ASTM D5075-01(2012)e1
(Test Method)Standard Test Method for Nicotine and 3-Ethenylpyridine in Indoor Air
Standard Test Method for Nicotine and 3-Ethenylpyridine in Indoor Air
SIGNIFICANCE AND USE
In order to estimate ETS concentrations, there needs to be a marker or tracer for ETS that is unique or highly specific to tobacco smoke, in sufficient concentrations in air to be measured easily at realistic smoking rates, and in constant proportion to the other components of ETS for a variety of tobacco blends and environmental conditions. Nicotine and 3-ethenylpyridine have been used as tracers of the vapor phase of ETS. Nicotine is the major alkaloid of tobacco and a major constituent of ETS. The determination of nicotine concentration has often been used to estimate the concentration of ETS; however, due to its unpredictable decay kinetics, nicotine may not be an ideal tracer. Because nicotine readily adsorbs to building materials and room furnishings and is depleted from ETS at a rate faster than most other components, some have suggested that nicotine concentrations underestimate ETS concentrations. Although this is true in many environments during the generation of smoke, the converse is true in environments with a recent past history of smoking. The adsorbed nicotine slowly desorbs over time, resulting in an overestimation of ETS concentrations. Thus, measured concentrations of nicotine precisely assess only airborne nicotine and indicate only that smoking has taken place; they do not necessarily indicate the presence, and certainly not the concentrations, of other ETS constituents. 3-Ethenylpyridine, on the other hand, has been shown to track exactly the vapor phase of ETS as measured by CO and FID response (3). It is for these reasons that 3-ethenylpyridine may be a better tracer of ETS (1,4,5). The ETS at high concentrations is known to be annoying and irritating to individuals, and concerns over potential health effects have also been expressed. There is a definite need to have reliable methods for the estimation of ETS levels in order to evaluate its effect. The NIOSH has previously set a threshold limit value (TLV) for nicotine in the workplace of 0.5...
SCOPE
1.1 This test method covers the sampling/analysis of nicotine and 3-ethenylpyridine (3-EP) in indoor air. This test method is based upon the collection of nicotine and 3-EP by adsorption on a sorbent resin, extraction of nicotine and 3-EP from the sorbent resin, and determination by gas chromatography (GC) with nitrogen selective detection. (1)
1.2 The active samplers consist of an XAD-4 sorbent tube attached to a sampling pump. This test method is applicable to personal or area sampling.
1.3 This test method is limited in sample duration by the capacity of the XAD-4 tube for nicotine (about 300 μg). This test method has been evaluated up to 24-h sample duration; however, samples are typically acquired for at least 1 h (sometimes only 1 h). (2)
1.4 For this test method, limits of detection (LOD) and quantitation (LOQ) for nicotine at a sampling rate of 1.5 L/min are, respectively, 0.11 μg/m3 and 0.37 μg/m3 for 1-h sample duration and 0.01 μg/m3 and 0.05 μg/m3 for 8-h sample duration. The LOD and LOQ for 3-EP at a sampling rate of 1.5 L/min are, respectively, 0.06 μg/m3 and 0.19 μg/m3 for 1-h sample duration and 0.01 μg/m3 and 0.02 μg/m3 for 8-h sample duration (2). Both LOD and LOQ can be reduced by increasing the sensitivity of the thermionic specific detector.
1.5 Units—The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.6 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. Specific precautionary information is given in 13.6.
General Information
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Designation: D5075 − 01 (Reapproved 2012)
Standard Test Method for
Nicotine and 3-Ethenylpyridine in Indoor Air
This standard is issued under the fixed designation D5075; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
ε NOTE—Reapproved with editorial change to 1.5 in April 2012.
1. Scope 2. Referenced Documents
1.1 This test method covers the sampling/analysis of nico- 2.1 ASTM Standards:
tine and 3-ethenylpyridine (3-EP) in indoor air. This test D1356Terminology Relating to Sampling and Analysis of
method is based upon the collection of nicotine and 3-EP by Atmospheres
adsorption on a sorbent resin, extraction of nicotine and 3-EP D1357Practice for Planning the Sampling of the Ambient
from the sorbent resin, and determination by gas chromatog- Atmosphere
raphy (GC) with nitrogen selective detection. (1) D3631Test Methods for Measuring Surface Atmospheric
Pressure
1.2 The active samplers consist of an XAD-4 sorbent tube
D5337Practice for Flow RateAdjustment of Personal Sam-
attached to a sampling pump.This test method is applicable to
pling Pumps
personal or area sampling.
E260Practice for Packed Column Gas Chromatography
1.3 This test method is limited in sample duration by the
E355PracticeforGasChromatographyTermsandRelation-
capacity of the XAD-4 tube for nicotine (about 300 µg). This
ships
test method has been evaluated up to 24-h sample duration;
however, samples are typically acquired for at least 1h
3. Terminology
(sometimes only 1 h). (2)
3.1 Definitions—For definitions of terms used in this test
1.4 For this test method, limits of detection (LOD) and
method, refer to Terminology D1356 and Practice E355.
quantitation(LOQ)fornicotineatasamplingrateof1.5L/min
3.2 Definitions of Terms Specific to This Standard:
3 3
are, respectively, 0.11 µg/m and 0.37 µg/m for 1-h sample
3.2.1 environmental tobacco smoke (ETS)—an aged, dilute
3 3
duration and 0.01 µg/m and 0.05 µg/m for 8-h sample
composite of exhaled tobacco smoke and smoke from tobacco
duration.TheLODandLOQfor3-EPatasamplingrateof1.5
products.
3 3
L/min are, respectively, 0.06 µg/m and 0.19 µg/m for 1-h
3.2.2 nitrogen-phosphorus detector (NPD)—a highly sensi-
3 3
sampledurationand0.01µg/m and0.02µg/m for8-hsample
tivedeviceselectivefordetectionofnitrogen-andphosphorus-
duration (2).BothLODandLOQcanbereducedbyincreasing
containing organic compounds.
the sensitivity of the thermionic specific detector.
3.2.3 XAD-4 resin—macroreticular polystyrene-
1.5 Units—The values stated in SI units are to be regarded
divinylbenzene copolymer beads.
asstandard.Nootherunitsofmeasurementareincludedinthis
standard.
4. Summary of Test Method
1.6 This standard does not purport to address all of the
4.1 A known volume of air is drawn through a sorbent
safety concerns, if any, associated with its use. It is the
sampling tube containing XAD-4 resin to adsorb the nicotine
responsibility of the user of this standard to establish appro-
and 3-EP present.
priate safety and health practices and determine the applica-
4.2 The XAD-4 sorbent tube contents are transferred to a
bility of regulatory limitations prior to use. Specific precau-
2-mLautosamplervial,andthenicotineand3-EParedesorbed
tionary information is given in 13.6.
with ethyl acetate containing 0.01% triethylamine and a
known quantity of quinoline, the internal standard.
This test method is under the jurisdiction of ASTM Committee D22 on Air
Quality and is the direct responsibility of Subcommittee D22.05 on Indoor Air.
Current edition approved April 1, 2012. Published July 2012. Originally
approved in 1990. Last previous edition approved in 2007 as D5075-01(2007). For referenced ASTM standards, visit the ASTM website, www.astm.org, or
DOI: 10.1520/D5075-01R12E01. contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
The boldface numbers in parentheses refer to a list of references at the end of Standards volume information, refer to the standard’s Document Summary page on
the text. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
´1
D5075 − 01 (2012)
4.3 An aliquot of the desorbed sample is injected into a gas quantifying nicotine in indoor air. Other methods for the
chromatograph equipped with a thermionic-specific (nitrogen- determination of nicotine in indoor air have also been reported
phosphorus) detector. (6,10,11,12). 3-Ethenylpyridine concentrations typically are
about one third the concentrations of nicotine in real-world
4.4 The areas of the resulting nicotine and 3-EP peaks are
environments (13).
each divided by the area of the internal standard peak and
compared with area ratios obtained from the injection of
6. Interferences
standards.
6.1 UseofpackedGCcolumnsmayresultinreadingslower
than expected because nicotine can adsorb onto undeactivated
5. Significance and Use
glass, metal, and solid support particles. Fused silica capillary
5.1 In order to estimate ETS concentrations, there needs to
columns and the modified extraction solvent prescribed here
be a marker or tracer for ETS that is unique or highly specific
can circumvent this problem.
to tobacco smoke, in sufficient concentrations in air to be
6.2 Quinoline (internal standard) is present in ETS at a
measured easily at realistic smoking rates, and in constant
concentration approximately 1% of that for nicotine and is
proportion to the other components of ETS for a variety of
collectedbytheXAD-4resin.If>10µgnicotineiscollectedon
tobacco blends and environmental conditions. Nicotine and
the resin, there will be sufficient quinoline present to cause a
3-ethenylpyridine have been used as tracers of the vapor phase
detectable bias in results (approximately 1%). (For example,
of ETS. Nicotine is the major alkaloid of tobacco and a major
this quantity of nicotine would be collected if a nicotine
constituent of ETS. The determination of nicotine concentra-
concentrationof167µg/m wassampledat1L/minfor1h.)In
tion has often been used to estimate the concentration of ETS;
these cases, one of the following alternative procedures should
however, due to its unpredictable decay kinetics, nicotine may
be followed:
not be an ideal tracer. Because nicotine readily adsorbs to
6.2.1 Quantitatively dilute the sample with the same modi-
building materials and room furnishings and is depleted from
fied solvent containing internal standard (described in 11.2)
ETS at a rate faster than most other components, some have
usedtoextracttheoriginalsample;thatis,decreasetheamount
suggested that nicotine concentrations underestimate ETS
of quinoline (and also nicotine) present in the sample while
concentrations. Although this is true in many environments
keeping the quinoline concentration in the solvent constant.To
during the generation of smoke, the converse is true in
prevent significant interference, the nicotine concentration in
environments with a recent past history of smoking. The
the most concentrated sample should be less than or equal to
adsorbed nicotine slowly desorbs over time, resulting in an
the quinoline concentration in the solvent.
overestimationofETSconcentrations.Thus,measuredconcen-
6.2.2 Use an alternate internal standard [N'-ethylnornico-
trations of nicotine precisely assess only airborne nicotine and
tine is recommended (14)].
indicate only that smoking has taken place; they do not
necessarily indicate the presence, and certainly not the
7. Apparatus
concentrations, of other ETS constituents. 3-Ethenylpyridine,
7.1 Sample Collection:
on the other hand, has been shown to track exactly the vapor
7.1.1 XAD-4 Sorbent Tube—Glass tube with both ends
phase of ETS as measured by CO and FID response (3).Itis
flame-sealed, approximately 7 cm long with 6-mm outside
for these reasons that 3-ethenylpyridine may be a better tracer
diameter and 4-mm inside diameter, containing one section of
of ETS (1,4,5).The ETS at high concentrations is known to be
120 mg of 20/40 mesh XAD-4 resin. A glass wool plug is
annoying and irritating to individuals, and concerns over
located at the front end (inlet) and back end of the tube. The
potential health effects have also been expressed. There is a
glasswoolplugattheinletendofthetubeisheldinplacewith
definite need to have reliable methods for the estimation of
a metal lockspring.
ETS levels in order to evaluate its effect. The NIOSH has
7.1.2 Tube Holder,withclipattachmentforattachingtubeto
previously set a threshold limit value (TLV) for nicotine in the
clothing or objects.
workplace of 0.5 mg/m .
7.1.3 Tube Breaker,tobreaksealedendsfromsampletubes.
5.2 Studies show that more than 90% of nicotine in indoor
7.1.4 NIOSH-approved Plastic Caps,forcappingtubesafter
airisfoundinthevaporphase (6,7).Thedescribedtestmethod
sampling.
collects vapor-phase nicotine quantitatively. Early studies on
7.1.5 Barometer and Thermometer, for taking pressure and
freshly generated ETS indicated that some but not all of the
temperature readings at the sampling site (optional).
particulate phase was trapped on the XAD-4 resin (7). Amore
7.1.6 Bubble Flowmeter, for sample pump calibration.
recent investigation of the trapping of particulate materials by
7.1.7 Personal Sampling Pump,portableconstant-flowsam-
sorbent beds suggests that the trapping of the particles from
pling pump calibrated for the flow rate desired (up to 1.5
indoor air may be nearly quantitative (8). 3-Ethenylpyridine is
L/min).
found exclusively in the vapor phase.
7.2 Analytical System:
5.3 Nicotine concentrations typically range from ND (not 7.2.1 Gas Chromatograph, with a nitrogen-phosphorus
detected) to 70 µg/m in various indoor environments with (thermionic) detector and autosampler.
values usually at the lower end of this range (9). Because such 7.2.2 GC Column—A 30-m by 0.32-mm inside diameter
low concentrations of nicotine are often encountered, sophis- fusedsilicacapillarycolumn,coatedwitha1.0-µmfilmof5%
ticated analytical procedures and equipment are required for phenyl methylpolysiloxane (DB-5).
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D5075 − 01 (2012)
7.2.3 Chromatography Data Acquisition System, for mea- 9.2.3 AftertheXAD-4sorbenttubeiscorrectlyinsertedand
suring peak areas electronically. positioned, turn on the power switch for the pump to begin
sampling. Record the start time.
7.2.4 Sample Containers, borosilicate glass autosampler
vials, 2-mL capacity, with PTFE-lined septum closures.
NOTE 1—Most pumps have microprocessing capabilities for preset
7.2.5 Dispensing Pipets, 1.25-mL.
sampling periods.
7.2.6 Triangular File,forscoringandbreakingopensample
9.2.4 Record the barometric pressure and ambient tempera-
tubes.
ture (optional).
7.2.7 Forceps,forassistingtransferofsorbenttubecontents
9.2.5 Turn off the pump at the end of the desired sampling
from tube to autosampler vial.
period, and record the elapsed time in minutes.
7.2.8 Glass Wool Removal Tool, for assisting transfer of
9.2.6 Measure and record the flow rate after sampling so
sorbent tube contents from tube to autosampler vial.
that an average of initial and final flow rates can be used in
7.2.9 Wrist-action Shaking Device, for solvent extraction.
subsequent calculations.
9.2.7 Remove the sorbent tube from the sampling system
8. Reagents and Materials
and place plastic caps over both ends of the tube.
9.2.8 Treat a minimum of two sorbent tubes in the same
8.1 Purity of Reagents—Reagent grade chemicals shall be
manner as the sample tubes (break, measure flows, cap, and
used in all tests. Unless otherwise indicated, it is intended that
transport). Label and process these tubes as flow blanks.
all reagents conform to the specifications of the Committee on
9.2.9 Transport capped sorbent tubes to the laboratory for
Analytical Reagents of theAmerican Chemical Society where
analysis.
such specifications are available. Other grades may be used,
provided it is first ascertained that the reagent is of sufficiently
NOTE 2—If the samples are not prepared and analyzed immediately,
high purity to permit its use without lessening the accuracy of
they should be stored at 0°C or less. All sorbent tube samples should be
analyzed within eight weeks after sample collection. It has been estab-
the determination.
lished that samples are stable for at least eight weeks at−10°C.
8.2 Ethyl Acetate, chromatographic quality.
10. Analysis
8.3 Quinoline (internal standard), 99+%.
10.1 System Description:
8.4 Triethylamine, 99+%.
10.1.1 Analysis is performed using a GC fitted with a
8.5 Nicotine, 99+%.
nitrogen-phosphorus detector and an autosampler equipped for
split/splitless injection.
8.6 4-Ethenylpyridine (4-EP), 95%, commercially avail-
10.1.2 The GC column is as listed in 7.2.2.
able isomer of 3-ethenylpyridine.
10.1.3 The GC conditions are as listed in Table 1.
8.7 Helium Cylinders,forcarrierordetectormakeupgas,or
10.1.4 The autosampler uses default settings for the injec-
both, 99.995% grade.
tion sequence, and 1 or 2 µL of sample is injected with a 30-s
8.8 Hydrogen Cylinders, for detector gas, 99.995% grade. splitless period.
10.1.5 Peak areas are measured electronically with a chro-
8.9 Air, for detector gas (<0.1 ppm hydrocarbon).
matography data acquisition system.
10.2 Systems Performance Criteria:
9. Sampling
9.1 General—For planning sampling programs, refer to
Practice D1357.
TABLE 1 Summary of Gas Chromatograph Conditions
Temperatures
9.2 Procedure:
Injector 225°C
9.2.1 Prepare XAD-4 sampling tubes immediately before
Oven
sampling. Break both ends of the sealed sorbent tube using a
Initial temperature 50°C
Hold time 1 min
tube breaker tool. The opening should measure at least 2 mm
Program Step 1
in diameter.
Rate 10°C/min
9.2.2 Connect the sorbent tube to the personal sampling
Final temperature 215°C
Hold time 0 min
pump with tubing. Position the sorbent tube so that the air
Program Step 2
being sampled will pass first through the front section of resin
Rate 20°C/min
and then through the backup section. The inlet end of the tube Final temperature 295°C
Hold time 1 min
is exposed directly to the atmosphere, and the outlet end is
Detector 300°C
inserted in the tubing; or the tube itself is put into a safety
Gas flows
casinginthepersonalsamplingsetupandattachedaccordingly. He, carrier 4 mL/min (15 psig)
H , detector 3 mL/min
Adjust the potentiometer on the sampling pump until the
Air, detector 75 mL/min
desired flow rate (≤1.5 L/min) is obtained. With the bubble
He, makeup 15 mL/min
flowmeter connected to the inlet end of the sorbent tube, Retentio
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