OO
Mass 49.OO
Mass
Mass
Mass
MASS
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
41.00
151.00
.63.00
61. OO
•83.00
62. OO
97.00
76. OO
117.0O
63.00
130, OO
75.0O
75.00
97.00
91.00
1O7.0O
166.00
112.OO
91. OO
91. OO
104.00
83.00
91.00
105. OO
1OS.OO
105.00
146.OO
91. OO
146. OO
146.00
180.OO
225.00
amu
afliu
amu
amu
amu
amu
amu
amu
amu
amu
amu
amu
amu
amu
-amu
amu
amu
amu
amu
amu
amu
amu
amu
amu
amu
amu
• amu
amu
amu
amu
amu
amu
amu
amu
amu
amu
amu
amu
amu
amu
amu
Compound
Name
FREOW 12
METHYLCHLORI
FREON 114
VINYLCHLORID
METHVLBROMID
ETHYLCHLORIB
FREON 11
VINDENECHLOR
DICHLOROMETH
AL.LYLCHLORID
3CHL3FLUETHA
1.1DICHLOETH
c-1 ,2DICHLrr
CHLOROFORM
1,2DICHLETHA
METHCHLOROFO
BENZENE
CARBONTETRAC
1,2DICHLFROP
TRICKLETHENE
c-l,3DICHLPR
t-l,3DICHLPfi
1,1,2CHLETHA
TOLUENE
EDB
TETRACHLETHE
CHLOROBENZEN
ETHYLBENZENE
m,p-XYLENE
STYRENE
TETRACHLETHA
o-XYLENE
4-ETHYLTOLUE
1,3,5METHBEN
1,2,4METHBEN
m-DIOR_B£N2E
BENZYLCHLORI
p-DICHLBENZE
o-DICHLBENZE
1,2,4CHLBEN2
HEXACHL.BUTAD
Area
12893
4445
7067
2892
2401
2134
25069
5034
4803
761
5477
5032
4761
.3327
50O9
6656
8352
SSSQ
3283
4336
2328
1626
2721
14417
4070
6574
5648
11084
17989
3143
4531
9798
7694
67S1
7872
3046
3380
6090
2896
562
6309
Amount
4011 pptv
2586 pptv
1215 pptv
1929 pptv «•
1729 pptv
2769 pptv *
6460 pptv
17OO pptv
2343 pptv
8247
1672
1733
1970
1679
2263
2334
2167
1915
179?
2109
987.
689.
1772
2733
1365
2O65
1524
1842
3790
1695
1376
2010
1481
1705
2095
1119
1006
2164
1249
767.
1789
PPtv »
PPtv
pptv *
pptv
PPtv
pptv
pptv
PPtv
PPtv
pptv +
pptv
3 pptv
2 pptv
pptv
pptv
pptv *
PPtv
PPtv
pptv
PPtv
pptv
pptv
pptv
PPtv
PPtv
PPtv
pptv
PPtv
pptv
pptv
1 PPtv
PPtv
Reproduced from Hf*^
best available copy. ^j^
Revised 9/30/89
Page 49
-------
Method IP-1A
VOCs
Table 7. Typical Retention Time (min) and Calibration Response
Factors (ppbv/area count) for Targeted VOCs Associated
with FID and ECD Analytical System
Peak
Number1
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
Compound
Freon 12
Methyl chloride
Freon 114
Vinyl chloride
Methyl bromide
Ethyl chloride
Freon 11
Vinylidene
chloride
Dichloromethane
Trichlorotri-
fluoroethane
1,1-Dichloroe-
thane
cis-l,2-Dichlo-
roethylene
Chloroform
1,2-Dichloroe-
thane
Methyl chloro-
form
Benzene
Carbon tetra-
chloride
1,2-Dichloro-
propane
Trichloroe-
thylene
cis-l,3-Dich-
loropropene
trans-l,3-Dich-
loropropene
1,1,2-Trich-
loroethane
Tol uene
1,2-Dibromoe-
thane (EDB)
Tetrachloroe-
thylene
Retention
Time (RT),
minutes
3.65
4.30
5.13
5.28
6.44
7.06
8.60
9.51
9.84
10.22
11.10
11.99
12.30
12.92
13.12
13.51
13.64
14.26
14.50
15.31
15.83
15.93
16.17
16.78
17.31
FID
Response
Factor (RF)
(ppbv/area
count)
3.465
0.693
0.578
0.406
0.413
6.367
0.347
0.903
0.374
0.359
0.368
1.059
0.409
0.325
0.117
1.451
0.214
0.327
0.336
0.092
0.366
0.324
ECD
Response
Factor
(ppbv/area
count x 10'5)
13.89
22.32
26.34
1.367
3.955
11.14
3.258
1.077
8.910
5.137
1.449
Revised 9/30/89
Page 50
-------
Method IP-1A
VOCs
Table 7. (cont
0
FID ECD
Response Response
Retention Factor (RF) Factor
Peak
Number1
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
Compound
Chlorobenzene
Ethyl benzene
m,p-Xylene
Styrene
1,1,2,2-Tetra-
chloroethane
o-Xylene
4 -Ethyl toluene
1,3,5-Trime-
thyl benzene
1,2,4-Trimethyl-
benzene
m-Dichloro-
benzene
Benzyl chloride
p-Di chloro-
benzene
o-Dichloro-
benzene
1,2,4-Trlch-
lorobenzene
Hexachloro-
bitatadiene
Time (RT),
minutes
18.03
18.51
18.72
19.12
19.20
19.23
20.82
20.94
21.46
21.50
21.56
21.67
22.12
24.88
25.82
(ppbv/area (ppbv/area
count) count x 10 }
0.120
0.092
0.095
0.143
9.856
0.100
0.109
0.111
0.188
0.188
0.667
0.305 1.055
Refer to Figures 15 and 16 for peak location
Revised 9/30/89
Page 51
-------
Method IP-1A VOCs
Table 8. Typical Retention Time (minutes) for
Selected Organics Using GC-FID-ECD-PID* Analytical System
Retention Time (minutes)
Compound CD ECD Elfi
Acetylene 2.984 —- ----
1,3-Butadiene 3.599 -— 3.594
Vinyl chloride 3.790 —- 3.781
Chloromethane 5.137
Chloroethane 5.738
Bromoethane 8.154 rt~I,I
Methylene Chloride 9.232 — - 9.218
trans |