Sorbent & Solution

Sampling Guide

Table Of Contents

1.0 Introduction
2.0 Sorbent Sampling
2.1 Considerations for Sorbent Sampling 5
2.2 Method Specific Sampling Instructions
EPA Method TO-4A 8
EPA Method TO-10A 10
EPA Method TO-13A High Volume 12
EPA Method TO-13A Low Volume 14
EPA Method 0010/8270C by MM5 Train 16
EPA Method TO-17 18
EPA Method VOST, 0030/5041A 22
NIOSH Methods 24
3.0 Solution Sampling
3.1 Method Specific Sampling Instructions
EPA Method TO-5 26
EPA Method TO-11A 28
CARB 430 Method 30
EPA Methods 0011/316 32
Air Toxics Ltd. Method - Siloxanes 34
4.0 Filter Sampling
4.1 Method Specific Sampling Instructions
EPA Method PM10 & TSP 36
 1. 0 I n t r o d u c t i o n

Air Toxics Ltd. presents this guide as a resource for air sampling. Air sampling can be
more involved than water or soil sampling due to the reactivity of chemical compounds
in the gas matrix and sample interaction with the sampling equipment and media.
Ensuring that air samples are collected properly is an important step in acquiring
meaningful analytical results. This guide is not a substitute for experience and cannot
address the multitude of actual field conditions. Note that this guide is intended for
typical projects involving sampling of volatile and semi-volatile organic compounds
(VOCs and SVOCs) with sorbent tubes and impingers, and airborne particulates with
filters. Air Toxics Ltd. also provides a “Guide to Air Sampling and Analysis – Canisters
and Tedlar Bags” for whole air sampling of VOCs.

2.0 Introduction To
Sorbent Sampling

Using a sorbent to collect an air sample normally involves “active” sampling, unlike an
evacuated canister that can be filled “passively” by simply opening the valve. The most
common method to draw an air sample through a sorbent device is to use a small pump
with low flow rates between 10 to 200 milliliters per minute (mL/min) and tubing for
connecting the components. For high volume applications, a high volume air sampler
can be used with a larger sorbent cartridge.

Determining the Safe Sampling Volume

Determining the appropriate volume of air sample to draw through a sorbent tube is
critical to achieving the data quality objectives. The tendency is to increase the sampling
volume in order to lower the final reporting limit.

Note that over-sampling may saturate the sorbent tube and allow the
target compound to breakthrough. See method for volume guidelines.

2
 2.0 Introduction To
Sorbent Sampling

It is imperative to know the flow rate through the sorbent tube and the sampling interval.
A “set up” sorbent tube is often used to set the pump flow rate. It must be very similar to
the actual sorbent tube being used for sample collection. The pressure drop through the
sorbent tube determines the flow rate for a given pump setting. The flow rate through the
sorbent tube should be monitored continuously (or at least periodically) using a
rotometer or electronic flow sensor. If the sampling flow rate is greater than 200 mL/
min, simple rotometers and electronic flow sensors cannot be used. It is necessary to use
a device capable of measuring high flow rates. Refer to the method for information on
the proper method of measuring the flow.

Common Sorbent Sampling Trains

The sampling train generally includes a sorbent tube, pump, and optional components
such as a needle valve, particulate filter, and rotometer or electronic flow sensor. The
sorbent tube is generally the first component in a sampling train, with the tubing and
pump located downstream to minimize contamination of the sample.

The sorbent tube should be upstream of the pump.

For thermal desorption methods, it is critical that the air be drawn through the inlet side of the tube. The
inlet side may be marked with a ring or the sampling direction may be indicated with an arrow. Proper
orientation is especially important when using the multi-bed sorbent tubes described in
EPA Method TO-17. If the low vapor pressure compounds are adsorbed on the high
surface area sorbent (i.e., the one designed for gaseous compounds like vinyl chloride),
they cannot be removed at the desorption temperatures routinely used.

For thermal desorption methods, the sorbent tube must be sampled in

the appropriate direction.

3
 2.0 Sorbent Sampling

Possible Components of a Sorbent Sampling Train

Tubing and Fittings: The components in the sampling train are connected with
tubing and fittings as needed. Because tubing used to connect the sorbent
tube to the pump does not come in contact with the air sample, the tubing
material can be selected on its ability to seal. Tygon is an excellent material for
this purpose, although Nylon and Teflon can be used. The length of tubing
connecting the pump to the sorbent tube is not critical. Many sorbent tubes
accept 1/4 in. Swagelok fittings and 1/4 in O.D. tubing.

Note that if the tubing is in the sample stream then it is necessary to

select the appropriate grade material.

Needle Valve: If a variable speed/adjustable rate air sampling pump is not

available, a needle valve can be used to adjust the flow rate. A rotometer (see
the following section) with a built-in needle valve can provide an economical
solution to adjust and measure sampling flow rate.

Rotometer or Electronic Flow Sensor: Although the flow rate for an air
sampling pump can be calibrated before use, it is often desirable to include a
flow measuring device in the sampling train. Note that the flow rate
produced by a pump can decrease as more components are added to the
sampling train. A rotometer is a relatively inexpensive meter that indicates
flow with a small weight in a tapered column. As flow increases, air resistance
of the weight increases and raises the weight until it is equilibrium with
gravity. For best results, the rotometer must be kept vertical and free of
particulates or moisture. An electronic flow sensor can provide more precise
flow measurement than a rotometer, but is considerably more expensive.
Both devices have optimum working ranges of flow rate (e.g., a typical
rotometer may provide measurement from 100 to 500 mL/min).

4
 Particulate Filter: If the air sample is known to have high levels of particulate
matter, it may be necessary to place a filter at the sorbent tube inlet. In this
case, the connecting tubing between the filter and the sorbent tube will be in
the sampling stream and it should be new Teflon and as short as possible.

2.1 Considerations For

Sorbent Sampling

Sorbent sampling requires the determination of the optimal sampling parameters: sample
volume, flow rate and duration.

Appropriate sample volume should be determined by the media capacity and the required
RLs. Matrix constituents such as water vapor and other non-target compounds should
also be considered. See method specific sections for media capacity information and use
the calculation provided to determine sample volume needed to meet specific RLs.

Determine the Final Reporting Limit for the Target Compound: the concentration
may be a risk-based action level or EPA preliminary remediation goal (PRG).
Determine the Method Reporting Limit: the mass value is provided by the laboratory
and is based on the analytical method selected and the sensitivity of the
instrumentation. The method reporting limit may vary for each target compound.
Calculate the Sampling Volume: use the equation on the next page to determine the
volume of air sample that must be drawn through the sorbent in order to achieve the
final reporting limit.
Compare the Sampling Volume to the SSV: Refer to tables of safe sampling volume
(SSV) for the sorbent being used – (e.g., Table 1 and Appendix 1 in Method TO-17).
If the SSV for the compound of interest is not available, use the SSV of a compound
in the same class (e.g., toluene for xylene, chloroform for carbon tetrachloride, etc.)
and ensure that the compound will not breakthrough when sampling the volume
calculated using the equation above. If breakthrough is a possibility, select a sorbent
with greater sorbent strength (i.e., surface area).

5
 2.1 Considerations For
Sorbent Sampling

1) Calculate Minimum Sample Volume

Minimum Volume (L) = Reporting Limit (ug) * 1000 L
Action Level (ug/m3) m3

Example: Screening Level = 0.08 ug/m3

Minimum Volume (L) = 0.05 ug * 1000 L = 625 Liters
3 3
0.08 ug/m m

2) Calculate Minimum Flow Rate if time duration is set.

Minimum Flow Rate (L/min) = Minimum Volume (L)
Duration (min)
Example: TWA of 24 hours
Minimum Flow Rate (L/min) = 625 L * hour = 0.44 L/min
24 hour 60 min

3) Calculate if Overloading of tube is possible.

For a source-impacted environment, estimate total concentration to estimate maximum
volume. A safe sampling volume is considered to be 75% or less of the cartridge capacity.

Example: the standard TO-11A cartridge supplied by Air Toxics has a capacity
of approximately 75 ug total carbonyls.

Estimated maximum volume (L) = (0.75 * 75 ug) * 1000 L

3
Est. Form. Conc (ug/m ) m3
Example: Source-impacted site 3 ppmv (3700 ug/m3) Formaldehyde
Estimated maximum volume (L) = 0.75 * 75 ug * 1000 L = 15 L
3700 ug/m3 m3

6
 2.1 Considerations For
Sorbent Sampling

Avoid Over Sampling: The adage, “more is better”, often finds its way into sorbent
sampling practice. In attempting to ensure low reporting limits, you may over sample
a sorbent tube – especially if concentrations of target compounds are higher than
expected.

Use a Backup Sorbent Tube: The use of a second, or “backup”, sorbent tube in series
can help prevent compound breakthrough. Even if a safe sampling volume was
calculated and not exceeded during sampling, a backup sorbent tube can provide
insurance. The backup sorbent tube is only analyzed if a predetermined level of a
given compound or total mass is found on the first tube. While the use of a backup
sorbent tube will increase media costs, it usually has little effect on sampling costs. It
will, however, provide definitive support for data integrity.

7
 2.2 Method Specific
Sampling Instructions

EPA Method TO-4A

Determination of Pesticides and Polychlorinated Biphenyls (PCBs) in Ambient Air using
High Volume Polyurethane Foam (PUF) Sampling followed by Gas Chromatographic /
Electron Capture Detector (GC/ECD)
[Link]

This method is applicable for the sample collection and analysis of pesticides and PCBs in
ambient air. See pages 4A-32 and 4A-34 of the method for sampling diagrams.

TO-4A

Media PUF Cartridge (high volume) with Filter (quartz fiber)

Type of Pump High volume sampler; flow rate capability of (~10cfm)

Sampling Rate and 0.225 m3/min for up to 24 hours

Interval
Sampling Volume Up to 300 m3. Determined by user (as needed to achieve
project reporting limits)
Sample Handling Handle with aluminum foil and keep chilled at 4ºC

Media Hold Time 30 days from date of media certification

Extraction Hold 7 days from sampling to extraction at 4ºC

Time
Sample Hold Time 40 days from extraction to analysis at 4ºC

Field QC At least 1 field blank; it is to be treated exactly like a sample

except no air is drawn through the cartridge

8
 2.2 Method Specific
Sampling Instructions

PS1 Sampler

TO-4A Cartridge

12.5 cm
4ft 5in*
PUF

6.5 cm

1ft 3in*
Note: This method was developed using the PS-1 semi-volatile sampler provided by
General Metal Works, Village of Cleves, OH as a guideline. EPA has experience in use of
this equipment during various field monitoring programs over the last several years.
Other manufacturers' equipment should work as well. However, modifications to these
procedures may be necessary if another commercially available sampler is selected.
* Manufacturers include: Tisch Environmental, Anderson Instruments, and Thermo
Environmental Instruments. Equipment specifications may vary by manufacture.

9
 2.2 Method Specific
Sampling Instructions

EPA Method TO-10A

Determination of Pesticides and Polychlorinated Biphenyls in Ambient Air using Low
Volume Polyurethane Foam (PUF) Sampling followed by Gas Chromatographic /
Electron Capture Detector (GC/ECD)
[Link]

This method is applicable for the sample collection and analysis of pesticides and PCBs in
ambient air. See pages 10A-26 through 10A-28 of the method for sampling diagrams.

TO-10A

Media PUF Cartridge (low volume) with or without filter

Type of Pump Personal/portable continuous flow sampling pump; flow

rate capability of 1-5 L/minute
Sampling Rate and 1 to 5 L/min for 4 to 24hrs
Interval
Sampling Volume Determined by user (as needed to achieve project RLs)

Sample Handling Handle with aluminum foil and keep chilled at 4ºC

Media Hold Time 30 days from date of media certification

Extraction Hold 7 days from sampling to extraction at 4ºC
Time
Sample Hold Time 40 days from extraction to analysis at 4ºC
Field QC At least 1 field blank; it is to be treated exactly like a sample
except no air is drawn through the cartridge

10
 2.2 Method Specific
Sampling Instructions

TO-10A PUF Cartridge - Low Volume

2.6 mm

12.7 cm

0.6 mm

11
 2.2 Method Specific
Sampling Instructions

EPA Method TO-13A

Determination of Polycyclic Aromatic Hydrocarbons (PAHs) in Ambient Air using Gas
Chromatography / Mass Spectrometry (GC/MS)
[Link]

This method is applicable for the analysis of PAHs in ambient air. The high volume
PUF/XAD sampling procedure is applicable for a 24-hr sampling period. See pages 13A-
55 and 13A-56 of the method for sampling diagrams.
TO-13A

Media PUF/XAD Cartridge (high volume) with Filter (quartz fiber)

Type of Pump High volume sampler*; flow rate capability of (~10cfm)

Sampling Rate and 0.225 m3/min for up to 24 hours

Interval
Sampling Volume Up to 300 m3. Determined by user (as needed to achieve
project reporting limits)
Sample Handling Handle with aluminum foil and keep chilled at 4ºC

Media Hold Time 30 days from date of media certification

Extraction Hold 7 days from sampling to extraction at 4ºC
Time
Sample Hold Time 40 days from extraction to analysis at 4ºC

Field QC At least 1 field blank; it is to be treated exactly like a sample

except no air is drawn through the cartridge

12
 2.2 Method Specific
Sampling Instructions

PS1 Sampler

TO-13A PUF/XAD Cartridge

PUF
12.5 cm XAD
4ft 5in*
PUF

6.5 cm

1ft 3in*
Note: This method was developed using the PS-1 semi-volatile sampler provided by
General Metal Works, Village of Cleves, OH as a guideline. EPA has experience in use of
this equipment during various field monitoring programs over the last several years.
Other manufacturers' equipment should work as well. However, modifications to these
procedures may be necessary if another commercially available sampler is selected.
* Manufacturers include: Tisch Environmental, Anderson Instruments, and Thermo
Environmental Instruments. Equipment specifications may vary by manufacture.

13
 2.2 Method Specific
Sampling Instructions

Modified EPA Method TO-13A Low Volume

Method TO-13A was intended for sampling SVOCs in ambient air and is generally
unsuitable for indoor air applications. Placement of a high volume sampler in a home or
office would be considered intrusive and impractical, at best. TO-13A can be modified
such that the PUF and XAD-2 sorbent can be packed into a TO-10A cartridge or a XAD
tube instead of the usual TO-13A cartridge. The TO-10A cartridge is packed with a
combination of XAD-2 and PUF and may be used with or without a particulate filter (see
Image 1). The XAD tube is packed with XAD-2 and also may be used with or without a
filter (see Image 2). Both of these configurations are illustrated and can be provided by
Air Toxics Ltd. on a project-specific basis, upon request.

Because of the pressure drop associated with having a packed bed of XAD-2 resin in the
sampling tube, personal sampling pumps (e.g. normally used with small NIOSH sorbent
tubes) may prove inadequate, given the large volume of air that must be sampled. These
small pumps will have difficulty pulling flows greater than a few mL/min through the
tube. A high capacity Kneuberger pump is powered by 12v – using a 12 volt converter or
a 12 volt car battery (see Image 3).

Application Media Type Considerations

Indoor Air PUF/XAD Cartridge - Desired volume to meet required reporting
Low Volume limits and desired duration of sampling i.e.
8hrs for an office or 12hrs for a home need
to be calculated given the capacity of the car-

Soil Gas XAD tube Desired volume to meet required reporting

limits considering the amount of vapor that
can be collected from soil gas as well as the
required flow rate of sampling need to be cal-
culated given the capacity of the tube.

14
 2.2 Method Specific
Sampling Instructions

Image 1

PUF/XAD Cartridge - Low Volume

2.6 mm
Image 2

PUF XAD Tube

12.7 cm Tenax

PUF
10.8 cm

0.6 mm

Image 3

Rotometer
or
Flow Sensor

15
 2.2 Method Specific
Sampling Instructions

EPA Method 0010/8270C

Modified Method 5 Sampling Train
Determination of Destruction and Removal Efficiency (DRE) of Semivolatile Principal
Hazardous Compounds (POHCs) from Incineration Systems and Stationary Sources.

Method 0010 - [Link]

Method 8270C - [Link]

0010/8270C Modified Method 5 Sampling Train

Media Filter (quartz fiber) and sorbent trap (20 g XAD-2)

Type of Pump Metering system. Pump capable of 4 cfm free flow.

see section [Link] of method 0010
Sampling Rate and Determined by user (isokinetic)
Interval
Sampling Volume Determined by user (3 dscm min or as needed to achieve
project reporting limits)
Sample Handling Wrap XAD-2 trap in aluminum foil, and keep chilled at 4ºC

Media Hold Time 30 days from date of media certification

Extraction Hold 14 days from sampling to extraction at 4ºC
Time
Sample Hold Time 40 days from extraction to analysis at 4ºC

Components of the 1. Probe 2. Heated Filter 3. XAD-2 Sorbent Trap

Sample Train 4. Impingers 5. Condensates

16
 2.2 Method Specific
Sampling Instructions

17
 2.2 Method Specific
Sampling Instructions

EPA Method TO-17

Determination of Volatile Organic Compounds in Ambient Air using Active Sampling
Onto Sorbent Tubes.
[Link]
This method replaces earlier sorbent-based EPA Methods TO-1 and TO-2 and provides
an alternative to canister-based EPA Method TO-15. The target compound list is the
same as TO-15 (i.e., subsets of the 97 VOCs listed as hazardous air pollutants in the
Clean Air Act Amendments of 1990). However, TO-17 can collect VOCs over a wider
volatility range than TO-15, by using a tube with multiple sorbents packed in increasing
sorbent strength. Both single and multi-bed sorbent tubes are described in TO-17. Tube
Style 3 (i.e., Carbotrap 300 by Supelco) can be used for compounds ranging in volatility
from n-C3 to n-C16 for air volumes of 2 L at relative humidity below 65% and
temperatures below 30°C. Volumes greater than 5 L can be collected, but C3 compounds
are not quantitatively retained. Single bed tubes, such as Tenax TA, can be used to
effectively collect Naphthalene and middle distillate fuels in indoor air.

Media Sorbent tube (e.g., Carbotrap 300) with optional particulate

filter and ozone scrubber
Type of Pump Low flow rate pump (10 to 200 mL/min) or high flow pump
with low flow adapter
Sampling Rate and 17 and 67 mL/min for 1 hour (example flow rates)
Interval
Sampling Volume 1 and 4 L (example volumes not mandated)
Sample Handling Cap ends, place in culture tube, keep chilled at 4ºC
Media Hold Time Not specified - recommend 30 days at 4ºC
Sample Hold Time 30 days from collection at 4ºC
Field QC Field Blanks - two per sampling event
Distributed Pair One location sampled at two volumes

18
 2.2 Method Specific
Sampling Instructions

Although the method suggests sampling volumes of 1 and 4 L, there is considerable

mention of calculating a safe sampling volume. The sampling volume you select should
include consideration of both the desired final reporting limit and the safe sampling
volume of the sorbent being used (see Section 2.1) . The thought process is outlined
below.
Determine the Final Reporting Limit for the Target Compound: the concentration
may be a risk-based action level or EPA preliminary remediation goal (PRG).
Determine the Method Reporting Limit: the mass value is provided by the laboratory
and is based on the analytical method selected and the sensitivity of the
instrumentation. The method reporting limit may vary for each target compound.
Calculate the Sampling Volume: use the equation on page 6 of this guide to determine
the volume of air sample that must be drawn through the sorbent in order to achieve
the final reporting limit.
Compare the Sampling Volume to the SSV: Refer to tables of safe sampling volume
(SSV) for the sorbent being used – (e.g., Table 1 and Appendix 1 in Method TO-17).
If the SSV for the compound of interest is not available, use the SSV of a compound
in the same class (e.g., toluene for xylene, chloroform for carbon tetrachloride, etc.)
and ensure that the compound will not breakthrough when sampling the volume
calculated using the equation above. If breakthrough is a possibility, select a sorbent
with greater sorbent strength (i.e., surface area).
To illustrate the thought process, an example is provided below:
1. Assume Benzene is the target compound and must be reported at a final reporting limit of
0.0005 ug/L.
2. The laboratory provides a method reporting limit of 10 ng (0.010 ug).
3. Using Equation 3, the sampling volume = 0.010/0.0005 = 20 L.
4. TO-17 Appendix 1 shows that for Benzene, a SSV of up to 26 L can be collected using a
Type 3 (CarboTrap 300) multi-sorbent tube.
In this example, Benzene can theoretically be reported at a final reporting limit of 0.0005 ug/L
with a sampling volume of 20 L.

19
 2.2 Method Specific
Sampling Instructions
TO-17 Sampling Instructions
Application: Soil Gas
Media: TO-17 tube, 1/4”Teflon tubing, 1/4”Tygon tubing, 1/4” to 1/4”Union, 1/4”fittings
with ferrules, a sample pump and a low flow holder maybe required if using a higher flow pump

Typical Sampling Parameters: Sample Flow Rate = 50mL/min Total Vol. = 200 mL Du-
ration = 4 min. These parameters may change depending on project objectives.

Instructions:
1) In order to calibrate the pump use a “set-up” tube. Using the Tygon tubing connect the sam-
pling pump to the outlet of the sorbent tube, if using a higher flow pump a low flow holder
may be necessary to lower the flow rate, then connect the inlet (the ringed side) to the calibra-
tor. Adjust setting to desired flow rate and record.
2) Replace the “set-up” tube with a sample tube. Again using the Tygon tubing connect the
sampling pump to the outlet of the sample tube. Attach the inlet to the union fitting using a
Swagelok nut. Using a 9/16” wrench on the nut and a 7/16” wrench on the union, tighten
the nut. In the same manner, attach the union to the Swagelok nut on the soil gas probe tub-
ing. DO NOT OVERTIGHTEN.
3) Start the sample pump and record the start time. After the desired duration, stop the pump
and record the end time.
4) Replace the end plugs on both ends of the sample tube. Record the sample ID, tube ID and
the collection date/time on the COC.
5) When completed with a set of samples, re-attach the “set-up” tube to the calibrator and
measure the post-sampling flow. Record post-sampling flow rate. This should match within
10% of the pre-sample flow rate.
6) Record sample volume on the COC using the average of the pre- and post- flow rates.
7) Send tubes to the lab in the cooler with ice.

20
 2.2 Method Specific
Sampling Instructions
TO-17 Sampling Instructions
Application: Indoor Air
Media: TO-17 tube, 1/4”Tygon tubing, sample pump & optional dual adjustable flow holder
Parameters: Typical flows should be between 10 to 200 ml/min. Consult with the laboratory to
insure appropriate volumes are collected to meet desired reporting limits.

Instructions:
1) Connect the sampling pump to the outlet of a “set-up” tube using Tygon tubing, connect the
inlet (the ringed side) to the calibrator. Adjust setting to desired flow rate and record. A low
flow holder may be required for a higher flow pump.
2) Replace the “set-up” tube with a sample tube. Using the Tygon tubing connect the sampling
pump to the outlet of the sample tube.
3) The picture above shows a distributed pair using an adjustable 2-tube flow holder. This al-
lows you to take replicate or distributed samples. The flow is adjusted by tightening the
screw on the holder. Two different flows can be used to collect two volumes for a distrib-
uted pair. A 2-tube holder is not necessary for single sample collection. If using a dual
holder it is important to notate which arm corresponds to each recorded flow measurement.
4) Start the sample pump and record the start time. After the desired duration, stop the pump
and record the end time.
5) Replace the end plugs on both ends of the sample tube. Record the sample ID, tube ID and
the collection date/time on the COC.
6) When completed with a set of samples, re-attach the “set-up” tube to the calibrator and
measure the post-sampling flow. Record post-sampling flow rate. This should match within
10% of the pre-sample flow rate.
7) Record sample volume on the COC using the average of the pre- and post- flow rates.
8) Send tubes to the lab in the cooler with ice.

21
 2.2 Method Specific
Sampling Instructions

EPA Method 0030/5041A (VOST)

This method describes the collection of volatile principal organic hazardous constituents
(POHCs) from the stack gas effluents of hazardous waste incinerators. For the purpose
of definition, volatile POHCs are those POHCs with boiling points less than 100°C. If
the boiling point of a POHC of interest is less than 30°C, the POHC may break through
the sorbent under the conditions of the sample collection procedure.
ATL has validated a method of “diluting” a VOST sample prior to analysis in the case of
high level matrices. The first step is to inject surrogate benzene-d6 onto the sample
tube(s). Recovery is monitored as a means of ensuring the integrity of the sample
transfers. The VOST tubes are then thermally desorbed into a Tedlar bag. This gaseous
sample is screened using GC/FID and an acceptable amount of sample is transferred
back onto a clean set of VOST tubes which are subsequently thermally desorbed per the
method. High quality data is obtained from every tube.
Method 0031
M0031 was written in part to specify which organic compounds are appropriate for
collection in contrast to M0030 which provided guidelines based on boiling point alone.
Moreover, polar and reactive compounds are identified as poor performers for the
M0031 collection strategy. In Method 0031 the VOST consists of three glass tubes
containing Tenax, Tenax, and Anasorb, respectively, to trap the organic mass.
0030/5041A VOST
Media One pair of glass sorbent tubes (1.6 g Tenax; 1.0 g Tenax
/ 1.0 g petroleum based charcoal)
Media Hold Time 2 weeks at 4ºC
Type of Pump see method for sampling equipment
Sampling Rate/Interval 1 L/min for 20 min (FAST-VOST); 250 mL/min for 20
min and 500 mL/min for 40 min (SLOW-VOST)
Sampling Volume 20 L (FAST-VOST); 5 and 20 L (SLOW-VOST)
Sample Handling Cap ends, place in culture tube, keep chilled at 4ºC
Hold Time to Analysis 14 days at 4ºC

22
 2.2 Method Specific
Sampling Instructions

VOST Sample Train

23
 2.2 Method Specific
Sampling Instructions

NIOSH 1500/1501
Media Coconut Shell Charcoal tube, 100mg/50mg tube
Media Hold Time Use manufactures expiration date listed on tube
Type of Pump Personal Sampling Pump
Sampling Rate 0.01 - 0.2 L/min
Sampling Volume Ranges from a minimum of 1L to a maximum of 30L
Dependant on contaminant; see method
Sample Handling Ship cold after sampling
Sample Hold Time 30 days at 5°C
Field QC 10% field blanks

NIOSH 1550

Media Coconut Shell Charcoal tube, 100mg/50mg tube

Media Hold Time Use manufactures expiration date listed on tube
Type of Pump Personal Sampling Pump
Sampling Rate 0.01 - 0.2 L/min
Sampling Volume Minimum - 1.3 L; Maximum - 20 L
Sample Handling Ship cold after sampling
Hold Time to Ex- 7 days at 25°C
traction
Extract Hold Time 2 to 10 field blanks per set

24
 2.2 Method Specific
Sampling Instructions

NIOSH 5515
Media 5515 filter + Sorbent (37 mm PTFE + 100mg/50mg XAD-
2 tube)
Media Hold Time Use manufactures expiration date listed on tube
Type of Pump Personal Sampling Pump, capable of operating up to 8hrs at
2 L/min
Sampling Rate 2 L/min
Sampling Volume Minimum - 200 L; Maximum - 1000 L

Sample Handling Handle with aluminum foil and keep chilled at 4°C and keep
out of sunlight
Sample Hold Time Unspecified; ATL uses 7 days
Field QC 2 to 10 field blanks; 6 to 10 media blanks

NIOSH 5503
Media 5503 filter + Sorbent (13 mm glass fiber + 100mg/50mg

Media Hold Time Use manufactures expiration date listed on tube

Type of Pump Personal Sampling Pump
Sampling Rate and 0.05 - 0.2 L/min
Interval
Sampling Volume Minimum - 1 L; Maximum - 50 L

Sample Handling Handle with aluminum foil and keep chilled at 4°C and keep
out of sunlight
Hold Time Unspecified for filter; ATL uses 7 days. Method allows 2
months for Florisil tube
Field QC 2 to 10 field blanks per set

25
 3.0 Solution Sampling

The gas can be drawn (bubbled) through a solution in an impinger to dissolve the
compounds in the gas phase. The sampler records the flow rate and sampling interval for
calculating compound concentration by volume. The impinger vial is subsequently
capped, chilled (as required), and transported to the laboratory for analysis. Sampling
with a solution is similar to sorbent sampling in that compounds are concentrated and the
gas matrix is not collected. However, the solution is chosen so that the compounds of
interest are either dissolved (and consequently remain in solution) or form a derivative in-
situ (and the derivative remains in solution). The compounds/derivatives are analyzed
directly or by chemical extraction. The solution (e.g., methanol, DNPH, water) is
selected according to the type of air sampling and compounds targeted. An acidic
solution of dinitrophenylhydrazine (DNPH) is used to derivatize C1-C3 carbonyl
compounds.
3.1 Method Specific
Sampling Instructions

EPA Method TO-5

Method for the determination of aldehydes and ketones in ambient air using High
Performance Liquid Chromatography (HPLC). [Link]
TO-5
Media One pair of 40 mL glass vials with Teflon screw caps and
25 mL midget impingers in ice bath
Impinger Solution 10 mL 2,4-dinitorphenylhydrazine (DNPH) and 10 mL iso-
octane
Sampling Volume Up to 80 L
Sampling Rate 100 to 1,000 mL/min
Sample Handling Cap vials and keep chilled at 4 ± 2°C
Media Hold Time 48 hrs from date of media preparation at 4ºC
Extraction Hold 7 days from sampling to extraction at 4ºC
Time
Sample Hold Time 30 days from extraction to analysis at 4ºC

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 3.1 Method Specific
Sampling Instructions

Sampling Train

• Front and Back impingers are to be combined at the laboratory.

• Iso-octane can be used

Field QC:
Field Blank—At least one FB with each group of samples. FB is treated identically to the
samples except that no air is drawn through the reagent.

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 3.1 Method Specific
Sampling Instructions

EPA Method TO-11A

Formaldehyde and other carbonyl compounds (aldehydes and ketones) in air are collected
by drawing sample through a DNPH-coated silica gel cartridge using a sampling pump.
TO-11A can be applied to indoor air, ambient air, and source-impacted sites. Collection
times up to 24 hours are used for low ppbv environments, and short-term sampling (5 to
60 minutes) can be used for higher concentration sites.
[Link]

TO-11A
Media Sep-Pak cartridges (DNPH-coated silica gel) an ozone scrubber
is strongly recommended
Sampling Rate Range: 0.1 to 2 L/min. Typical rate for ambient air <1 L/min
when using a personal sampling pump.
Cartridge Capacity S10 Supelco = Approximately 75 ug total carbonyls. Cartridges
with higher capacity are available. If breakthrough is a concern,
use a back-up tube.
Sample Handling Cap ends, place in foil-lined envelope included in shipment.
Label envelope with sample information. Keep chilled at ~ 4ºC
and keep out of sunlight.
Media Hold Time Manufacturer’s expiration date listed on cartridge
Sample Hold Time 14 days
Field QC Samples Field Blank – Treat in the same manner as samples, but do not
draw air through cartridge. Field Duplicate – Collect a collocated
sample using a second sampling port attached to the sample
pump. Back-up tube – If breakthrough is a concern, a back-up
tube can be connected to the sample tube.
Sampling QC QC Measure and record the flow rate before and after sample
collection. Flow rates should not vary more than 10% over the
sampling duration.

28
 3.1 Method Specific
Sampling Instructions

Interferences: Atmospheric ozone can result in a loss of formaldehyde and other

carbonyl derivatives. An ozone scrubber is recommended to minimize interference.
Particulate-laden atmospheres (>50 ug/m3) may result in flow drops during sampling.
Additionally, acrolein and crotonaldehyde may partially degrade using DNPH-coated
silica gel cartridges.

Special Considerations: Compound breakthrough can occur if too much volume is

collected and the sorbent becomes overloaded. If breakthrough is a concern, cartridges
may be sampled as a train. The two cartridges are analyzed separately by the laboratory to
monitor breakthrough.

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 3.1 Method Specific
Sampling Instructions

CARB Method 430

This method applies to the determination of formaldehyde and acetaldehyde emissions
from stationary sources. The method is based on the use of high performance liquid
chromatography (HPLC).

[Link] See sections 8.0 - 8.2 on pages 18 - 23

for sampling procedures.
CARB 430
Media One pair of 25 mL glass vials with Teflon screw caps and 35
mL midget impingers in ice bath
Impinger Solution 10 mL 2,4-dinitorphenylhydrazine (DNPH)

Sampling Volume Up to 80 L
Sampling Rate 100 to 1,000 mL/min
Sample Handling Cap vials and keep chilled at 4 ± 2°C
Media Hold Time 48 hrs from date of media preparation at 4ºC
Extraction Hold 7 days from sampling to extraction at 4ºC
Time
Sample Hold Time 30 days from extraction to analysis at 4ºC

30
 3.1 Method Specific
Sampling Instructions

Sampling Train

• Each vial will be treated as an individual sample, do not combine.

• Iso-octane should not be used.

Field QC:
Trip Blank
Field Blank
Field Spike (as requested)

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 3.1 Method Specific
Sampling Instructions

EPA Method 0011 Sampling for selected aldehyde and ketone emissions from
stationary sources. [Link]
Method 0011 sampling is comprised of an isokinetic sampling train containing DNPH
filled impingers. Formaldehyde and other aldehydes and ketones react with the DNPH to
form derivatives. The derivatives are extracted and analyzed by HPLC/UV.

Method 0011

Media DNPH filled impingers

Sampling Rate Determined by user (isokinetic)
Sampling Volume Determined by user
Sample Handling Cap vials and keep chilled at 4 ± 2°C
Media Hold Time 5 days from date made and 2 days from date opened in the
field
Extraction Hold 7 days from sampling to extraction at 4ºC
Time
Sample Hold Time 30 days from extraction to analysis at 4ºC
Quality Control Field Spike - typically ~ 800 ug of formaldehyde. (Place the
field spike into an impinger containing 200 mL of DNPH
solution, recover, and return for analysis.)
Sample Blank - add a volume of DNPH reagent and Me-
thylene chloride equal to the total volume of the combined
impingers and rinses.
Matrix Spike Sample - this additional sample may be col-
lected for use as a matrix spike sample as described in Sec. 8.0
of Method 8315.
Field blanks - may be submitted with the samples collected
at each sampling site.

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 3.1 Method Specific
Sampling Instructions

EPA Method 316

Sampling and Analysis for Formaldehyde Emissions from Stationary Sources in the
Mineral Wool/Wool Fiberglass Industries. [Link]
Method 316 sampling is comprised of an isokinetic sampling train containing reagent
grade water filled impingers. Formaldehyde is absorbed in the DI water. The contents of
the impinger and DI train rinses are analyzed for by a modified pararosaniline method.
Samples are derivatized with pararosaniline and sodium sulfite to create a purple
chromophore. The chromophore is analyzed by spectrophotometer set at 570nm.

EPA Method 316

Media Reagent grade water filled impingers
Sampling Rate Determined by user (isokinetic)
Sampling Volume 30 cubic ft minimum sample volume
Sample Handling Cap vials and keep chilled at 2°C
Sample Hold Time 14 days from date of collection at 2ºC
Field Blank 1 per set

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 3.1 Method Specific
Sampling Instructions

Air Toxics Method @ 71 Siloxanes

Siloxanes are a family of organic compounds containing chains of silicon, oxygen, and
methyl groups. These organosilicon compounds, commonly called silicones, differ from
naturally occurring inorganic forms of silicon (i.e., silicates). Siloxanes are manufactured
in a wide variety of forms including low to high viscosity fluids, gums, elastomers, and
resins.
Building on results of the 1997 Dow Corning landfill consortium investigation, the ATL
method is based on drawing air-phase samples through a series of two midget impingers
containing methanol (see Table 1). Siloxanes present in the air-phase dissolve in the
chilled methanol solution and are subsequently capped and kept chilled until analysis.
The suggested media hold time is 30 days and the suggested sample hold time until
analysis is 21 days.

Air Toxics @ 71 Siloxanes

Media One pair of 24 mL borosilicate glass vials with Teflon screw

Impinger Solution Up to 15 mL methanol (6 mL suggested)

Sampling Volume Determined by user (20 L suggested)

Sampling Rate Determined by user (112 mL/min for 3 hours suggested)

Sample Handling Cap vials and keep chilled at 4 ± 2°C

Media Hold Time 30 days from date of certification

Sample Hold Time 21 days from collection

34
 3.1 Method Specific
Sampling Instructions

Collect the sample by attaching inert, flexible tubing from the source air stream to the
inlet of the first impinger (see Figure 4). Additional tubing connects the outlet of the first
impinger to the inlet of the second impinger and both impingers are chilled in an ice bath.
If the source is not under pressure, a low-volume pump can supply the vacuum required
to draw the sample though the impingers.

Air Flow Rotometer

Tygon Tubing

Needle Valve

Midget Impinger

Methanol vial

A needle valve and rotameter can be used to adjust and measure the flow rate of sample
through the impingers. The user must determine optimum sampling rate and volume to
achieve the data quality objectives of the sampling program. Sampling rates from 100 to
1,000 mL/min are appropriate as long as there is not significant loss of impinger solution.
The amount of sample air drawn through the impingers and the amount of methanol in
the impinger determine the final reporting limit concentration. The more sample air
drawn through the impingers equates to more target constituent concentrated in the
solution and thus lower reporting limits. Be careful not to over sample and saturate the
solution. Less impinger solution equates to lower reporting limits, but has less capacity to
dissolve the target constituents. For applications involving siloxanes removal from
methane gas sources, Applied Filter Technology suggests filling each impinger with 6 mL
of methanol and sampling at a flow rate of 112 mL/min for 180 minutes [4]. This
arrangement results in a sampling volume of approximately 20 L.

35
 4.0 Filter Sampling

Gas may be drawn through a filter to immobilize the compounds suspended in a gas
matrix (or adsorbed on particulates suspended in a gas matrix) onto the surface of the
filter material. The sampler records the flow rate and sampling interval for calculating
compound concentration by volume. The filter is bagged, chilled (as required), and
transported to the laboratory for analysis. Sampling with a filter is similar to sorbent and
solution sampling in that compounds are concentrated and the gas matrix is not collected.
The filter may be weighed before and after sampling to provide a gravimetric analysis of
the total particulates and compounds collected. In addition, the filter can undergo
solvent extraction or digestion to determine the presence of organic and inorganic
compounds. The filter (e.g., quartz fiber, mixed cellulose ester, Teflon) is selected
according to the type of air sampling and compounds targeted.

4.1 Method Specific

Sampling Instructions

PM10
This method provides for the measurement of the mass concentration of particulate
matter with an aerodynamic diameter less than or equal to a nominal 10 micrometers
(PM10) in ambient air over a 24-hour period for purposes of determining attainment and
maintenance of the primary and secondary national ambient air quality standards for
particulate matter.
[Link]
TSP
See PM10
The methods for TSP and PM-10 differ slightly in the conditioning requirements for the
filters. Air Toxics treats the two methods the same way using the more stringent
conditioning requirements.

36
 4.1 Method Specific
Sampling Instructions

PM10 & TSP

Media 8 X 10 inch glass fiber filter
Media Hold Time None specified.
Type of Pump High volume sampler*

Sampling Rate and 0.5 m3/min for 24 hours

Interval
Sampling Volume 700 m3
Sample Handling None Specified. Use protective packaging. Do not allow the
filters to get wet or damaged. Do not handle with bare

Hold Time to Air Toxics suggests 14-day sample hold time.

Analysis
Analytical Method Gravimetric
QC Samples Duplicates, Lab Blank, Trip Blank

* Manufacturers include: Tisch

Environmental, Village of Cleves-
Ohio; Anderson Instruments-500
Technology Ct, Smyma, GA; and
Thermo Environmental Instruments-
8 West Forge Parkway, Franklin, MA.

37