DIESEL PARTICULATE MATTER 5040

(as Elemental Carbon)

C AW: 12.01 CAS: none RTECS: none

METHOD: 5040: Issue 3 EVALUATION: FULL Issue 1: 15 May 1996

Issue 3: 15 March 2003

OSHA : no PEL PROPERTIES: nonvolatile solid

NIOSH: no REL
ACGIH: 20 :g/m as elemental carbon (proposed [1])
3

SYNONYMS (related terms): diesel particulate matter, diesel exhaust, diesel soot, diesel emissions

SAMPLING MEASUREMENT

SAMPLER: FILTER: quartz-fiber, 37-mm; size- TECHNIQUE: Thermal-optical analysis; flame ionization
selective sampler may be required [2]. detector (FID)

FLOW RATE: 2 to 4 L/min (typical) ANALYTE: Elemental carbon (EC). Total carbon
is determined, but an EC exposure
VOL-MIN: 142 L @ 40 :g/m3 marker was proposed. See [2] for
-MAX: 19 m3 (for filter load of ~ 90 :g/cm2 ) details.

SHIPMENT: Routine FILTER

PUNCH SIZE: 1.5 cm2 (or other [2])
SAMPLE
STABILITY: Stable CALIBRATION: Methane injection

BLANKS: 2 to 10 field blanks per set RANGE: 1 to 105 :g per filter portion (See also
[2].)

ACCURACY ESTIMATED LOD: 0.3 :g per filter portion

RANGE STUDIED: 23 to 240 :g/m3 (See also ref. [2].) PRECISION ( þ r ): 0.19 @ 1 :g C,
0.01 @ 10 to 72 :g C
BIAS: None (See also ref. [2].)

OVERALL
PRECISION ( Ö r T ): 0.085 at 23 :g/m3 (See also ref. [2].)

ACCURACY: ± 16.7% at 23 :g/m3 (See also ref. [2].)

APPLICABILITY: The working range is approximately 6 to 630 :g/m3 , with an LOD of ~ 2 :g/m3 for a 960-L air sample collected
on a 37-mm filter with a 1.5 cm2 punch from the sample filter. If a lower LOD is desired, a larger sample volume and/or 25-mm filter
may be used (e.g., a 1920-L sample on 25-mm filter gives an LOD of 0.4 :g/m3 ). The split between organic carbon (OC) and EC
may be inaccurate if the sample transmittance is too low. The EC loading at which this occurs depends on laser intensity. In general,
the OC-EC split may be inaccurate when EC loadings are above 20 :g/cm2 . High loadings can give low (and variable) EC results
because the transmittance remains low and relatively constant until some of the EC is oxidized. The split should be reassigned (prior
to EC peak) in such cases [3]. An upper EC limit of 800 :g/m3 (90 :g/cm2 ) can be determined.

INTERFERENCES: Total carbon (as OC and EC) is determined by the method, but EC was recommended as a measure of
workplace exposure because OC interferences may be present [2, 3]. Cigarette smoke and carbonates ordinarily do not interfere
in the EC determination. Less than 1% of the carbon in cigarette smoke is elemental. If heavy loadings of carbonate are anticipated,
a size-selective sampler (impactor and/or cyclone) should be used [2]. For measurement of diesel-source EC in coal mines, a
cyclone and impactor with a submicrometer cutpoint are required to minimize collection of coal dust. A cyclone and/or impactor may
be necessary in other workplaces if EC-containing dusts are present.

OTHER METHODS: Other methods for determination of EC and OC have been employed, but these are not equivalent to the
method described herein. Information on other methods is summarized elsewhere [2].

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition

 ELEMENTAL CARBON (DIESEL PARTICULATE): METHOD 5040, Issue 3, dated 15 March 2003 - Page 2 of 5

REAGENTS: EQUIPMENT:

1. A qu eo us so lu tio ns of re ag en t g ra de (99+ % ) 1. Sam pler: Quartz-fiber filter, precleaned (in low

sucrose, 0.1 to 3 mg C per m L solution. temperature asher 2 to 3 h, or muffle furnace
Ensure filter spike loading range brackets that for 1 to 2 h at ~ 800 °C), 37-mm , in a 3-piece
of samples. cassette with filter support (stainless steel
2. Ultra pure H 20, Type I, or equiva lent. screen, cellulose pad, or a second quartz filter).
3. UHP helium (99.999%), scrubber also Altern ative sam plers m ay be requ ired in dusty
required for removal of oxygen. environments. See ref. [2] for details.
4. Hydrogen, purified (99.995%), cylinder or NOT E 1: High purity, high efficiency, binder-
hydrogen generator source. free quartz-fiber filters must be used
5. Ultra Zero air (low hydrocarbon). (e.g., Pall Gelman Sciences Pallflex
6. 10% oxygen in helium balance, both gases Tissue qua rtz 250 0Q AT -UP .
UHP, certified mix. Precleaned filters are available from
7. 5% m ethane in helium balance, both gases several laboratories. Filters also can
UHP, certified mix. be p urchas ed a nd c leaned in-hou se.
Filte rs should be cleaned in a m uffle
furnace operated at 800-900 oC for 1-
2 ho urs. Che ck (ana lyze) filters to
ens ure rem oval of OC conta m inants.
A shorter cleaning period may be
effective. O C res ults im m ediate ly
after clean ing sh ould be below 0.1
µg/cm 2. OC vap ors readily adsorb
onto clean filters. Even when stored
in closed containers, OC loadings
may range from 0.5 µg/cm 2 after
several weeks.
NOT E 2: Cellulose supports give higher O C
blanks than screen s an d qu artz
filters. Bottom quartz filters can be
used to correc t for adsorbed vap or;
see ref. [2].
2. Personal sampling pump with flexible tubing.
3. Th erm al-optical analyzer; se e ref. [2].
4. Metal punch for removal of 1.5 cm 2 rectangular
portion of filter.
NOTE: A sm aller portion (e.g., taken with cork
borer) may be used, but the area must
be large enough to accomm odate the
entire laser beam (i.e., be am should
pass through the sample, not around
it). The area of the portion must be
accurately k nown , and the sam ple
must be carefully positioned (the filter
transmittance will decrease
dram atic ally when the sam ple is
properly aligned). A filter portion $0.5
cm 2 with diameter or width # 1 cm is
recomm ended.
5. Syringe, 10-:L.
6. Alum inum foil.
7. Needle (for lifting filter punch portion).
8. Forceps
9. Volumetric flasks, Class A.
10. Analytical balance.

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition

 ELEMENTAL CARBON (DIESEL PARTICULATE): METHOD 5040, Issue 3, dated 15 March 2003 - Page 3 of 5

SPECIAL PRECAUTIONS: Hydrogen is a flamm able gas. Users must be familiar with the proper use
of flamm able and nonflamm able gases, cylinders, and regulators. According to the instrument
manufacturer, the instrument is a Class I Laser Product. This designation means there is no laser
radiation exposure during normal operation. W eakly scattered laser light is visible during operation, but
does not pose a hazard to the user. The internal laser source is a Class IIIb product, which poses a
possible hazard to the eye if viewed d irectly or from a m irror-like surface (i.e., specular reflections).
Class IIIb lasers normally do not produce a hazardous diffuse reflection. Repairs to the optical system,
and other repairs requiring removal of the instrument housing, should be performed only by a qualified
service techn ician.

SAMPLING:

1. Calibrate each personal sampling pump with a representative sampler in line.

NOTE: Both ope n- an d clos ed-face d ca sse ttes have bee n us ed. Both configurations generally give even
deposits. At high er flow rates (e.g., 4 L/m in), sm all spots o ccasionally have been observed in
the cente r of the filters when closed-faced cassettes are used. This m ate rial likely consisted of
impacted diesel agglom erate s and/or non-diesel particulate m atte r. EC res ults for m ultiple
portions of the filters were in good agreement, so the spots had little analytical impact. Other
sam plers also can be used (see ref. [2]) provided an even deposit of diesel particulate results.
An even deposit is necess ary because the s am ple portion analyzed m ust be represe ntative of
the entire d epo sit. If the deposit is not homogeneous, the entire sample must be analyzed. An
impactor/cyclone may be needed in some cases. [2]
2. Attach sampler outlet to personal sampling pump with flexible tubing.
3. Sa m ple at an acc urate ly known flow rate. Typical rates are 2-4 L/min (note: Lower flows (e.g., 1 L/min)
have bee n used in m ines to prevent overloading).
4. After sampling, replace top piece of cassette, if removed, and pack securely for shipment to laboratory.
NOTE: Diesel particulate samp les from occupa tional settings generally do not require refrigerated
shipment unless there is potential for exposu re to elevated temp eratures (that is, well above
collection temperature). Filter samples normally are stable under laboratory conditions. Some
OC loss may occur over time if sam ples con tain O C from other sou rces (for exa m ple, cigarette
sm oke). Sorption of O C vapor after sam ple collection has not occurred, even with samples
having high (e.g ., 80% ) EC con tent.

SAMPLE PREPARATION:

5. Place sample filter on a freshly cleaned aluminum foil surface. Isopropyl alcohol or acetone can be
use d to clean the fo il. Allow residual solven t to vaporize fro m the surface p rior to use. P unc h ou t a
representative portion of the filter. Take care not to disturb deposited material and avoid hand contact
with sample. A needle inserted at an angle is useful for removal of the filter portion from the punch
body. Newer instruments have an externally mounted bracket to support the quartz sample holder
while the previous sample is removed and a new one is loaded. Through a hole in the side of the
sta ndard punch, a needle can be used to push the filter po rtion from the punch onto the sam ple
holder. Alternative approaches also can be used, depending on the user’s preference, as long as
con tam ination is avoided.

CALIBRATION AND QUALITY CONTRO L:

6. Analyze at least one rep licate sam ple. Fo r sets of up to 50 sam ples, replicate 10% of the sam ples.
Fo r sets over 50 sam ples, replicate 5% of the sam ples. If a filte r de posit appears uneven (this
should not be the case if the cassette is sealed pro perly), ta ke a second portion (step 5) for analysis
to check evenne ss o f dep osition.
NOTE: Precision of replicate analyses of a filter is usually better than 5% (1 to 3% is typical).

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition

 ELEMENTAL CARBON (DIESEL PARTICULATE): METHOD 5040, Issue 3, dated 15 March 2003 - Page 4 of 5

7. Analyze three quality control blind spikes and three analyst spikes to ensure that instrument
calibration is in control. Prepare spike as follows:
a. W ith 10-:L (or other) syringe, apply an aliquot of OC standard solution directly to filter portion taken
(step 5) from a precleaned filter. For best results, the precleaned filter punch should be cleaned
aga in in the s am ple oven p rior to applica tion of the aliquot.
NOTE: W ith sm all aliquots (e.g., # 10 :L), disperse standard solution over one end of filter
portion to ensure standard is in laser beam. To prevent possible solution loss to surface,
hold the portion off the surface. Larger volumes can easily penetrate to the underside of
the filter portion.
b. Allow wate r to eva pora te and an alyze spikes with sa m ples and blank s (steps 9 and 10 ).
NOTE: A pronounced decrease in filter transmittance during the first temperature step of the
analysis indicates water loss. Allow portions to dry longer if this occurs. Spiked punches
also can be dried in the oven, if desired. For quick drying, the ‘clean oven’ comm and on
the menu can be selected and canceled after about 4 seconds. The time allowed may
depend on instrument, but oven temperatures should be below 100 °C to avoid boiling the
solution. This approach is con venient and prevents p otential adsorption of organic vapors
in laboratory air.
8. De term ine instrum ent blank (results of ana lysis with fre shly clea ned filter portion ) for each sam ple se t.

MEASUREMENT:

9. Adjust analyzer settings according to manufacturer's recomm endations (see instrument operation manual
and background information in ref. [2]). Place sample portion into sample oven.
NOTE: F orm s of carbon that are difficult to oxidize (e.g., graphite) may require a longer period and
higher temperature during the oxidative mode to ensu re tha t all EC is removed (the EC peak
should never m erge with the calibra tion pe ak). Adju st time and tem pera ture a cco rdingly. A
m axim um tem pera ture a bove 94 0 °C sho uld no t be required.
10. Determine EC (and OC ) m ass , :g. Analyzer results are reported in units :g/cm 2 of C. The reported
values are normally based on a sample portion of about 1.5 cm 2, which is the area of the standard punch
provided by the manufacturer. If the portion area used differs from the value entered in the ocecpar.txt
file, m ultiply the result by 1.5 (or value in ocecpar.txt file) and divide the product by the actual area
analyze d to obtain the are a-correcte d re sult (i.e., reported re sult x 1.5/po rtion area = correcte d re sult in
:g/cm 2). This is m ost easily done in the data spreadsheet. Alternatively, the correct results will be obtained
with the data c alculation pro gram if the portion area is entered in the param ete r file (oc ecpar.txt), but th is
approac h is cum bersom e when punche s of different areas are used because correct results will not be
obta ined for all pu nch sizes.

CALCULATIONS:

11. Mu ltiply the repo rted (o r area-corrected ) EC resu lt (:g/cm 2 ) by filter deposit area, cm 2, (typically 8.5
cm 2 for a 3 7-m m filter) to ca lculate total m ass , :g, of EC on each filter samp le (W EC). Do the same for
the blanks an d calculate the m ass foun d in the average field blank (W b). The m ass of OC is calculated
similarly, but the mean O C field blank m ay underestimate the amount of OC contributed by adsorbed
vapor. A quartz filter placed beneath the sample filter can provide a better estimate of the adsorbed
OC . [2]
12. Calculate the EC concen tration (C EC) in the air volume sam pled, V (L):

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition

 ELEMENTAL CARBON (DIESEL PARTICULATE): METHOD 5040, Issue 3, dated 15 March 2003 - Page 5 of 5

EVALUATION OF METHOD:

Deta ils on the evaluation of this method are provided in a chapter of this NMAM Supplement. [2] The chapter
includes a summ ary of interlaboratory comparison work conducted since the initial publication of the method.
Background information and guidance on m ethod use, including sam pling requiremen ts, also are provided.
In general industry, 37-mm cassettes are no rm ally suitable for air s am pling, but there are ex cep tions. A
cyclone in series with an impactor having a submicrometer cutpoint must be used in coal mines, and the Mine
Safety and Health Administration (MSHA) has recomm ended use of a cyclone-impactor sampler in metal and
nonmetal m ines. [5 ] The im pacto r is c om m ercially available [6]. A size-selective sampler (either impactor
and/or cyclone) also may be required in other dusty environments [2], particularly if the dust is carbonaceous.
If a sample contains carbonate, the carbonate carbon (CC) will be quantified as OC. A carbonate-subtracted
result can be obta ined through acidificatio n of the sam ple portion or through separate integration of the
carbon ate peak [2] (note: Trona and other compounds containing sodium can etch the quartz oven wall at
elevated temperatures. Avoid spillage of these materials in the sample oven.) These procedures are described
in a Chap ter of th is Supplem ent. [2] The thermal-optical method is applicable to nonvolatile carbon species
(i.e., particulate OC, CC and EC). The method is not appropriate for volatile or semivolatiles, which require
sorben ts for efficient collection.

REFERENCES:

[1] AC GIH [2001]. Cincinnati, O H: Am erican C onference of Environm ental Industrial Hygienists. Diesel
Exhaust (Particulate and Particulate Adsorbed Com ponents), Draft TLV-TW A Docum ent, 2001.
NOTE: Recently, diesel exhaust has been taken off the ACGIH Notice of Intended Changes list. See
referenc e [2].
[2] NIOSH [2003]. Manual of Analytical Methods (NMAM). O’Connor PF, Schlecht, PC, Monitoring of Diesel
Particulate Exh aus t in the W ork place, Chap ter Q, Third Su pplem ent to NM AM , 4 th Edition, NIOSH,
Cinc innati, OH . DH HS (NIO SH ) Publication No. 2003-15 4.
[3] Birch, ME, C ary, RA [1996]. Elemental Carbon-based Method for Monitoring Occupational Exposures to
Pa rticulate D iesel Exhaust A erosol Sci T echnol 25:221-241.
[4] Birch, ME [1998]. Analysis of carb ona ceo us a eros ols: interlaboratory com parison, A nalyst, 123:851-857.
[5] Mine Safety and Health Adm inistration (MSH A) [20 01]. D epa rtm ent o f Labor, 30 CFR Part 57, Diesel
Particulate Matter Exposure of Underground Metal and Nonm etal Miners; Final Rule, Federal Register
Vol. 66, No. 13, January 19.
[6] SK C, E ight Sixty Three V alley View Road, E ighty Fo ur, PA 153 30.

METHOD WRITTEN BY:

M. Eileen Birch, Ph.D., NIOSH/DART

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition