ASTM D6877-13(2018)

This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D6877 − 13 (Reapproved 2018)
Standard Test Method for
Monitoring Diesel Particulate Exhaust in the Workplace
This standard is issued under the fixed designation D6877; 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.
1. Scope approximately 0.2-µg carbon per cm of filter was estimated
when analyzing a sucrose standard solution applied to filter
1.1 This test method covers determination of organic and
portions cleaned immediately before analysis. LODs based on
elemental carbon (OC and EC) in the particulate fraction of
media blanks stored after cleaning are usually higher. LODs
dieselengineexhaust,hereafterreferredtoasdieselparticulate
based on a set of media blanks analyzed over a six month
matter (DPM). Samples of workplace atmospheres are col-
period at a commercial laboratory were OC = 1.2 µg/cm , EC
lected on quartz-fiber filters. The method also is suitable for
2 2
= 0.4 µg/cm , and TC = 1.3 µg/cm , where TC refers to total
other types of carbonaceous aerosols and has been widely
carbon (TC = OC + EC). In practice, the LOD estimate
applied to environmental monitoring. It is not appropriate for
provided by a laboratory is based on results for a set of media
sampling volatile or semi-volatile components. These compo-
blanks submitted with the samples.To reduce blank variability
nents require sorbents for efficient collection.
(due to lack of loading), a manual OC-EC split is assigned at
NOTE1—Samplecollectionandhandlingproceduresforenvironmental
the time when oxygen is introduced. With manual splits, the
samples differ from occupational samples. This standard addresses occu-
pational monitoring of DPM in workplaces where diesel-powered equip-
SD for media blanks is typically about 0.02–0.03 µg EC/cm ,
ment is used.
givingLODs(3×SDblank)fromabout0.06–0.09µgEC/cm .
1.2 The method is based on a thermal-optical technique (1, The corresponding air concentration depends on the deposit
2). Speciation of OC and EC is achieved through temperature area (filter size) and air volume.
andatmospherecontrol,andanopticalfeaturethatcorrectsfor
1.5 OC-EC methods are operational, which means the
sample charring (carbonization).
analyticalproceduredefinestheanalyte.Thetestmethodoffers
1.3 A portion of a 37-mm, quartz-fiber filter sample is greater selectivity and precision than thermal techniques that
analyzed. Results for the portion are used to calculate the total donotcorrectforcharringoforganiccomponents.Theanalysis
mass of OC and EC on the filter. The portion must be method is simple and relatively quick (about 15 min). The
representative of the entire filter deposit. If the deposit is analysis and data reduction are automated, and the instrument
uneven, two or more representative portions should be ana- is programmable (different methods can be saved as methods
lyzed for an average. Alternatively, the entire filter can be for other applications).
analyzed, in multiple portions, to determine the total mass.
1.6 A method (5040) for DPM based on thermal-optical
Open-faced cassettes give even deposits but may not be
analysis has been published by the National Institute for
practical. At 2 L/min, closed-face cassettes generally give
Occupational Safety and Health (NIOSH). Method updates (3,
results equivalent to open-face cassettes if other dusts are
4)havebeenpublishedsinceitsinitial(1996)publicationinthe
absent. Higher flow rates may be employed, but closed-faced
NIOSHManualofAnalyticalMethods(NMAM).Both OCand
cassettes operated at higher flow rates (for example, 5 L/min)
EC are determined by NMAM 5040. An EC exposure marker
sometimes have uneven deposits due to particle impaction at
(for DPM) was recommended because EC is a more selective
the center of the filter. Other samplers may be required,
measure of exposure. A comprehensive review of the method
depending on the sampling environment (2-5).
and rationale for selection of an EC marker are provided in a
1.4 The calculated limit of detection (LOD) depends on the Chapter of NMAM (5).
level of contamination of the media blanks (5).A LOD of
1.7 The thermal-optical instrument required for the analysis
is manufactured by a private laboratory. As with most
This test method is under the jurisdiction of ASTM Committee D22 on Air
Quality and is the direct responsibility of Subcommittee D22.04 on WorkplaceAir The carbon analyzer used in the development and performance evaluation of
Quality. this test method was manufactured by Sunset Laboratory, 2017 19thAvenue, Forest
Current edition approved Oct. 1, 2018. Published October 2018. Originally Grove, Oregon 97116, which is the sole source of supply of the instrument known
ɛ1
approved in 2003. Last previous edition approved in 2013 as D6877–13 . DOI: to the committee at this time. If you are aware of alternative suppliers, please
10.1520/D6877-13R18. provide this information toASTM International Headquarters.Your comments will
2 1
The boldface numbers in parentheses refer to references at the end of this test receive careful consideration at a meeting of the responsible technical committee,
method. which you may attend.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D6877 − 13 (2018)
instrumentation, design improvements continue to be made. 3.3.4 σ (µg/cm )—standard deviation in collected mass
w
Different laboratories may be using different instrument mod- loading determination
els. 2
3.3.5 OC, EC, TC (µg/cm or µg)—organic, elemental, and
total carbon
1.8 The values stated in SI units are to be regarded as
standard. No other units of measurement are included in this
3.3.6 RSD—relative standard deviation
standard.
3.3.7 V (L)—sampled volume
1.9 This standard does not purport to address all of the
3.3.8 W (µg)—field blank filter’s EC mass reading
b
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro- 3.3.9 W (µg)—active filter’s EC mass reading
EC
priate safety, health, and environmental practices and deter-
mine the applicability of regulatory limitations prior to use. 4. Summary of Test Method
Specific precautionary statements are given in 7.1.5, 8.3, and
4.1 The thermal-optical analyzer has been described previ-
12.12.2.
ously (1-5). Design improvements have been made over time,
1.10 This international standard was developed in accor-
but the operation principle remains unchanged. OC-EC quan-
dance with internationally recognized principles on standard-
tificationisaccomplishedthroughtemperatureandatmosphere
ization established in the Decision on Principles for the
control. In addition, the analyzer is equipped with an optical
Development of International Standards, Guides and Recom-
feature that corrects for the char formed during the analysis of
mendations issued by the World Trade Organization Technical
somematerials.Opticalcorrectionismadewithapulseddiode
Barriers to Trade (TBT) Committee.
laser and photodetector that permit continuous monitoring of
the filter transmittance/reflectance.
2. Referenced Documents
4.2 The main instrument components (transmittance instru-
2.1 ASTM Standards:
ment) are illustrated in Fig. 1. The instrument output, called a
D1356Terminology Relating to Sampling and Analysis of
thermogram, is shown in Fig. 2. For analysis, a known area
Atmospheres
(normally 1.5 cm ) of the quartz-fiber filter sample is removed
with a sharp metal punch. Quartz-fiber filters are required
3. Terminology
because temperatures in excess of 850°C are employed. The
3.1 Definitions—For definitions of terms used in this test
portionisinsertedintothesampleoven,andtheovenistightly
method, refer to Terminology D1356.
sealed. The analysis proceeds in inert and oxidizing atmo-
3.1.1 limit of detection (LOD), n—a value for which ex-
spheres. First, OC (and carbonate, if present) is removed in
ceedence by measured mass indicates the presence of a
helium as the temperature is stepped to a preset maximum
substance at given false-positive rate: 3 × estimated standard
(usually ≥850°C in NMAM 5040; see 4.4). Evolved carbon is
deviation of estimated mass of a blank.
catalytically oxidized to CO in a bed of granular MnO . The
2 2
CO is then reduced to CH in a Ni/firebrick methanator, and
3.2 Definitions of Terms Specific to This Standard: 2 4
CH isquantifiedbya FID.Next,thesampleoventemperature
3.2.1 elemental carbon (EC), n—excluding char, light- 4
is lowered, an oxygen-helium mix (2% oxygen after dilution
absorbing carbon that is not removed from a filter sample
of the 10% oxygen in helium supply) is introduced, and the
heated to 870°C in an inert atmosphere.
temperature is increased to 900°C (or higher) to remove
3.2.2 organic carbon (OC), n—carbon volatilized in helium
(oxidize) the remaining carbon, some or all of which is EC,
while heating a quartz-fiber filter sample to 870°C. Includes
dependingonwhethercharisformedduringthefirstpartofthe
carbonates, if present, unless quantified separately. Also in-
analysis (a char correction is made if so). At the end of each
cludes char formed during pyrolysis of some materials.
analysis, calibration is made through automatic injection of a
3.2.3 thermogram, n—digitized output signal of thermal-
fixed volume of methane.
optical instrument. Shows detector and filter transmittance
4.3 Some samples contain components (for example, ciga-
signals at different temperatures in nonoxidizing and oxidizing
rette and wood smokes) that carbonize (convert to carbon) to
atmospheres.
form char in helium during the first part of the analysis. Like
3.2.4 total carbon (TC), n—sum of organic and elemental
EC typical of fine particle pollution, char strongly absorbs
carbon.
light, particularly in the red/infrared region. The char formed
3.3 Symbols and Abbreviations:
through pyrolysis (thermal decomposition) of these compo-
3.3.1 DPM—diesel particulate matter
nents causes the filter transmittance/reflectance to decrease.
Charring can begin at 300°C; the process may continue until
3.3.2 LOD (µg/cm )—limit of detection:3×s
w
the maximum temperature is reached. After OC removal, an
3.3.3 s (µg/cm )—estimate of σ
w w
oxygen-helium mix is introduced to effect combustion of
residual carbon, which includes char and any EC originally
present. As oxygen enters the oven, light-absorbing carbon is
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
oxidized and a concurrent increase in filter transmittance
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
occurs. The split (vertical line prior to EC peak in Fig. 2)
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. between OC and EC is assigned when the initial (baseline)
D6877 − 13 (2018)
FIG. 1 Schematic of Thermal-Optical Instrument (V = Valve) for Determination of Organic and Elemental Carbon in DPM and Other Car-
bonaceous Aerosols
NOTE 1—PC is pyrolytically generated carbon (char). Final peak is methane calibration peak. Carbon sources: pulverized beet pulp, rock dust
(carbonate), and diesel particulate matter.
NOTE 2—In the comparative test reported by Birch (6), participants used different maximum temperatures in helium (5). The actual maximum ranged
from about 850–900°C. NMAM 5040 specifies 870°C, which is near the middle of this range.
FIG. 2 Thermogram for Filter Sample Containing OC, Carbonate (CC), and EC
valueofthefiltertransmittanceisreached.Allcarbonremoved initial (baseline) value during the first part of the analysis (in
before the OC-EC split is considered organic; that removed helium), the OC-EC split is automatically assigned earlier, in
afterthesplitisconsideredelemental.Ifnocharisformed,the helium mode (5). A lower preset maximum (for example,
split is assigned prior to removal of EC. Ordinarily, the split is 650°C)canbeusedtoreduceEC/charlossinheliumsothatthe
assigned in the oxidative mode of the analysis. split occurs during the oxidative mode (5).
4.4 Occasionally, the sample EC (along with any char 4.5 OC and EC results are reported in units µg per cm of
formed) is lost during the fourth temperature step in helium. filter deposit. The total OC and EC on the filter are calculated
Loss of EC in helium is uncommon but sometimes occurs, bymultiplyingthereportedvaluesbythe depositarea(slightly
possiblyduetooxidantsinthesample.Incaseswhenlossisto less than the filter area). A homogeneous deposit is assumed.
an extent where the filter transmittance reaches/exceeds its The TC in the sample is the sum of OC and EC. If carbonate
D6877 − 13 (2018)
ispresent,thecarboninitisquantifiedas OCunlesscorrection selective measure of the diesel-source OC. It also provides a
is made. Additional details about carbonates are given in a better measure of the diesel-source EC if the dust contains EC
following section. (for example, carbon black, coal), which is less common. A
finely ground sample of the bulk material can be analyzed to
5. Significance and Use
determinewhetheradustposespotentialinterference.Depend-
ing on the dust concentration, size distribution, and target
5.1 The test method supports previously proposed occupa-
analyte (EC or TC), an impactor/cyclone may be required.
tional exposure standards (7, 8) for DPM.A DPM exposure
Additional details can be found elsewhere (5). Some OC
limit has since been promulgated for metal and nonmetal
interferences cannot be excluded on the basis of size (for
mines, but there currently are no limits for general occupa-
example, cigarette smoke and other combustion aerosols,
tional settings (a proposed limit (7) was withdrawn from the
condensation aerosol).
ACGIHNoticeofIntendedChanges(NIC)listin2003).Inthe
United States alone, over a million workers are occupationally
6.3 In metal and nonmetal mines, the Mine Safety and
exposed (9). An exposure standard for mines is especially
Health Administration (MSHA) recommended use of a spe-
important because miners’ exposures are often quite high.
cialized impactor (with cyclone) to minimize collection of
NIOSH (9), the International Agency for Research on Cancer
carbonates and other carbonaceous dusts (6, 8, 27-31).
(10) (IARC), the World Health Organization (11) (WHO), the
6.4 For measurement of diesel-source EC in coal mines, an
Calif
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