-------
I
I
u
"3
S
VI
i a
a «~ .
«a|§£~
f Isl-lfi
.§8l!f 8°
•
t
•a -e a
SI
"J
S
n
e
IfaitHcff
MwjSi-)^«o2
CO
•
1
eo
s«
CO pj
^ is
S *C
2 ^
£J
2§
I §
a?
<*-
o
"S
CO
«
f d
I" I
O«O 2
s^ s
«- I l-
« ' Bj
ig tS o
eo w
a-i £
Th
of
Gl
Me
Lo
8 a a
!|l
X -3 S
o
>
"
o si x S y
o
•o
u
55
5
•o
s s 1 w
as «• « -a
ESS e
S S
0
1
« « 0
'
S «N
eg g
s
!
en
T3
O
&
—M
o a <
2-22
-------
Cellulose-fiber filters consist of a tightly-woven paper mat. These filters meet
requirements inmost categories with the exception of sampling efficiency and water vapor
artifacts. Sampling efficiencies below 50% in the sub-micrometer region have been observed
but these are highly dependent on the filter weave. These efficiencies are generally lower thai!
Jose required for reference sampling. Cellulose-fiber is hygroscopic and requires precise relative
humidity control in the filter processing environment to obtain accurate mass measurements This
substrate has low elemental blanks and is commonly used for elemental and ionic analyses of the
deposit, but it is not suitable for carbon analysis. Cellulose-fiber filters can be impregnated with
gas-adsorbing compounds and located behind more efficient particle-collecting filters This
allows gases such as sulfur dioxide, nitrogen dioxide, and ammonia to be measured with
suspended particles. The most commonly used cellulose-fiber filters are Whatman 41 and
Whatman 3 1ET.
Glass-fiber filters consist of a tightly-woven mat of borosilicate glass filaments These
falters meet requirements in most categories with the exception of artifact formation and blank
levels. Sampling efficiency is very high for all particle sizes. The high alkalinity of these
substrates causes sulfur dioxide, nitrogen oxides, and gaseous nitric acid to be adsorbed (Coutant
1977; Spicer and Schumacher, 1977), and they do not attain the reference method requirements'
i ^ ^ , leVdS f°r m°St dements °f ***** m togh and variable (Witz * „/
1983). Particulate nitrate and ammonium losses have been observed when these samples are
stored at room temperature for long periods, but this is also true of deposits on other filter media
.(Witz et al., 1990). Glassrfiber filters adsorb organic carbon vapors which are measured as
Peculate i carbon during analysis. The most commonly used glass-fiber filters are Gelman Type
A/E and Whatman EP2000.
«. Tefl^-coated glass-fiber filters impregnate a Teflon slurry onto a loosely-woven glass-
fiber mat These filters meet requirements in all categories except blank element and carbon
levels. Though a small nitric acid artifact has been observed (Mueller et al., 1983) it is tolerable
in most situations. These filters are excellent for ion analyses but not for carbon analyses owing
TX*OHI20 aC°a ^ ^ COmmOnly USed Tefloir-c<*ted glass-fiber filters are Pallflex
Teflon-membrane filters consist of a porous Teflon sheet which is either stretched across
a plastic ring or supported by a loosely-woven Teflon mat. These filters meet requirements in
all categories except flow resistance and carbon blank levels. Because of their low porosity it
is not usually possible to attain the flow rates needed by the size-selective inlets in high-volume
sampling, though it is possible to obtain flow rates required for low-volume and medium-volume
JhTfiit, t f!^ ^/ma!vzed for carbon by thermal-methods because of its presence in
fee filter material, though they have very low blank levels for ions and elements. Most non-
destructive multi-elemental analysis methods use Teflon-membrane filters. The deposit of
pjrtides on the filter surface makes these substrates especially amenable to x-ray fluorescence
CXRF) and proton induced x-ray emission (PIXE) analyses. Gelman 1.0, 2.0, and 3.0 urn pore
size Teflon-membrane filters, which are made of polytetrafluoroethylene (PTFE) Teflon stretched
across a.polymethylpentane ring, are the most commonly used Teflon-membrane filters. Gelman
2-23
-------
Zefluor filters consist of PIPE Teflon mounted on a woven PTFE mat. The Zefluor filters are
. less desirable because their larger mass density decreases XKF and PIXE sensitivity, and because
the similar appearance of both sides often results in them being mounted upside down with the
particles drawn through the mat rather than onto the surface of the membrane.
Etched polycarbonate-membrane filters are constructed from a thin polycarbonate sheet
through which pores of uniform diameter have been produced by radioactive particle penetration
and chemical etching. These filters have low sampling efficiencies (<80%), even for small pore
sizes (Liu and Lee, 1976; Buzzard and Bell, 1980). This low efficiency is used as an advantage
when making size-specific measurements. Polycarbonate-membrane filters have low elemental
blank levels, except for bromine, and are appropriate for elemental and ion analysis. They are
the best filter media for single particle analysis by electron microscopy, but they cannot be
submitted to thermal carbon analysis owing to their composition. The filters hold an electrostatic
charge which influences mass measurements unless substantial effort is invested in discharging
them with a small radioactive source (Engelbrecht et al, 1980). Electrostatic discharging is good
practice for all filter media, even though others do not retain as much charge as the Nuclepore
membranes. The Nuclepore 8.0 urn and 0.4 urn filters are most commonly used in ambient
aerosol sampling. While the 0.2 urn pore size filter provides a higher sampling effectiveness, its
Higher flow resistance requires excessive vacuum for a reasonable flow rate.
Quartz-fiber filters consist of a tightly-woven mat of quartz filaments. These filters meet
requirements inmost categories and have artifact properties which are significantly lower than
those for glass-fiber filters, though quartz substrates adsorb hydrocarbon gases during sampling
(Eatough et al, 1990; McDow and Huntzicker, 1990). They should be baked at ~900°C prior to
sampling to remove adsorbed organic vapors. • Blank levels are high and variable for several
elements (especially aluminum and silicon), though newer formulations are cleaner than earlier
nf^f0^' ^^.^^y^edfor ion and carbon analyses. The greatest drawback
of quartz-fiber filters i is their fragility; they require extremely careful handling for accurate mass
measurements. The Whatinan QM/A quartz-fiber filter contains a 5% boroskate glass binder
which minimizes its friability while still attaining the reference method alkalinity standard This
filter is often used in high-volume PM10 samplers for mass measurements. Quartz-fiber filters
S?« 1°. I K SUlfkt! f d1nitrate ™^™> carbon "ndyata, and limited elemental analysis
when lots have been tested for background contaminants prior to sampling. The manufacturer
does not test these for Unk -levels, and many manufacturers contain LeJ£Zu£^
the matenals being sought for analysis. The Pallflex 2500 QAT-UP filter is jpure quartz and
undergoes a distilled water washing (thus the "UP", or "ultra-pure" designation). These filters
have low blank levels, but they are very brittle and flakes are often removed from them when
they are placed in a sampler filter holder. This- flaking makes these filters unsuitable for mass
analysis unless especially gentle handling is implemented to minimize flaking.
Nylon-membrane filters consist of thin sheets of porous nylon. They are used almost
S Ss? Its C±Cti°t °f ^ ^ tSn SeC°nd^ PartiC"6S « ^"nenSo3
2hSj5T?-ff originally manufactured for this purpose, however, and there is a
substantial difference among the properties of filters from different manufacturers. Nylon!
2-24
-------
membrane filters have high flow resistance, which increases rapidly with filter loading These
filters passively adsorb nitric acid, and their blank nitrate levels can be high, depending on how
long they have been exposed to an acid-rich environment They should be washed in a sodium
bi-carbonate solution followed by distilled deionized water (Chow et al., 1990a- 1993a- Watson
et al., 1990b, 1991d) prior to use in the field. Nylon-membrane filters may also adsorb small
quantities of sulfur dioxide (Japar and Brachaczek, 1984) which may interfere with sulfate
measurements. Schleicher and Schuell Grade 66 and Gelrrian Nylasorb are the nylon-membrane
filters most commonly used for ambient air sampling.
As noted above, blank levels must be low when filters are to be submitted to chemical
analysis. Even batches of ultra-pure filters have been found to be contaminated and a sample
from each batch of filters (1 out of 50 to 100 filters) should be submitted to the intended
chemical analyses prior to use in a field study. Though not reported in the literature, recent
studies have found elevated levels of lead, calcium, and nitrate in batches of blank teflon-
membrane filters. Filters may also become contaminated in the field or during handling by
passive deposition before and after sampling starts. Dynamic field blanks can be placed in the
field under situations similar to that of the sampled filter. These are then analyzed so average
blank levels can be subtracted from the chemical measurement.
2.4 Filter Holders
Filter are protected from contamination prior to, during, and after sampling by placing the
filter in a filter holder. These holders must: 1) mate to-the sampler and to the flow system
without leaks; 2) be composed of inert materials which do not adsorb acidic gases- 3) allow a
uniformly distributed deposit to be collected; 4) have a low pressure drop across the empty
holder; 5) accommodate the sizes of commonly available air sampling filters (e.g. 37 or 47 mm)-
and 6) be durable and reasonably priced.
Most filter holders are configured as in-line or open-faced. In-line holders often
concentrate the particles in the center of the substrate, and this will bias the results if analyses
are performed on portions of the filter., Tombach et al. (1987) and Fujita and Collins (1989)
show differences as high as 600% between chemical measurements in the middle and at the
edges of filters sampled with in-line filter holders. Open-faced filter holders are a better choice
for ambient aerosol sampling systems. All PM10 reference samples use open-face filter holders
iSSbTfi i ?J !h°WS^e
-------
inlet Tliis cartridge is optional for mass measurements, where the filter is often changed with
bare hands in the field. This cartridge is essential when samples are to be submitted to chemical
analyses to prevent contamination by body oils and dirt The cartridge should be loaded and
unloaded in a clean indoor work area using gloved hands.
The Gehnan stainless steel filter holder accommodates 28 and 47 mm filters and though
it has an open-faced adapter, it is sometimes used with an in-line coupler. As noted above this
in4uie holder results in a spot in the center of the filter. Since these filter holders are expensive,
they are often loaded and unloaded in the field which increases the potential for contamination.
The Nuclepore polycarbonate plastic filter holders accommodate 25, 37, and 47 mm
diameter filters. Since the cost of these filter holders is modest it is feasible to have a sufficient
number of them such that filters can be loaded in the laboratory for transport to the field These
holders can be modifiecTby widening the outlet hole to reduce flow resistance, using multiple
extender sections for filter stacking, and replacing the rubber O-ring with a Viton O ring to
minimize carbon adsorption from the rubber.
The Savfflex PFA Teflon 47 mm filter holder is made of injection molded PFA Teflon
which was previously noted as having the least inclination to adsorb nitric acid These fi£
a eXtende" SeCti°n (Call6d a ~P**0 w*ch can be mated to a sampler
a retamer ^ SeVeral ^ and ** ™ZS can be stacked within the
„ « ffi « * ?• ^ C°St °f ttoe filter holder combinations is low enough to
allow a sufficient quantity to be purchased for laboratory loading.
37
P°Iyeth^ene f lter holders « *»»&** rings which accommodate
y ™ exclusively "** ^ Sierra-Andersen 240 series of virtual
P , "" mexPensive "d can be loaded in the laboratory and placed in
plastic Petn dishes for shipment to field sites. pwteu m
Flow Measurement and Control
accur^measure of fl»"«fr Posing through each filter is needed to obtain accurate
concentration measurements for PM10. Though a filter may be very good for chem S
analysis, it may provide too much flow resistance to allow a sampler to operate properly
**? 214° r Teflon-memb^ fibers are available L ^Wg
c "tT^: y PrOVlde SUCh a ^ PreSSUie ^ *at no more than 20
can pass trough them using the standard high-volume blower motor. This low flow
the cut-point of the inlet such that the sample taken is no longer representative f of PM*
a
p i, * I?*88? thr°Ugh ^ samPling substrates by means of a vacuum created
Rubow and Furtado (1989) describe commercially available air pumps,
operating principles. Rogers et al (1989) have found that a 3/4
2-26
-------
is sufficient to draw in excess of 120 fi/min through a 47 mm Teflon-membrane filter Smaller
ug/m pumps can be used for lower flow rates and filter media with lower resistances.
Regardless of the.pump used, the quantity of air per unit time must be precisely measured
and ^controlled to determine particle concentrations and to maintain the size-selective properties
of the sampling inlet. Four general methods are used in particle sampling systems: 1) manual
volumetric; 2) automatic mass; 3) differential pressure volumetric; and 4) critical orifice
volumetric flow controls.
Manual control is accomplished when the operator initializes a setting, such as a valve
adjustment, and then relies on the known and constant functioning of sampler components such
as pumps and tubing, to maintain flows within specifications. Flow rates which are set manually
change over a sampling period as the collection substrate" loads up and presents a higher flow
resistance. For most filter loadings (<200 ug/m3), the flow will not change by more than 10%
during sampling, and the average of flow rates taken before and after sampling provides an
accurate estimate of the actual flow. * PIWVHK* dn
Automatic mass flow controllers use thermal anemometers to measure the heat transfer
between two points in the gas stream. To a first approximation, the heat transfer is proportional
to the flux of gas molecules between the two points, and hence the mass flow controller is able
to sense the flux of mass. Mass flow controllers require compensating circuitry to avoid errors
due to absolute temperature variations of the gas itself as well as the controller sensing probe
Wedding (1985) estimates potential differences in excess of 10% between mass and volumetric
measurements of the same flow rates, depending on temperature and pressure variations.
Differential pressure volumetric flow control maintains constant pressure across an orifice
(usually a valve which can be adjusted for a-specified flow rate) by a diaphragm-controlled valve
ocated between the filter and the orifice (Chow «r a/., 1993a). The diaphragm is controlled by
tiie pressure between the orifice and the pump. When this pressure. increases (as it does when
filters load up), the diaphragm opens the valve and allows more air to pass.
Wh™ t °f E SmaU CilCular °penmS between «« filter ^d *e pump.
When the pressure at the minimum flow area downstream of the orifice is less than 53% of the
SSJT P?SSUre' ^ /ir VdOCity ^^ *" Speed °f SOUnd and * wil1 remain constant,
regardless of increased flow resistance. Critical orifices provide very stable flow rates but they
require large pumps and low flow rates (typically less than 20 fi/min with commonly 'available
HS h TV , ^h PLessure di^rences. Wedding et al. (1987) have developed a
critical throat which uses a difruser arrangement to allow recovery of over 90% of the energy
*™^T?y^ed% baCk PreSSUre behlnd a crftad °rifi- ™- des "
flow rates to be obtained with a given pump than does a simple critical orifice
2-27
-------
2.6 PM10 Sampling Systems for Chemical Analysis
Tables 2-1 and 2-2 identify several reference and non-reference sampling systems which
can be applied to PM10 sampling intended for chemical analysis. Rubow and Furtado (1989)
Perry (1989), and Bering (1989) also describe commercially-available systems for ambient
aerosol sampling. The most widely used of these are the high-volume PM10 samplers
manufactured by Graseby-Andersen (formerly Sierra-Andersen) and Wedding & Associates that
are designated reference methods for .the PM10 NAAQS. These samplers use a low-pressure
blower to draw air through 20.32 cm x 25.40 cm fiber filters. The peaked roof dust cover which
wa^ formerly used to measure TSP is replaced with one of the high volume inlets specified in
Table 2-3. Procedures for these samplers are well established (e.g., Watson et al 1989a) and
mass concentration from high-volume sampling with PM10 inlets at over 2,000 sites within the
U.S. is the most commonly available measurement. As noted above, frequent inlet cleaning is
necessary for accurate size sampling by these units, and filters must be carefully handled if
chemical analysis is anticipated. Whatman QM/A quartz-fiber filters which have been submitted
to acceptance testing can be used in these samplers for most chemical analyses. The materials
m these filters contain large amounts of sodium, aluminum, and silicon, so these species cannot
be measured with this system. The thickness of the quartz-fiber filter also raises the background
in x-ray fluorescence analysis, thereby decreasing the sensitivity of these analyses. Several
elements which might be helpful in identifying sources are often below detection limits on these
filters, while they can be measured with high sensitivity from a Teflon-membrane filter High-
volume PM10 samplers are commercially available in a number of configurations from Graseby-
Andersen and Wedding & Associates.
The Graseby-Andersen low-volume dichotomous sampler is also commercially available
f6^ ence/amPIer' ™* ** "nit is often used with appropriate filter media when
ft '°™ and,Carb°n ^f68 m desked- ™s ^ampler uses a virtual impactor to
separate the PM^ and coarse particle size fractions. Flow rates are controlled by a differential
pressure regulator. Ten percent of the PM2.5 particles are sampled on the coarse particle filters
^1™ t T rS^ ^^ ^r and Ryan' 1983) t0 *° coarse P^16 measurements to
compensate for the difference John et al. (1988) describe how dichotomous samplers can be
SS^I? ? , Sampl?lg- ^ Met and Virtual ****»• should be ^assembled and
toougbly cleaned on a regular schedule. The virtual impactor can be assembled in a reverse
orientation, with the impactor jet over the PU^ filter rather than over the coarse particle filter
and care must be taken to correctly re-assemble this unit. When two or more dichotomous
iSe r nurX00?^ **£* filtef materiaIS Can bC n"d fa each «* to accornm0orte J
larger number of analyses. These samplers have been applied to PM10 source apportionment
"
r , oo
TX (Stevens et al, 1979); St Louis, MO and Elkaman, TN (Dzubay, 1980); Charleston
enVer' C° (Helsler Stal> 1980a' 1980b>' Buffalo,NY, E %£
(Ch°W et al" 1981; Watson et < 1981a); East Halena MT (Houck
ho A CBkwdC 3t *• 1982b); She^oah Valley VA (SteveL ef J. ^984)
Phoenix, AZ (Chow et al., 1991a); Tucson, AZ (Chow et al., 1991b; 1992a)- Tacoma WA
(Conner and Stevens, 1991); and Southern Ontario, Canada (Conner et al., 1993?' Ma^
2-28
-------
are operated with Teflon-membrane filters for mass and elemental analysis to assess
concentrations of toxic metals near major industries and remediation sites.
The sequential filter sampler (SFS) equipped with the SA-254 inlet became a reference
method under application from the State of Oregon. The SFS was originally designed in the late
1970s for use in the SUlfate Regional Experiment (SURE, Mueller et al., 1983) and the Portland
Aerosol Characterization Study (PACS, Watson, 1979) and has been applied in over a dozen
subsequent studies related to PM10 and visibility impairment The SFS consists of an aluminum
plenum to which the PM10 inlet is attached. Up to 12 sampling ports within the plenum are
controlled by solenoid valves which divert flow from one channel to the next by means of a
programmable timer. These ports accept filters which have been pre-loaded into open-faced
47 mm Nuclepore filter holders. The sample flow can be divided for simultaneous collection on
two or more filter media. A differential pressure volumetric flow controller splits the flow
between filters and maintains a constant flow rate despite filter loading. The State of Oregon
sought and obtained reference status for the SFS because it desired two filter media taken
simultaneously for different-chemical analysis and because it needed to take multiple sequential
samples without having to send someone to the site for frequent sample changing (Federal
Register, 1987i). The SFS is especially useful when less than 24-hour average samples are
sought. These samples are useful for distinguishing between sources with' similar chemical
profiles. For example, chemical profiles for residential wood combustion and for agricultural
burning may be chemical indistinguishable, but agricultural burning contributions occur during
daylight hours while the majority of residential wood combustion contributions occur at night
Four- to six-hour average sampling intervals can be applied using the SFS to provide this
differentiation. The SFS has been applied to PM10 source apportionment studies which required
chemical analysis in Portland, OR (Cooper and Watson, 1979; Cooper et al 1979- Watson
1979) Medford, OR (DeCesar and Cooper, 1982a; 1982b), San Jose, CA (Chow et al. 1994a)
Santo Barbara County, CA (Countess, 1991), Reno, NV (Chow et al., 1988d; Watson et al
1988a)f Phoenix AZ (Chow et al, 1991a), Tucson, AZ (Chow et al., 1991b; 1992a), and Denver!
CO (Heisler et al, 1980a, 1988b; Watson et al., 1988b, 1988c, 1988d).
Two types of continuous monitors have achieved equivalence for PM10 monitoring with
hourly averages, the Tapered Element Oscillating Microbalance (TEOM) and the Beta
Attenuation Monitor (BAM). These monitors have potential for providing samples which can
be chemically analyzed.
The TEOM (Patoshnick and Rupprecht, 1991; Rupprecht and Patashnick, 1992) uses a
hollow tapered tube. The wider end of the tube is fixed, while the narrow end oscillates in
response to an applied electric field. Air is drawn through an inlet, then through the filter and
me tapered tube and past a flow controller to the pump. The frequency of oscillation is a
function of the restoring force constant of the tapered element, the mass of the tapered element
the mass of the filter, and the mass of the aerosol particle deposit on the filter. The filter loading
efrm?nta ^ C^ge Which 1S ftect^d M-a chanSe * the frequency of oscillation of the tapered
element. The filter is only about 0.5 cm in diameter, and while it might be submitted to
2-29
-------
chemical analysis, the deposit on it is small and the analytical sensitivity would be low The
filter is usually changed weekly, so analysis for a 24-hour period would not be possible.
The TEOM draws air through this filter at a flow rate of 3 fl/min. This flow is extracted
from a total flow of 16.7 tfmin which is drawn through the SA-246 PM10 inlet. The make-up
air flow of 13.7 «/min can be diverted through one or more larger filters which can then be
submitted to chemical analysis after sampling. A sequential sampling feature, similar to that of
the SFS, could be added to allow sequential 24-hour filter samples, or every sixth day samples
to be taken between maintenance visits."
t T??M tapered element and sensinS head a16 thermostatted at user-programmable
values. The default value for these settings is 50'C, and this may cause mass measurements to
be lower than those measured with other reference samplers when PM10 contains volatile species
u f ^°mUm mtrate Jaid"certain organic carbon compounds. There is no inherent reason
why the TEOM cannot be thermostatted at an ambient temperature value, but temperatures which
change too rapully set up gradients in the tapered element, in turn changing its resonant
frequency.
Several Beta Attenuation Monitors have attained equivalence status for PM10 monitoring
as shown in Table 2-1. The attenuation of beta rays (moderately high energy elections) emitted
by a radioactive source when they pass through an aerosol filter deposit indicates the mass of that
filter deposit (e.g., Lilhenfeld and Dulchinos, 1972; Husar, 1974; Lillienfeld 1975- Macias and
Husar, 1976; Lillienfeld, 1979). The equivalent PM10 systems consist of . fiSt^tSfS
first drawn across the path between the beta emitter and a detector to measure blank attenuation
fcen across a sampling area in which ambient air is deposited on the tape, and finally across the
detection path to measure the combined attenuation of the filter and the deposit. The beta
attenuation is caused by the inelastic collision of the incident electrons with the orbital electrons
PleS ?r/neTS 16SS ^ l MeV' ^ filter SP°ts m approximately five
''. depending on the filter media used, these might be submitted to
^?un0t ^ been attemPted> however> and development is required before
these filter deposits should be considered for chemical characterization.
lv referfnce samplers cannot be adapted to every application which requires chemical
lysis of aerosol samples This is especially the case for source apportionment studies in areas
which have many fugitive ^dust sources and in areas with large contributions from secondary
aeroso formation Non-reference portable PM10 survey samplers have been developed to allow
spatiaUy-dense PM sampling networks to be deployed. These battery-powered units can™
SSS8 ^ ^ T311!^ d° ^ require comP'icated sampler siting efforts
th 't £ Thcy Can *6 Placed m ^ aromd fc**™ dust missions sources to help
™ T ******? c°ntnbutors to high PM10 caused by dust emissions. The portable
survey samplers consist of a pump, timer, tubing and fittings, removable filter holder, flow meter
impactor inlet, and battery pack. All of these are packaged in a plastic cylindrica encbsure
^^^heT T rd 18 fadtt' Iong- A C^ bale ^£^™o
be hung from a hook or hanging bracket. The sampler weighs about 15 pounds, most of which
2-30
-------
is due to the weight of the battery. It can be located and removed from elevated locations with
a grappling pole.
Removable 47 mm diameter Nuclepore filter holders used on this sampler are similar to
those used on the SFS. These are loaded with Teflon-membrane filters in the laboratory for
placement in the survey sampler. Two removable battery packs accompany each sampler so that
one may be charging while the other is sampling. Every time a filter is changed, the spent
battery is replaced with a recharged battery. At least six hours are needed to assure that batteries
are fully charged for the next sample.
is collected through an impactor inlet which contains a small amount of vacuum
grease on tiie impaction plate to trap the larger particles. .The 50% size-cut is preserved at 10
urn when the sampler's nominal flow rate is 5 fi/min. At this flow rate, the pump can operate
for over 24-hours with a fully-charged battery pack. Flow rates are determined with a calibrated
orifice or reference rotameter and verified by an in-line rotameter. An internal timer turns the
sampler on and off at pre-set times. Portable PM10 survey samplers have been used in recent
PM10 studies where emissions inventories were questionable. These include studies in El Paso
TX (Kemp 1990), Rubidoux, .CA (Zeldin, 1993), Omaha, NB (Kelly, 1991), Tacoma WA
(Schweiss, 1991), and Calexico, CA (Watson et al, 1991b).
rsrAn ****?* ^ Technology (CIT) and Southern California Air Quality Study
(SCAQS) samplers are of similar design, though inlets and flow rates differ. These samplers
Sft, S^Ce aPPortionment d^ set* in California's South Coast Air Basin (Solomon et al
1989; Wolff* al., 1991; Chow et al, 1992b; Solomon et al, 1992; Chow et al °994a 1994b'
Watson et al 1994b) and San Joaquin Valley (Chow et al, 1992C; 1993b) whtch wS
±T Lm^ "? SUbnUtted t0 reCept°r m°deImS- Both samPlers ™*e intended to
™T<^ A™"" ?' , SaSeCT ComP°nents of te aeroso1 on substrates for chemical analysis.
The SCAQS sampler took samples of 4- to 6-hours duration in Los Angeles and samples of 24-
hours duration, with lower flow rates, in the San Joaquin Valley. These systems draw air through
m S6rieS USing °elman ^^ fllter h°lders' ** use critical orifi'e
Aif °tetl a?°ve' ""I?1? denuder systems ^ designed for the measurement of acidic
^'?168^ T6 Tffk?W!0atod inlets' =»« Sow controllers, and in-line filter holders.
Nitnc acid, sulfur dioxide and other gases are adsorbed on the inner surfaces of the denuder inlet
and are removed by washing with an extraction solution (Stevens et al, 1990). These systems
are still undergoing. design changes. The system developed by Koutrakis et al. (1988) haTSn
applied in a nationwide network and has developed a degree of standardization. These systems
are useful when an examination of the chemistry of secondary particles and their precursors^
2-31
-------
2.7 Summary of Potential Sampling Artifacts
5 */- (1989b) and Countess et aL (1989) identify several sampling artifacts
including those discussed above, which can bias PM10 mass and chemical concentrations These
must be evaluated at the time of sampling if the integrity of the data is to be preserved The
potential artifacts and methods to avoid them are as follows:
• Passive Deposition of windblown dust on the filter prior to and following sampling
can positively bias PM10 measurements. For the peaked roof high-volume TSP
samplers (Federal Register, 1982; 1983), Rogers and Watson (1984) observed biases
of 10% to 15% for samples which were left in the sampler prior to and following the
sixth-day sampling schedule. This bias can be minimized by more frequent sample
changing and by the use of a "Sample Saver" ,- a device which covers the filter inside
. the sampler until the pump blower starts.
• Re-entrainment of large particles collected in the size-selective inlets can positively
bias PM10 measurements. As noted above, impaction inlets may become saturated
Frequent cleaning and greasing of inlet impaction surfaces will minimize re-
entrainment biases to chemical concentrations.
• Recirculation of pump exhaust can positively bias PM10 measurements Every flow
mover contains fragments of its brushes and armatures in the exhaust (Countess
1974). Most high vacuum pumps have outlet filters which should be installed and
changed at least quarterly. New pumps should be broken in for at least 48-hours
prior to taking the first sample, and the break-in filter should be replaced A piece
of clothes-dryer duct can be attached to the high-volume exhaust plenum to direct
pump exhaust away from the sampler inlet.
• Volumetric Flow Rate errors may be caused by infrequent performance tests and
calibrations of flow controllers. This is especially true of mass flow controllers for
which the set-pomt is temperature dependent. Wedding (1985) observed that flow
rate biases of 10% to 20% will occur when flow rate measurements are taken durine
fce winter using a calibration representative of summertime temperatures. Frequent
flow meter calibrations and performance tests are required to assure that the sampled
volume is accurate. '
• Artifact Formation, the adsorption of gases on filter media, was identified in Section
«, rf a ?£Slt^f Tf?r °ertain Chemical species' esPec*Hy for sulfate and nitrate
onglass-fiber filters. Use of quartz-fiber and Teflon-membrane filters is the best way
to minimize adsorption artifacts.
• Volatilization of chemical compounds which are in equilibrium with their
environment causes losses of ammonium nitrate and certain organic compounds The
most accurate monitoring of these species involves denuder-type °
2-32
-------
This bias can be minimized by removing samples soon after sampling, storing them
in sealed containers under refrigeration, and keeping them in coolers for transport
between the sampling site and laboratory.
* Particle Loss During Transport occurs when a large deposit is collected and
samples experience rough handling during movement from the field site to the
laboratory (Dzubay and Barbour, 1983). Shorter sample durations and lower flow
rates may be required in very polluted environments, especially those in which
fugitive dust is a large contributor, to prevent overloading. Careful handling during
transport will also minimise the loss of particles from the filter surface.
• Filter Contamination involves the presence of species to be measured in the filter
material, or their inadvertent introduction during filter.Jiandling prior to sampling
This can be minimized by acceptance testing of several blank filters from each
manufacturing lot to assure that blank levels are low. Subsequent contamination can
be reduced by loading and unloading filters in a laboratory setting, keeping them in
containers before and after sampling, and eliminating contact of the filters with bare
hands. . •
• Filter Integrity is compromised by handling which causes some of the filter to be
lost after the pre-exposure weighing. Teflon-membrane filters are the least likely to
lose filter mass, and these are best for gravimetric mass measurements. Careful
laboratory loading and unloading into filter holders also reduces over compression
which sometimes causes portions of the filter to adhere to the holder
2-33
-------
-------
3.0 PMM CHEMICAL ANALYSIS METHODS
Once filter deposits have been obtained by one or more sampling methods, they can be
submitted to a variety of chemical analyses. It is important that all the analyses to which the
sample might be submitted are identified prior to performing the first one, since some analyses
may invalidate the filter for subsequent analyses. Some methods are non-destructive and these
are preferred because they reserve the filter for other uses. Methods which require destruction
of the filter are best performed on a section of the filter rather than on the entire filter This
leaves a portion of the filter for other re-analyses or to be used as a quality control check on the
same analysis method. As noted in the previous section, filter sectioning requires that the
particles are homogeneously deposited across the filter surface so that the concentrations
measured on a portion of the filter can be extrapolated to the entire deposit area.
Table 3-1 compares minimum detectable concentrations achievable by different analysis
methods for elements, ions, organic carbon, and elemental carbon. The values in Table 3-1 are
nominal, and actual detection limits should be supplied by the laboratory performing the analysis
2Sor to sampling, so that sample durations and flow rates can be adjusted to acquire sufficient
samples for the intended analyses. The most common aerosol analyses can'be divided into the
categories of 1) mass, 2) elements, 3) water-soluble ions, and 4) organic and elemental carbon
Less common analytical methods which are applied to a small number of specially-taken samples
include Carbon-14 (Currie, 1982); organic compounds (Rogge etal., 1993a; 1993b); and single-
particle characterization (Cassuccio et al, 1989). The reader is referred to the cited references
for greater detail^on sampling and analysis methods for these highly-specialized methods.
3.1 Mass Measurement Methods
Particulate mass concentration is the most commonly made measurement on aerosol
samples. It is used to determine compliance with PM10 standards and to select certain samples
for more detailed, and more expensive, chemical analyses. As noted in Section 2 the beta
attenuation and inertial microbalance methods have been incorporated into in situ measurement
systems which acquire real-time mass measurements. Gravimetric analysis is used almost
exclusively to obtain mass measurements of filters in a laboratory environment. U S EPA
(1976) and Wateon et al. (1989a) have . published detailed procedures for mass analyses
associated with 20.32 cm x 25.40 cm fiber filters, but the guidance for other types of filters
used for chemical analyses is less well documented. .
Gravimetry measures the net mass on a filter by weighing the filter before and after
sampling with a balance in a temperature- and relative humidity-controlled environment PM,n
reference me Jods require that filters be equilibrated for 24 hours at a constant (SSSn ±5%
**
to
to
t0 mmimize ** n
-------
Table 3-1
Analytical measurement specifications for air filter samples
Minimum TWor*tirm T ?,
.Species
Be
Na
Mg
Al
Si
•
P
S
Cl
K
Ca
Sc
Ti
V
Cr
Mn
Fe
Co •
^T*
Ni
Cu
Zn
Ga
As
Se
Br
Rb
Sr
Y
Zr
Mo
Pd
Ag
Cd
In
Sn
Sb
ICP/
AESb-d
0.06
NA '
0.02
20
3
50
10
NA
NA
0.04
0.06
0.3
0.7
2
0.1
0.5
1
2
0.3
1
42
50
25
NA
NA
0.03
0.1
0.6
5
42
1
0.4
63
21
31
AA
Flameb-d
2d
0.2d
0.3
30
85
100,000
NA
NA
2"
ld
50
95
52
2
1
4
6d
5
4
1
52
100
WO
NA
NA
4
300
1000
31
10
4
1
31
31
31
AA
Furnaceb
0.05
<0.05
0.004
0.01
0.1
40
NA
NA
0.02
0.05
NA
NA .
0.2
0.01
0.01
0.02
0.02
0.1
0.02
0.001
NA
0.2
0.5
NA
NA
0.2
NA
NA
"0.02
NA
0.005
0.003
NA
0.2
0.2
INAA"-f
NAh
2
300
24
NA
NA
6,000
5
24
94
0.001
65
0.6
0.2
0.12
4
0.02
NA
30
3
0.5
0.2
0.06
0.4
6
18
NA
NA
NA
NA
0.12
4
0.006
NA
0.06
PIXE8
NA
60
20
12
9
s
8
8
w
5
4
NA
3
3
2
2
2
NA
1
1
1.
1
A
i
L
1
1
2
2
NA
3
5.
NA
NA
NA
NA
NA
NA
,3 a
APh T<"ypb
•"•V 1UK.
NA
NA
NA
5
3
3
2
5
3
2
NA
2
1
1
0.8
0.7
0.4
0.4
0.5
0.5
0.9
0.8
0.6
0.5
0.5
0.5
0.6
0.8
1
5
>
6
6
6
8
9
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
. NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
.NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
3-2
-------
Table 3-1 (continued)
Analytical measurement specifications for air filter samples
Species
I
Cs
Ba
La
Au
S8
Pb
Ce
Sm
Eu
Hf
Ta
W
Th
U
Cl-
NO3-
so;
NH;
oc
EC
ICP/
AESM
NA
NA
0.05
10
2.1
26
42
10
52
52
0.08
16
26
31
63
21'
NA
NA
NA
NA
NA
NA
AA
Flameb-d
NA
NA
8d
2,000
21
500
21
10
NA
2,000
21
2,000
2,000
1,000
NA
25,000
NA
NA
NA
NA '
NA
NA
AA
Furnace1'
NA '
NA
0.04
NA
0.1
21
0.1
0.05
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
INAAb'f
1
0.03
6
0.05
NA
NA
' NA
NA
0.06
0.01
0.006
0.01
0.02
0.2
0.01
NA
NA
NA
NA
NA
NA
NA
PIXE
NA
NA
NA
NA
NA
NA
NA
3
NA
NA
NA •
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
XRFC
NA
NA
25
30
2
1
1
1
NA
NA
NA
NA
NA
NA
NA
1
NA
NA
NA
NA
NA
NA
ICb
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
50
50
50
NA
NA
NA
AC"
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
- NA
NA
NA
50
NA
NA
TOR"
B- -^^£>^.
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
100
100
Minimum detection Itait is three times the standard deviation of the blank for a filter of 1 mg/cm' areal density.
ICP/AES - Inductively Coupled Plasma with Atomic Emission Spectroscopy.
AA = Atomic Absorption Spectrophotometry.
PIXE = Proton Induced X-ray Emissions Spectrometry.
XRF =« Non-Dispersive X-ray Fluorescence Spectrometry.
INAA = Instrumental Neutron Activation Analysis.
1C = Ion Chromatography.
AC " Automated Colorimetry.
TOR = Thermal Optical Reflectance.
*" eXtraCti°n * ** * * ^ *** * 15 "" °f **"*«"*•»«» W with a nominal flow rate of 20 e/min
Harman (1989).
Fernandez (1989).
Olmez(1989).
Eldred (1993).
Not Available.
3-3
-------
Balances used to weigh 20.32 cm X 25.40 cm filters from high volume PM10 samples
must have a sensitivity of at least 100 «. Balances used for medium volume PM ° samples
should have a sensitivity of at least 10 «. .and those used for low-volume PM10 samples should
have a sensitivity of at least 1 M. Modifications to the balance chamber are sometimes needed
to accommodate filters of different sizes. All filters, even those from high-volume PMIO
samplers, should be handled with gloved hands when subsequent chemical analyses are a
possibility. J
n»« r e established before »"d after each weighing session using
Class M and Class S standards, and they should be verified with a standard mass every ten
filters. Approximately one out often filters should be re-weighed by a different person at a later
time^ These re-weights should be used to calculate the precision of the measurement as outlined
oy Watson et al. (1989b).
e*amined ** gravimetric measurement of lightly loaded membrane
ata o mi r if? preC'S10n "nd aCCUraCy" ™6 Sensitivity of ** electrobalance is
iS mn ™ ™g' *°Ug 2lerance! on '^eights of Teflon-membrane filters are typically
±0.010 mg. The main interference in gravimetric analysis of filters results from electrostatic
ft \ *D?ebrecht « aL <1980> found «at residual charge on a filter could produce a£
electrostatic interaction between the filter on the pan and the metal casing of the elecLbalancT
y exposing *• mter to a radioactive poionium source bef°re
th* «. u attenuatran™ethDds have been applied in the laboratory as well as in the field, and
tiie results are comparable to those of gravimetric measurements. The precision of beta-gauge
measurements has been shown to be ±5 «/rf or better for counting intervals of one minufe pS
sample, which translates into ±32 ^/filter for 37 mm diameter substrates This is subSantiaMv
higher than the ±6 ^filter precision detenru^ed by gravimetric analysis^
Sques a^ me tLJSedVin Saf s ^^ ^ 6qUiValent Cy and Preci^ for '
mass measurements to differ by less than ±5%.' PatashnS^and^upprecht
mi* from TEOM samplers operated alongside filter-based PM10 samplers and
co-npanso. al, ^c^^rSrea^^"^011"" "^ ^
3.2 Elemental Analysis Methods
*ff * . mterest in elemental composition derives from concerns about health
effects and Ae utility of these elements to trace the sources of suspended parlto
nmtiron activation analysis (INAA), atomic absorption spectropLometi^ AAS
Sefcen^^1^01111: "ff^ *ccto«W aCP/AES), S^
2S! ? ,
-------
measurements when the particles are extracted in deionized distilled water (DDW) Since air
filters contain very small particle deposits (20 to 100 jig/cm2), preference is given to methods
which can accommodate small sample sizes. XRF and PIXE leave the sample intact after
analysis so that it can be submitted to additional examinations by other methods.
In INAA (Dams et al., 1970; Zoller and Gordon, 1970; Olmez, 1989), a sample is
irradiated in the core of a nuclear reactor for periods ranging from a few minutes to several
hours. The neutron bombardment chemically transform many elements into radioactive isotopes
The energies of the gamma rays emitted by these isotopes identify them, and therefore their
parent elements. The intensity of these gamma rays is proportional to the amount of the parent
element present in the sample. Different irradiation times and cooling periods are used before
counting with a germanium detector. INAA does not quantify some of the abundant species in
ambient paniculate matter such as silicon, nickel, tin, and lead. While INAA is technically
nondestructive, sample preparation involves folding the sample tightly and sealing it in plastic
and the irradiation process makes the filter membrane brittle and radioactive. These factors limit
the use of the sample for subsequent analyses.
In AAS (Ranweiler and Movers, 1974; Fernandez, 1989), the sample is first extracted
m a strong solvent to dissolve the solid material; the filter or a portion of it is also dissolved
during this process. A few milliliters of this extract are introduced into a flame where the
elements are vaporized. Most elements absorb light at certain wavelengths in the visible
spectrum, and a light beam with wavelengths specific to the elements being measured is directed
through the flame to be detected by a monochromater. The light absorbed by the flame
containing the extract is compared with the absorption from known standards to quantify the
elemental concentrations. AAS requires an individual analysis for each element, and a large
filter or several filters are needed to obtain concentrations for all of the elements specified in
laoie 3-1. AAS is a useful complement to other methods, such as XRF and PIXE for species
such as beryllium, sodium, and magnesium which are not well-quantified by these methods A
typical double-beam AAS system is schematically illustrated in Figure 3-1. Airborne particles
are chemically complex and do not dissolve easily into complete solution, regardless of the
strength of the solvent. There is always a possibility that insoluble residues are left behind and
soluble species may co-precipitate on them or on container walls.
tr on (FaSSd "^ Kirisd«*. 1974; McQuaker et al., 1979; Lynch et a/., 198O
Harman, 1989), the dissolved sample is introduced into an atmosphere of argon gas seeded with
free [electrons ; induced by high voltage from a surrounding Tesla coil. The high temperatures
in the induced plasma raise valence electrons above their normally stable states When these
electrons return to their stable states, a photon of light is emitted which is unique to the element
m^slT Tp/AF?18 "^ iS,deteCted Et SpeCified wavelenStns to identify the elements in
the sample ICP/AES acquires a large number of elemental concentrations using small sample
volumes with acceptable detection limit, for atmospheric samples. As with AAS,
requires complete extraction and destruction of the sample.
3-5
-------
E
-------
In XRF (Dzubay and Stevens, 1975; Jaklevic et al. , 1977) and PIXE (Cahill et al 1990-
y9?'. ±S fflter dep°sit b tadllltod by tig* energy x-rays (XRF) or protons'
(PIXE)which eject uiner shell electrons from the atoms of each element in the sample When
a higher energy electron drops into the vacant lower energy orbital, a fluorescent x-ray photon
is released. The energy of this photon is unique to each element, and the number of photons
is proportional to the concentration of the element. Concentrations are quantified by comparing
photon counts for a sample with those obtained from thin-film standards of known concentration
Emittedx-rays with energies less than ~ 4 kev (affecting the elements sodium, magnesium
aluminum, silicon, phosphorus, sulfur, chlorine, and potassium) can be absorbed in the filter'
m a thick particle deposit, or even by large particles in which these elements are contained'
Very thick filters also scatter much of the excitation radiation or protons, thereby lowering the
signal-to-noise ratio for XRF and PIXE. For this reason, thin membrane filters with deposits
in the range of 10 to 50 jig/cm2 provide the best accuracy and precision for XRF and PIXE
analysis.
Avrm me*°dsrcan be bf>,adly divided mto t*0 categories: wavelength dispersive
CWDXRF) which utilizes crystal diffraction for observation of fluorescent x-rays, and energy
dispersive (EDXRF), which uses a silicon semiconductor detector. The WDXRF method is
characterized by high spectral resolution, which minimizes peak overlaps WDXRF requires
high power excitation to overcome low sensitivity which results in excessive sample heating and
potential degradation. Conversely, EDXRF features high sensitivity but less spectral resolution
requiring complex spectral deconvolution procedures.
XRF methods can be further categorized as direct/filtered excitation, where the x-ray
beam from the tube is optionally filtered and then focused directly on the sample, or secondary
target excitation, where the beam is focused on a target of material selected to produce x-rays
of the desired energy. The secondary fluorescent radiation is then used to excite the samples
The direct/filtered approach has the advantage of delivering higher incident radiation flux to the
sample for a given x-ray tube power, since about 99% of the incident energy is lost in a
secondary fluorescer. The secondary fluorescer approach, however, produces a more nearly
monochromatic excitation which reduces unwanted scatter from the filter, yielding better
detection limits. &
XRF and PIXE are usually performed on Teflon-membrane filters for sodium
1Un\ Um' ^^ PhosPhorus> »«*. chlorine, potassium, calcium, titanium;
vanadium, chromium, manganese, uron, cobalt, nickel, copper, zinc, gallium, arsenic, selenium
b; mbld;um' str°?tium, yttrium, zirconium, molybdenum, palladium, silver, cadmium
, tin, antimony, barium, lanthanum, gold, mercury, thallium, lead, and uranium.
A typical XRF system is schematically illustrated in Figure 3-2 The x-rav outnnt
stabUity should be within ±0.25% for any 8-hour period within a^Zhour duration InaS
are typically controlled, spectra are acquired, and elemental concentrations aTcalcutTed by
software on a computer which is interfaced to the analyzer. wicwarea oy
3-7
-------
Sample
•Characteristic x-rays /Silicon detector
FET preamp
X-ray excitation
Secondary ( \Primary
Secondary target
Signal processing
Analog-to-
digital
converter
X-ray tube
• ly.
Data output
9 v
"-V
^
1 ./
m^mm^^^mfmmtm
Multi-channel
analyzer
ft-
Data handling
Video display
Mini-computer
Figure 3-2. Schematic of a typical x-ray fluorescence (XRF) system (Kevex, 1985).
3-8
-------
Separate XRF analyses are conducted on each sample to optimize detection limits for the
specified elements. A comparison of the minimum detectable limits of Teflon-membrane and
quartz-fiber filters is listed in Table 3-2. Figure 3-3 shows an example of an XRF spectrum.
Three types of XRF standards are used for calibration, performance testing, and auditing-
1) vacuum-deposited thin-film elements and compounds (Micromatter); 2) polymer films
(Dzubay et at., 1981); and 3) the National Institute of Science and Technology (NIST- formerly
NBS) thin-glass films. The vacuum deposits cover the largest number of elements and are used
to establish calibration curves. The polymer film and NIST standards are used as quality control
measures. NIST produces the definitive standard reference material, but these are only available
for the species aluminum, calcium, cobalt, copper, manganese, and silicon (SRM 1832) and
iron lead, potassium, silicon, titanium, and zinc (SRM 1833). A separate Micromatter thin-film
standard is used to calibrate the system for each element.
Sensitivity factors (number of x-ray counts per /tg/cm2 of the element) are determined
for each excitation condition. These factors, are then adjusted for absorption of the incident and
emitted radiation in the thin film. These sensitivity factors are plotted as a function of atomic
number and a smooth curve is fitted to the experimental values. The calibration sensitivities are
fen read from these curves for the atomic numbers of each element in each excitation condition
Polymer film and NIST standards should be analyzed on a periodic basis using these sensitivity
factors to verify both the standards and the stability of the instrument response. When deviations
from specified values are greater than ±5%, the system should be re-calibrated.
The sensitivity factors are multiplied by the net peak intensities yielded by ambient
samples to Obtain the /*g/cm2 deposit for each element. The net peak intensity is obtained by
1) subtracting background radiation; 2) subtracting spectral interferences; and 3) adjusting for
x-ray absorption. ' J s
The elemental x-ray peaks reside on a background of radiation scattered from the
sampling subside. A model background is formed by averaging spectra obtained from several
blank filters of the same type used in ambient sampling. It is important to retain blank filters for
purpose when XRF or PIXE analyses are anticipated. This model background has £e Tame
* u S3mple SpCCtra (minUS ** elemental Peaks> ^ the deposit mass is small
*e,SUbStrate "»« CRuss, 1977). This model background is normalized to an
f '°a scatter Peak m each sample spectrum to account for the difference in scatter
intensity due to different masses.
are
°f *? characteristic ™? &» relative » detector resolution
A f lement Can mterfere with a Peak from ^ther element
Vanety °f methods has been used to ****** ^se peak overlaps (Arinc et
c r et?\ 19?9; Drane et *" 1983>' tastadfa« least s^s fittmg to U^rarV
spectra, Gaussian and other mathematical functions, and the use of peak overlap coefficients
3-9
-------
Table 3-2
X-ray fluorescence air filter analysis interference-free minimum detectable limits"
using DRI standard analysis protocols
Element
Al
Si
P
S
Cl
K
Ca
Ti
V
Cr
Mn
Fe
Co
Ni
Cu
Zn
Ga
As
Se
Br
Rb
Sr
Y
Zr
Mo
Pd
Ag
Cd
la
Sn
Sb
Ba
La
Au
Hg
Condition
Numbed
5
5
5
5
4
4
4
3
•3 '
3
3
3
3
3
3
3
2
2
2
2
2
2
2
2
4
1
1
1
1
1
- 1
1
1
2
Quartz-Fiber Filter"
Protocol QA-A
us/cm2 '
NAf
NA
NA
40*
30
40 -
100
.50
20
8
7
15
5
4
4
6
8
9
5
5
5
8
8
10
20
20
20
25
30
40
50
170
190
NA
20
Teflon-Membrane Filter's
Protocol A
ne/cm2 d
10
6.3
5.6
5.0
10
6.1
4.5
2.9
2.5
1.9
1.6
1.5
0.88
0.89
LI
LI
1.9
1.6
1.2
1.0
1.0
1.1
1.3
1.7
2.7
11
12
12
13
17
18
52
62
3.1
2.6
Protocol B
ng/cm2
7;2
4.4
4.0
3.5
7.4
4.3
3.2
2.1
1.7
1.4
LI
1.1
0.62
0.63
0.76
0.76
1.4
1.1
0.86
0.72
0.68
0.78
0.92
1.2
1.9
7.6
8.6
8.6
9.5
12
13
37
44
2.2
1.8
Protocol C
ng/cm2
3.6
2.2
2.0
1.8
3.7
2.2
1.6
1.0
0.87
0.67
0.56
0.54
0.31
0.31
0.38
0.38
0.68
0.56
0.43
0.36
0.34
0.39
0.46
0.59
0.95
3.8
4.3
4.3
4.8
6.2
6.4
. 18
22
1.1
0.91
Protocol D
ng/cm2
2.5
1.4
1.4
1.2
2.6
1.5
1.1
0.73
0.62
0.48
0.40
0.38
0.22
0.22
0.27
0.27
0.48
0.39
0.31
0.25
0.24
0.28
0.33
0.42
0.67
2.7
3.0
3.0
3.4
4.4
4.5
13
16
0.77
0.65
3-10
-------
Table 3-2 (continued)
X-ray fluorescence air fitter analysis interference-free minimum detectable limits*
using DKI standard analysis protocols
Element
Tl
Pb
U
Condition
Number*
2
2
2
Quartz-Fiber Filter3
Protocol QA-A
ng/cm2 e
NA
14
NA
Protocol A
ng/cm2 d
2.5
3.0
2.3
Protocol B
ng/cm2
1.8
2.2
1.7
Protocol C
ng/cm2
0.88
1.1
0.83
Protocol D
ng/cm2
0.62
0.76
0.59
« MDL defined as three times the standard deviation of the blank for a filter of 1 mg/cm2 areal density.
" Analysis times are 100 sec. for Conditions 1 and 4, and 400 sec. for Conditions.2 and 3. Actual MDL's for
quartz filters vary from batch to batch due to elemental contamination variability.
c Analysis times are 100 sec. for Conditions 1, 4 and 5, and 400 sec. for Conditions 2 and 3 for Protocol A- 200
8°° SeC' f°r Conditions 2 "d 3 for Protocol B; 800 sec. for Conditions 1 4
for ***** C; - 160° ~ for conditions '•
" dto°t f°de «xcitation ^ a primary excitation filter of 0.15 mm thick Mo. Tube voltage is 50
.T!f? B °'6 ^ C°ndition 2 fa direct mode excitation wi* a primary excitation filter of 0 13
.mm thick Rh Tube voltage is 35 KV and tube voltage is 2.0 mA. ConditionTuses Ge second^ target
.excxtetm with ttie secondary excitation filtered by a Whatman 41 filter. Tube voltage is 30 KV and tubeconL
is 33 mA. Condition 4 uses Ti secondary target excitation with the secondary excitation filtered by 3 8 am thick
mylar film. Tube voltage is 30 KV and tube current is 3.3 mA. Conditions uses direct mode exciS wS
'111100118/8^ °f 3 ^^ °f Whatman 41 mters- Tube ™l*& is 8 KV Jd mbe curTem
^
'
f Information not available.
* For condition 4.
3-11
-------
OS
O
(J,
|
•§
(U
X,
-------
Peak overlap coefficients are applied to aerosol deposits. The most important of these
overlaps are the K-beta to K-alpha overlaps of elements which increase hi atomic number from
potassium to zirconium, the lead L-alpha to arsenic K-alpha interference, and the lead M line
to sulfur K line interference. The ratios of overlap peaks to the primary peak are determined
from the thin film standards for each element for the spectral regions of the remaining elements
These ratios are multiplied by the net peak intensity of the primary peak and subtracted from the
spectral regions of other elements. •
The ability of an x-ray to penetrate matter depends on the energy of the x-ray and the
composition and thickness of the material. In general, lower energy x-rays, characteristic of
light elements, are absorbed hi matter to a much greater degree than higher energy x-rays XRF
analysis of air paniculate samples has had widest application to samples collected on membrane-
type filters such as Teflon- or polycarbonate-membrane filter substrates. These membrane filters
collect the deposit on then- surfaces, which eliminates biases due to absorption of x-rays by the
filter material. These filters also have a low areal density which minimizes the scatter of
incident x-rays, and their inherent trace element content is very low.
Quartz-fiber filters used for high-volume aerosol sampling do not exhibit these features
As noted earlier, blank elemental concentrations hi quartz-fiber filters which have not undergone
acceptance testing can be several orders of magnitude higher than the concentrations in the
particulate deposits. They vary substantially among the different types of quartz-fiber filters
available, and even within the same filter type and manufacturing lot. Blank impurity
concentrations and their variabilities decrease the precision of background subtraction from the
XRF spectral data, resulting in higher detection limits. Impurities observed in various types of
glass- and quartz-fiber filters include aluminum, silicon, sulfur, chlorine, potassium, calcium
iron, nickel, copper, zinc, rubidium, strontium, molybdenum, barium, and lead. Concentrations'
for aluminum, silicon, and phosphorus cannot be determined for quartz-fiber filters because of
the large silicon content of the filters.
Quartz-fiber filters also trap particles within the filter matrix, rather than on its surface
This causes absorption of x-rays within the filter fibers yielding lower concentrations than would
otherwise be measured. The magnitude of this absorption increases exponentially as the atomic
number of the analyte element decreases and varies from sample to sample. Absorption factors
generally are 1.2 or less for iron and heavier elements, but can be from two to five for sulfur.
Quartz-fiber filters are much thicker than membrane filters resulting hi the scattering of
more x-rays with a consequent increase in background and degradation of detection limits The
increased x-ray scatter also overloads the x-ray detector which requires samples to be analyzed
at a lowered x-ray intensity. These effects alone can result in degradation of detection limits bv
up to a factor of ten with respect to Teflon-membrane substrates.
Larger particles collected during aerosol sampling have sufficient size to cause absorption
of x-rays within the particles. Attenuation factors for PM2J are generally negligible
1976), even for the lightest elements, but these attenuations can be significant
3-13
-------
particles (policies with aerodynamic diameters from 2.5 to 10 /mi). Correction factors have
been derived usrng the theory of Dzubay and Nelson (1975) and should be applied to the coile
particle measurements for SFS PMW samples.
with th H. iS' fflten$ ** removed from lWr Petri slides and placed
whth e^fS fit'8 ^ *t0 mter CaSSetteS' Tbe* CaSS6tteS «» loaded *«> * medLsm
which exposes the filter deposits to protons for PKE and x-rays for XRF. The sample chamber
^ evacuated^ a computer program controls the positioning of the •B^SS'ffcSSS
conditions. The vacuum in the x-ray chamber and the heat induced by the absorption of ™
to votiuze- For ^ reason' labae ^- -SK^iS
°n a quartz-flber fflter wwch sam^les ******* with
fr°m previous batches should be Analyzed for
or tf * qUaI.ity C°ntro1 results differ from specifications -by more C
i i'n H ! replicate concentrations differ from the original values (assuming they are ^
least 10 times detection limits) by more than ±10%, the samples should be ™
f " 7 /JT tiVe' bUt * iS kSS desirable because of ^ expense r^uSd ^to eTtoct S
sample and the destruction of the filter sample. «qmrea 10 extract the
3.3 Water-Soluble Ion Measurement Methods
nnrt- ^ OSO1 ^j18/6^ to chemical compounds which are soluble in water The water-soluble
chlondc, and fluonde may also be measured by these meehodsfaLg with ZpolyaTo'mtc
3-14
-------
All ion analysis methods require a fraction of the filter to be extracted in DDW and then
filtered to remove insoluble residues prior to analysis. The extraction volume needs to be as
small as possible, lest the solution become too dilute to detect the desired constituents at levels
typical of those found in PM10. Each square centimeter of filter should be extracted in no more
than 2 ml of solvent for typical sampler flow rates of 20 to 30 */min and sample durations of
24 hours. This often results in no more than 20 ml of extract which can be submitted to the
different analytical methods, thereby giving preference to those methods which require only a
small sample. Sufficient sample deposit must be acquired to account for the dilution volume
required by each method.
When other analyses are to be performed on the same filter, the filter is first sectioned
using a precision positioning jig attached to a paper cutter. For rectangular filters (typically
20 32 cm x 25 40 cm), a 2.54 x 20.32 cm wide strip is cut from the center two-thirds of the
filter. High-volume PM10 samplers have a 1.27 cm border around them, making the exposed
area -406 cm2 and the i area of the deposit on the filter strip 33.9 cm2. The analysis results must
be multiplied by - 12.0 to estimate the ion deposit on the entire filter. These values should be
verified by measurement, since different filter frames may have different dimensions. Circular
filters are usually cut in half for these analyses, so the results need to be multiplied by two to
obtain the deposit on the entire filter. Filter materials for these analyses must be chosen so that
they can be easily sectioned without damage to the filter or the deposit. The cutting blade
should be cleaned between each filter cutting. The filter section is placed in an extraction vial
which is capable of allowing it to be fully immersed in ~ 10 ml of solvent (the Falcon #2045 16
x 150 mm polystyrene vials are good choices). Each vial should be properly labeled with the
52? , ^ * ^t SInCe mU'h °f ** dep°slt is ^ a flber filter> aSita*°* « needed to
extract the water soluble particles into the solution. Experiments show that sonication for ~ 1
hour, shaking for ~ 1 hour, and aging for ~ 12 hours assures complete extraction of the deposited
material m the solvent. The sonicator bath water needs to be periodically replaced or
recirculated to prevent temperature increases from the dissipation of ultrasonic energy in the
water. After extraction, these solutions should be stored under refrigeration prior to analysis
The unused filter sections should be placed back into their labeled containers and stored under
refngeration. These can be used for other analyses or they can serve as a backup if the original
solution becomes contaminated or is insufficient for the planned ionic analyses
The operating principle for AAS was described above. For potassium the
n '
t - ; ^ bandPass' Approximately one to two ml of the extract are
into an air/acetylene flame at approximately 0.5 ml/min. The output of the
photpmultipher can be recorded on a data acquisition computer at rates of approximately two
to±f rrr1' ™d ** °Vera11 3° SeCOIia aV6rage Can be *"« to atten"2 variability Se
to ^fluctuation. This averaging should begin only after the sample has been aspirated for
at least 30 seconds to assure that the flame has equilibrated. Two ml of DDW should be run
*" SamplC lfne- A blank «* a Sown
Span ^ baseline- Ten «rcdtt of
mnlTh M £ y 6Ve,? tCn Sample$ t0 Verify ^ Span ^ baseline- Ten P«rcdtt of
the samples should be run in replicate at a later time, when there is sufficient extract, to evaluate
3-15
-------
analysis precision American Chemical Society (ACS) reagent grade salts are dissolved in
carefully measured volumes of DDW to create calibration and performance testing standards
mterference M elimmated fey additi°n of cesium chloride to samples and standard
1C can be used for both anions (fluoride, phosphate, chloride, nitrate, sulfate) and cations
(potassium, ammonium, sodium) with separate columns. Applied to aerosol samples, the anions
are most common^ analyzed by 1C with the cations being analyzed by a combination of AAS
^ f£« ^T (Sn?V™ ' 'c19?5; MuUk &t al" 1976> 1977» Butler * <*•• 1978; Mueller et
cl ; ?"? ^ " 1978;,SmaI1' 1978>> ** samPle «tract passes through an ion-exchange
column which separates the ions in time for individual quantification, usually by a
electroconductivity detector Figure 3-4 shows a schematic representation of the 1C system.
Prior to detection, the column effluent enters a suppressor column where the chemical
composition of one element is altered, resulting in a matrix of low conductivity. The ions are
identified by their elution/retention times and are quantified by the conductivity peak area or
peak height. 1C is especially desirable for particle samples because it provides results for
SS T T^ ***?** and it uses a small portion of the filter extract Slow
S^^St .^^^^^^^^^^ICanionchromatogram. 1C analyses can
pler which can conduct unattended anaiysis °f
2 ** °f ^ ^ ***** m fa*!Ctod mto IC system- The resulting
to concentrations using calibration curves derived from solution
standards. Standard solutions of sodium chloride, sodium nitrate, and sodium sulfate can be
prepared with t reagent grade salts which are dehydrated in a desiccator several hours prior to
SS^^S^ ±1*1 ^ water fs^ (Standard Reference Materiais= SRM
2694-1 and SRM 2694-n) and the Environmental Research Associates (ERA) standard solution
are available as independent quality control checks for the ions commonly measured by C
fh± h standards should be analyzed every ten samples, and one tenth of all PM10 exacts
should be re-analyzed in the next analysis batch to estimate precision.
Though automated data processing is usually applied to 1C output, the chromatoerams
comato^ \for,rf SOftWare t0 detCCt deViatl0nS from measurement assumpS S
chromatogram should be examined individually to verify: 1) proper operational settings 2)
-
3-16
-------
Delivery Module
Chromatography Module
Detector Module
Eluent.
Reservoir
Pump
Sample
Injector
Guard
Column
Separator
Column
Suppressor
Device
Conductivity
Cell
Waste
Figure 3-4.
°f ^ ^ Chromato^phy 00 system (Chow and
3-17
-------
9000
6600
nS
Figure 3-5. Example of an ion chromatogram (Chow et al, 1993d).
3-18
-------
Since 1C provides multi-species analysis for the anions, ammonium is most commonly measured
oy
The AC system is illustrated schematically in Figure 3-6. The heart of the automated
colorimetric system is a peristaltic pump, which introduces air bubbles into the sample stream
at known intervals. These bubbles separate samples hi the continuous stream. Each sample is
mixed with reagents and subjected to appropriate reaction periods before submission to a
colorimeter. The ion being measured usually reacts to form a colored liquid. The liquid
absorbance is related to the amount of the ion hi the sample by Beer's Law. This absorbance
is measured by a photomultiplier tube through an interference filter which is specific to the
species being measured.
The standard AC technique can analyze ~ 50 samples per hour per channel, with minimal
operator attention and relatively low maintenance and material costs. Several channels can be
set up to simultaneously analyze several ions. The methylthymol-blue (MTB) method is applied
to analyze sulfate. The reaction of sulfate with MTB-barium complex results in free ligand
which is measured colorimetrically at 460 nm. Nitrate is reduced to nitrite which reacts with
sulfamlamide to form a.diazo compound. This is then reacted to an azo dye for colorimetric
determination at 520 nm. Ammonium is measured with the indophenol method. The sample is
mixed sequentially with potassium sodium tartrate, sodium phenolate, sodium hypochlorite
sodium hydroxide, and sodium nitroprasside. The reaction results in a blue-colored solution with
an absorbance measured at 630 nm.
Formaldehyde has been found to interfere with ammonium measurements when present
in an amount which exceeds 20% of the ammonium content, and hydrogen sulfide interferes in
concentrations which exceed 1 mg/ml. Nitrate and sulfate are also potential interferents when
present at levels which exceed 100 times the ammonium concentration. These levels are rarely
exceeded in ambient samples. The precipitation of hydroxides of heavy metals such as
magnesium and calcium is prevented fey the addition of disodium ethylenediamine-tetracetate
(EDTA) to the sample stream (Chow et al., 1980; Chow, 1981). It was learned in the SUlfate
Eegional Experiment (SURE) (Mueller et al., 1983) that the auto-sampler should be enclosed
in an atmosphere which is purged of ammonia by bubbling air through a phosphoric acid
solution.
The automated colorimetric system requires a periodic standard calibration with the daily
prepared reagents flowing through the system. Lower quantifiable limits of automatic
colonmetry for sulfate and nitrate are an order of magnitude higher than those obtained with ion
chromatography.
Intercomparison studies between automated colorimetry and ion chromatography have
been conducted by Butler et al. (1978); Mueller et al. (1978); Fung et al. (1979)- and Pven and
Fishman (1979). Butler et al. (1978) found excellent agti^betw^l^tS^
measurements by automated colorimetry and ion chromatography.. The accuracy of both
methods is within the experimental errors, with higher blank values observed from automated
3-19
-------
.
V)
I
o
CJ
o:
a>
a
9
ce
o
c
_
Q.
O
V)
O)
o
9
O)
o
o
at
01
O
Q!
I
O
J
f
I
GO
*•*
I
O
'S
I
o
8
1
03
2
-------
colorimetric techniques. Comparable results were also obtained between the two methods by
Fung et al. (1979). The choice between the two methods for sample analysis are dictated bv
sensitivity, scheduling, and cost constraints.
The major sampling requirement for analysis of water-soluble species is that the filter
material be hydrophilic, allowing the water to penetrate the filter and fully extract the desired
chemical compounds. Small amounts of ethanol or other wetting agents are sometimes added
to the filter surface to aid the wetting of hydrophobic filter materials, but this introduces the
potential for contamination of the sample.
3.4 Carbon Measurement Method Selection
. Three classes of carbon are commonly measured in ambient aerosol samples collected on
quartz-fiber filters: 1) organic, volatilized, or non-light absorbing carbon; 2) elemental or light-
absorbing carbon; and 3) carbonate carbon. Carbonate carbon (i.e K2CO3 Na CO
^SC?3'™C03) Can be determmed on a separate filter section by measurement of the carbon
dioxide (CCg evolved upon acidification (Johnson et aL, 1981). Though progress has been
made in the quantification of specific organic chemical compounds in suspended particles (e g
Rogge et al., 1991), sampling and analysis methods have not yet evolved for use in practical
monitoring situations. yi«.i»*u
Several analytical methods for the separation of organic and elemental carbon in ambient
S partlculuate; samPles fc™ been evaluated (Cadle and Groblicki, 1982; Stevens et al
These methods include:
Solvent extraction of the organics followed by total carbon analysis (Gordon 1974-
Grosjean, 1975; Appel et aL, 1976, 1979; Daisey et aL, 1981; Muhlbaier and
Williams, 1982; Japar et aL, 1984). '
Nitric acid digestion of the organics followed by total carbon analysis (McCarthy and
Moore, 1952; Kukreja and Bove, 1976; Pimenta and Wood, 1980).
Absorption of radiation using an integrating plate to determine elemental carbon
Infrared absorbance (Smith etaL, 1975), Raman spectroscopy (Rosenetal 1978)'
and visible absorbance (Lin et aL, 1973; Weiss et aL, 1979; Gerber' 1982:
. Heintzenberg, 1982) are variations of this method.
'^ustion mcludmS both temperature programmed (Muhlbaier and
liams, 1982) and step-wise pyrolysis followed by oxidation using either carbon
dioxide or methane detection (Mueller et aL, 1971, 1981; Patterson, 1973; Merz
L JQ^TQ^ H™t?cker' 1979' Johnson *«*. 1980; Malissa, 1979; Cadle et
19*2 Wolff e?* * *" ^ ^ N°V*0V' 1981; ^^ «
3-21
-------
• A combination of thermal and optical methods (Appel et aL , 1976- Dod et al 1979-
Macias et aL, 1979; Cadle et al., 1980a, 1980b; Johnson et aL, 1981; Novakov'
1982; Huntzicker et aL, 1982; Rosen et aL, 1982; Chow et aL, 1993c).
Table 3-3 summarizes different carbon analysis methods and reports typical carbon
concentrations in urban and non-urban areas.
The definitions of organic and elemental carbon are operational (i.e., method dependent)
and reflect the method and purpose of measurement (Grosjean, 1980). Elemental carbon is
sometimes termed "soot", "graphitic carbon", or "black carbon." For studying visibility
reduction, light-absorbing carbon is a more useful concept than elemental carbon For source
apportionment by receptor models, several consistent but distinct fractions of carbon in both
source and receptor samples are desired, regardless of their light-absorbing or chemical
properties. Differences in ratios of the carbon concentrations in these fractions form part of the
source profile which distinguishes the contribution of one source from the contributions of other
sources (Watson et al., 1994c).
Light-absorbing carbon is not entirely graphitic carbon, since there are many organic
materials which absorb light (e.g., tar, motor oil, asphalt, coffee). Even the "graphitic" black
carbon in the atmosphere has only a poorly developed graphitic structure with abundant surface
chemical groups. "Elemental carbon" is a poor but common description of what is measured
For example, a substance of three-bond carbon molecules (e.g., pencil lead) is black and
completely absorbs light, but four-bond carbon in a diamond is completely transparent and
absorbs very little light. Both are pure, elemental carbon.
« ™l?/* (1"3c) document several variations of the thermal (T), thermal/optical
reflectance (TOR), thermal/optical transmission (TOT), and thermal manganese oxidation (TMO)
methods for organic and elemental carbon. The TOR and TMO methods have been most
commonly applied in aerosol studies.
3.4.1 Thermal Manganese Oxidation Method for Carbon
The thermal manganese oxidation (TMO) method (Mueller et al. , 1982- Fung 1990) uses
manganese dioxide present and in contact with the sample throughout the analysis, as the
oxidizing agent. Temperature is relied upon to distinguish between organic and element
SSL S r f 0lTg at 5?5°C IS daSSified M °rganic carbon' and caibon evol^T*
850 C is classified as elemental carbon.
bee° used for ** five y^ SCENES (the Subregional Cooperative
v ™ PfTT °f ^ ',Tati0nal Pa± ServiC6S' ^ EnviroLentalprotection
Agency Study) (i.e., Mueller and McDade, 1986; Sutherland and Bhardwaja, 1986; Mueller et
3-22
-------
Table 3-3
Carbon analysis method characteristics
Typical Ambient
Concentration
fag/nrt
Urban sites
(0 to 2.5
OC1 2.7 to 12.9
EC 0.9 to 7.0
TC 3.6 to 19.0
Non-urban sites
(0 to 2.5
OC 1.2 to 4.3
EC 0.5 to 2.2
TC 1.5 to 6.0
Measurement
Method
Solvent
Extraction
Precision*
S to 15%«
Accuracy*
20 to 54%'
Nitric Acid
Digestion
1.4 to 5.8%e 15 to 32%«
Integrating Plate NA'
Method
Thermal
Combustion
Method
1 to 2%'
Advantages and
LOL" Disadvantages
NA' Only 30 to 50% of
volatilizable carbon can be
removed
The procedure underestimates
volatilizable carbon and
overestimates elemental
carbon by 9 to 20%
Pyrolytic conversion of
volatilizable to elemental
carbon is minimized
These methods require
significant quantities of
sample and are time
consuming and expensive
NA' Some elemental carbon is
measured as volatilizabie
carbon because nitric acid «
converts elemental carbon to
• • volatilizable carbon
NA' Relies on poorly determined
absorption coefficients and is
subject to interferences
Interference by non-absorbing
species such as (NH^ SO4 on
elemental carbon
measurements
14-15%** 0.3Mg/cm2 for Different thermal combustion
oc analyzers with different
procedures often yield
0.5/ig/cma different values for identical
for EC samples
Overestimates elemental
carbon due to the
carbonization of volatilizable
material
Underestimates elemental
carbon due to the
measurement of volatilizable
carbon at high temperatures
NAf
3-23
-------
Table 3-3 (continued)
Carbon analysis method characteristics
Typical Ambient
Concentration
Measurement
Method
Precision"
Thermal/ Optical 2 to 4%J
Method
Accuracy1*
2to5%"
LOLC
Q-Spg/cwP
forOC
Advantages and
Disadvantages
Separates volatilizable from
elemental carbon*'
0.2f«g/cm2 for Corrects for pyrolysis
EC
Carbonate carbon is measured
as volatilizable and elemental
carbon if present as more than
5% at total carbon
* ±. one standard deviation, per filter, unless otherwise specified
* jh absolute error
QU3ntifiabIe Ltait; °ften deteraiined °y variability in blank analysis or minimum detectable limit - whichever is
* From Shah (1981)
* From Cadle and Groblicki (1982)
' NA — not available
* From Mueller et aL (1983)
From Watson et al. (1981)
From Stevens et al. (1982)
From Johnson (1981)
From Rau (1986) and Chow et al. (1993b)
OC: Organic Carbon
EC: Elemental Carbon
TC: Total Carbon
3-24
-------
al., 1986; Watson et aL, 1987) visibility network, as weU as Southern California Air Quality
Study (SCAQS, Chow et al., 1994b, 1994c; Watson et al., 1993, 1994b, 1994d).
3.4.2 Thermal Optical Reflectance/Transmission Method for Carbon
The thermal/optical reflectance (TOR) method of carbon analysis developed by
Huntzicker et al. (1982) has been adapted by several laboratories for the quantification of-
organic and elemental carbon on quartz-fiber filter deposits. While the principle used by these
laboratories is identical to that of Huntzicker et al. (1982), the details differ with respect to
calibration standards, analysis time, temperature ramping, and volatilization/combustion
temperatures.
In the most commonly applied version of the TOR method (Chow et al 1993c) a filter
is submitted to volatilization at temperatures ranging from ambient to 550°C in a pure' helium
atmosphere, then to combustion at temperatures between 550° C to 800°C in a 2% oxygen and
98% helium atmosphere with several temperature ramping steps. The carbon which evolves at
each temperature is converted to methane and quantified with a flame ionization detector The
reflectance from the deposit side of the filter punch is monitored throughout the analysis ' This
reflectance usually decreases during volatilization in the helium atmosphere owing "to the
pyrolysis of organic material. When oxygen is added, the reflectance increases as the light-
absorbing carbon is combusted and removed. An example of the TOR thermogram is shown
in Figure 3-7.
Organic carbon is defined as that which evolves prior to re-attainment of the original
reflectance, and elemental carbon is defined as that which evolves after the original reflectance
has been attained. By this definition, "organic carbon" is actually organic carbon that does not
absorb light at the wavelength (632.8 nni) used and "elemental carbon" is light-absorbing carbon
(Chow et al. , 1993c). The thermal/optical transmission (TOT) method applies to the same
thermal/optical carbon analysis method except that transmission instead of reflectance of the
filter punch is measured.
Chow et al. (1993c) document several variations of die thermal (T) thermal/optical
reflectance (TOR), thermal/optical transmission (TOT), and thermal manganese oxidation (TMO)
SSSL *&&** flem«ntal carbon. Chow et al. (1993c) also examine results from
collocated elemental carbon measurements by optical absorption (OA), photoacoustic
spectroscopy, and nonextractable mass. TOR was consistently higher than TMO for elemental
carbon especially in woodsmoke-dominated samples, where the disparity was as great as seven
? SUmv °rgEfC and elemental carbon> mese ^thods reported agreement within
ambient and source samples (Houck et al. , 1989; Kusko et al 1989- Countess
^^
then becomes a matter of assessing how they differentiate between organic and
elemental carbon. The TMO method attributes more of the total carbon to organic carbon and
less to.elemental carbon than the TOR and TOT methods
3-25
-------
800
1000 1200 1-H30 1^00 1300 -2000 2200
TIKE
Figure 3-7. Example of a thermal optical reflectance (TOR) thermogram (Chow et al., 1993c).
3-26
-------
Comparisons among the results of the majority of these methods show that they yield
comparable quantities of total carbon in aerosol samples, but the distinctions between organic
and elemental carbon are quite different (Countess, 1990; Bering et al., 1990). None of them
represents an ideal separation procedure of organic from elemental carbon.
3.4.3 Filter Transmission for Light Absorbing Carbon
Teflon-membrane and quartz-fiber filters can be submitted to a light transmission
measurement before and after sampling on a transmission densitometer. An example of the
measurement system is illustrated in Figure 3-8. Each filter is placed in a jig over a diffused
vertical light beam. The spectral distribution is approximately Gaussian, peaking near 550 nm
with full- width at Tialf maximum of about 150 nm. A detector is brought to a constant height
above the filter and is precisely positioned with a shim to prevent contact with the filter Itself
The filter density is displayed by the densitometer and can be later converted to transmittance"
The same measurement is repeated on the exposed filter.
The instrument is calibrated with neutral density filters, and one of these standards is
analyzed every 10 filters to verify instrument stability. If the response to these standards differs
from specifications by more than 0.03 density units, the instrument is re-calibrated and the
measurements are repeated on the previous ten samples. Replicate analyses are performed on one
out of every ten samples, and when replicates deviate by more than ±0.05 density units from
their original levels, samples are re-measured.
Informal intercomparisons among different filter transmission methods have shown high
correlations of absorption, but differences of up to a factor of two in absolute values (WatsSn
etal., 1988c). These differences are functions of: 1) the type of filter; 2) filter loading- 3) the
chemical and physical nature of the deposit; 4) the wavelengths of light used; 5) caUbration
standards; and 6) light diffusing methods. At the current time, there is no agreement on which
combination most accurately represents light absorption, in the atmosphere. This method is
applied with the knowledge that absolute differences in absorption may be found between the
measurements made on Teflon-membrane and quartz-fiber filters and with respect to absolute
absorption measurements made on the same samples hi other laboratories.
3,5 Filter Selection, Preparation, Handling, and Storage
No chemical analysis method, no matter how accurate or precise, can provide an accurate
representation of atmospheric constituents if the filters to which these methods are applied are
improperly selected or handled. The different filter media available for PM10 sampling for
Sfi P? Tre deSC?6d fa SeCti°n 2' ™> «*H**taa describes how theL filter
should be selected, prepared, handled, and stored from a laboratory standpoint Mass
concenttations associated with PM10 are usually measured in micrograms, one million* of one
gram. These are very small quantities, and even the slightest contamination can bias these mass
3-27
-------
.0
00
oo
o
.22
13
i
-------
measurements. Most of chemical species which constitute PM10 are measured in nanograms
one-bilhonth of one gram. The potential for contamination from these chemical components is
ten to one-thousand times greater than it is for contamination of mass concentrations Small
biases in chemical concentrations can greatly affect the decisions which are made with respect
to source apportionment or health effects, so extra precautions are warranted when selecting and
using filters.
* * out in Section 2, the choice of filter type results from a compromise among
the following filter attributes: 1) mechanical stability; 2) chemical stability; 3) particle or ga!
sampling efficiency; 4) flow resistance; 5) loading capacity; 6) blank values- 7) artifact
formation; 8) compatibility with analysis method; and 9) cost and availability. Teflon-membrane
and quartz-fiber filters are most commonly used for the PM10 chemical analyses described above
though cellulose-fiber filters lend themselves nicely to impregnation for absorbing gaseous
precursors, and etched polycarbonate-membrane filters are best suited for microscopic analyses
Specific choices which have been found to be useful in previous receptor modeling source
apportionment studies are: 1) Gelman (Ann Arbor, MI) polymethylpentane ringed, 2.0 urn pore
size, 47 mm and 37 mm diameter PTFE Teflon-membrane filters (#R2PJ047 #R2PJ037) for
mass by gravimetry, elements by XRF or PDCE, and optical absorption measurements by filter
ttansmission; 2) Schleicher and Schuell (Keene, NH) 1.2 Mm pore size, grade 66 47 mm
diameter, nylon-membrane filters (#00440) for volatilized particle nitrate as well as total nitrite-
5) Pallflex (Putnam, CT) 47 mm diameter quartz-fiber filters (#2500 QAT-UP) for carbon bv
combustion methods as well as water-soluble chloride, nitrate, sulfate, ammonium, sodium and
potassium by 1C, AC, and AAS measurements; and 4) Whatman 41 (Maldstone England) 47
mm diameter cellulose-fiber filters (#1441047) impregnated with adsorbing chemicals for sulfur
dioxide and ammonia measurements. These filters have been used primarily in the low-volume
samplers described in Tables 2-1 and 2-2. High-volume PM10 samplers require 20 32 cm x
fflt^ S5S?SS mteKS> °f WWch *" °elman Zeflu°r Tefl°a-membrane, 2 jun pore size
filters (#F2996-25) have been most commonly used for elemental analyses and the Gelman
quartz-fiber (QM/A) filters have been used for other analyses. The manufacturer's identification
numbers are important specifications since only these particular filters have been found to
acceptably meet the requirements for chemical characterization in previous studies.
As noted in Section .2, filters require treatment and representative chemical analyses
before ttiey can be used (Chow, 1987). At least one filter from each lot purchased from the
specified manufacturers should be analyzed for all species to verify that pre-established
pecifications have been met. Table 3-4 tabulates filter acceptance test results between 1992 and
t?% °f °V6H ,° ^ f°r different fflterS' ^ m reJ6Cted for chemical analys* when blank
levels for individual species exceed 1 /^/filter. Table 3-4 shows that blank values are verified
7 **?"*? **** l71?eS' Each fflter sh°^ also be individually examined
dllCOl°ratl0n' Pmh°les' Creases' or other defects« T«ting of sample media
n ^* *« c°^e of a monitoring project. In addition to laboratory blanks?
to 10% of all samples are designated as field blanks, and these follow all handling
procedures except for actual sampling. Sample pre-treatments may include-
3-29
-------
S
J
£1
00
61
55
0
-H
0\
»-H
o
-H
VO
"3-
o
S
o
-H
S
o
-H
00
anufacturer
a
§
I
&
»•
53
o
1-
O VO
i sf s
<£ W £'Ci>
H H
"• *
•g
u.
o
So1
3-30
-------
3
O
en
tn
a*
M
81
•*•» I-H
"•a
"8 §
l«
IS-
fi, S
ill
111
1-*
S 2 -
^ -S '3
T* V ,C8
" W »
^ s ^
« «8 .2
J= ^ CA
ja £>>
CQ ?i eo
H S B
«•<
Is
S|
0 g
^2
5 *s
S S3
E W
s
CO
« I
*s
(Q~
•a c
« "5
•a .S3
c >
£ a
"*"
el
G
.-"5b
oo
^H^
o
-H
»— i
CN
^ 0
1
^"
"«3 . :
t-
J3
J
1
la
CO O
d8 f
C3
11
• ^4 M^
•s
S m
o rh
CO «0
"
en
.y. ^A
o S
5S
If
M N_^
a
S5
o
o
-H
§
o
eO
O
-H
00
CN
^ 2
is'S
S »H B
m
»—i
O
-H
oo
O
.§
g
• a r-
S 0 rf
-------
oo
I
E
oo
VO
CO
I I
•2.1
II
sa
bx
H
O
-H
o
00
»-H
o
•H
CS
O
-H
Ui
b
S
o
-H
t-
i-H
O
I*
O
-H
o\
T— (
0
S 1
g
•H o
I'"
u i
« c
"3 S °
S3 >-> «n
a
-
-
£ I_ >-< ~H
n3 ;> g in
8*1*
J5 rr fi
OSS
08 <
0 '$ ^
— S3 t^-
s -o S ^-
'S € S2
0 §5:5
-H eo^S
rj- g ^ ^
C S^'o •
1^^^
•5 «-. o o
i-lil
^ b u 53
r-
T]-
S.S
s ^
J3 0 C
s o a ^
« a. a P
Sa|S
§ ^^s:
C O g rj
E-^ ci s ^
^ S
o o
co en
3-32
-------
ON
en
s
>^
1
.S
1
1
T
en
«
2
S
•w
**4
tf $3
Q£
•*- -H
•sl
II
£^
ftg
ee
c
H
•^
1
H-
(9
"B.I
11
«2 "U
co Q
+
oi
1 .£ 1
iso 'Sb
=t =S!
^ ^
cn f~«i
0 0°
-H +1
^" *O
0 0
.
Manufacturer
a a
CO •-
0 VO C
•a eN 2
*O * f^» M
SfSSl S
vo
o
200
•*
t-J N^ ^"*
|||
CO "^ ^
o S '^
t^
TC
5
en
7—1
O
-H
o
6
e o
O vo
'& CN
"o *•« H *"*
llll
1
1
en
O
-H .
o
o .
e
lex Production Co.
S
&
PH
S
(N
"-*' F-H
oB
ti-
ll
i-H
g
OO
CN
o\
§
1
1
en
oo
O
o
-H
o\
0
ex Production Co.
§
V-,'
Q
1
u.
iU
U
3-33
-------
I
in
o
a
8
J$
•-I Me
si I
*
•eJ
-s «
G >
a «
co Q
-h
bi
>
<
s
o
-H
en
•^f
O
o
U
c
Ui
4J
*2
3
«S
1
O
•J3
o
s
o A
£ T,
« •?
•s 1
Ss
Q
^3
cs
^o ^^
o vo
H r-^
^ oo
s" °^
Is
fie
o
a
"O
o
O
-------
Pte-fmng of quartz-fiber filters. Quartz-fiber filters adsorb organic vapors over time
Blank quartz-fiber filters should be heated for at least three hours at 900°C A sample
of each batch of 100 pre-fired filters is tested for carbon blank levels prior to sampling
and sets of filters with carbon levels exceeding 1 Mg/cm2 are re-fired or rejected All
pre-fired filters should be sealed and stored in a freezer prior to preparation for field
sampling.
Washmgnvlon-membrane filters. Nylon-membrane filters absorb nitric acid over time
Blank nylon-membrane filters should be soaked for four hours hi 0 015 M sodium
carbonate then rinsed in DDW for 10 minutes, soaked overnight in DDW, rinsed three
times in DDW, then dried in a vacuum oven at 60°C for 5 to 10 minutes. Extraction
efficiency tests have shown that the sodium carbonate 1C eluent is needed to remove
nitrates from the active sites of the nylon filter* Sets of washed nylon filters with nitrate
levels exceeding 1 /xg/filter should be rejected. Pre-washed nylon filters should be sealed
and refrigerated prior to preparation for field sampling.
Equilibrating Teflon-membrane filters. On several occasions over the past 10 years
(e.g Tombach et al., 1987), batches of Gelman ringed Teflon-membrane filters have
yielded variable (by up to 100 /^/filter over a few days) blank masses. As the time
between manufacture and use increases, this variability decreases. Since Gelman has
minimized its long-term inventory of these filters and is manufacturing them on an as-
ordered basis, this variability is being observed with greater frequency. A one-month
storage period in a controlled environment, followed by one week of equilibration in the
weighing environment, has been applied in several studies, and this appears to have
reduced the variability to acceptable (within ±15 /Kg/filter for re-weights of 47 mm and
37 mm diameter filters) levels. Sets of Teflon-membrane filters which exceed twice XRF
detection limits for elements are rejected.
reflts °f a11 ?!ter ***«*. chemical analyses, and visual inspections should be
, ^ Wth *" 10t nUmberS' A S6t Of fflter IDs is ^signed to each lot so that
a record of acceptance testing can be associated with each sample.
«» h, I*!? 1Slge sec°ndary contributions to PM10, Whatman 41 cellulose-fiber filters
can be impregnated with gas-adsorbing solutions to collect gaseous ammonia and sulfur dioxide
Several impregnation solutions have been used, and these solutions differ with reTp* to fcet
Son CrP° n^ "^ f°f Ulations' ^ criteria **** ™st be met by the impregnation
solution are: 1) availability of pure reagents; 2) stability of the impregnation solution
composition before and after impregnation; 3) low degree of hazard or toxSty 4) Tack of
mterferences with other pollutants being sampled or with analytical methods; and' 5) mSna
effects of environmental factors such as temperature and water vapor content.
Ohira
d
and
19?1; ^PP et **- 1986>> oxalic a«d (Perm, 1979-
- and,LodSe' 1975), phosphoric acid, sodium carbonate Perm
acid (Stevens et a/., 1985) have been used as the active agent in the sampling
3-35
-------
of ammonia on a variety of substrates. Citric acid impregnating solutions best meet the criteria
described above.
Fung (1988) tested the ammonia absorption capacity of Whatman 41 cellulose-fiber filters
impregnated with 0. 13 pg of citric acid and 0.024 fig of glycerine. These filters adsorbed more
than 4,000 /tg of ammonia with better than 99% efficiency. Tests at temperatures ranging from
-20°C to 25 °C and at high and low relative humidities showed sampling efficiencies for
ammonia in excess of 99%.
Potassium carbonate or sodium carbonate with glycerine has been used in impregnated
filters for sulfur dioxide, nitric acid, or organic acid sampling (Forrest and Newman 1973-
Johnson and Atkins, 1975; Anlauf et al., 1985; Damn and Leahy, 1985; Hering et al ' 1993-
Tanner et al. , 1993). The carbonate in the impregnating solution presents interferences to both
the 1C and AC analyses of extracts from these filters, however. In 1C, the carbonate interferes
with the nitrate peak and broadens the sulfate peak. In colorimetric methylthymol-blue analysis
the reaction of the MTB-Ba complex needs to be acidic and the carbonate raises the pH Steps
can be taken to alleviate these in the preparation of the filter extract prior to analysis.
Triethanolamine (TEA) has been used as an absorbent for nitrogen dioxide and to
measure aerosol acidity (Dzubay et al., 1979). When used as a solution in a bubbler TEA is
\ ? ',1 ™ e£iva*ent method CNo. EQN-1277-028) for monitoring nitrogen dioxide. Alary
et al. (1974), Ohtsuka et al. (1978), Gotoh (1980), and Knapp et al. (1986) have applied TEA
solutions to filter media such as Whatman 31 chromatographic paper for the collection of
nitrogen dioxide. The TEA is usually mixed with glycol or glycerine to improve its absorbing
capacity (Doubrava and Blaha, 1980). Peroxyacetyl nitrate (PAN), organic nitrates, and sulfu?
dioxide are also collected by this substrate, and the nitrogen-containing compounds will appear
as nitrate during analysis. TEA oxidizes in air and light, so impregnated filters must be stored
in the dark in sealed containers.
Practical impregnation solutions consist of:
• 25% citric acid and -5% glycerol (balance being water) for ammonia sampling.
• 15% potassium carbonate and 5% glycerol solution (balance being water) for sulfur
dioxide sampling.
• 25% TEA and 5% ethylene glycol (balance being water) for nitrogen dioxide
sampling.
• 5% sodium chloride (balance being water) for nitric acid sampling.
cm H f?ters' cellulose-fiber filter disks are immersed in the impregnating
solution for approximately 30 minutes. These disks are then removed and placed in clean Petri
slides for drying in a vacuum oven for five to ten minutes. One hundred of
3-36
-------
impregnated filters are immediately sealed in polyethylene bags and placed under
for later loading into filter holders. One sample fromeach tot'of citric .£S£
to ammonium analysis prior to use. One sample from each lot should be extracted and analyzed
prior to field sampling to assure that filter batches have not been contaminated. It is also useful
to analyze each filter for a component of the impregnating solution (e.g., potassium on
^ t0^ *-mteIS "-•*« •-£*- «
3.6 FUter Analysis Protocol
The selection of appropriate analysis methods, filter media, and sampling hardware must
be complemented with detailed sample handling and analysis procedures. Figure 3-9 shows an
example of the flow diagram for a typical PM10 sampling system. This diagra^ also shows t^e
chemical analyses on different sampling channels to which these samples are submitted Figure
3-10 shows a flow diagram of the different operations which are applied in a typical aerSol
^ ^H m°,mt0nng Pr0gram' ^ b°X represents a set of actions which must be taken
as part of the overall measurement process. Flow charts such as these should be prepared prior
o aerosol sampling for chemical analyses. They show precisely how samples are to be loaded
and which analyses they wi 1 receive. This minimizes the possibility of submitting samples to
the wrong analyses when filters are returned to the laboratory.
3-37
-------
n
D
E
N
U
0
E
R
S
Single-stage
Nucleopore
Filter Holder
(TQ)
Solenoid
Valve
low
Controller
Ball
Valve
73 1pm 120 1pm
Make-up Flow
Teflon
Single-Stage
Nucleopore
Filter Holder
(TT)
Ball
Valve
Solenoid
Valve
Controller
Ball
Valve
To Pump
40 Elements
from Na to Pb
Figure 3-9. Flow diagram of the PM,0 sequential filter sampler (Chow et al, 1993d).
3-38
-------
Teflon filters
Qiura filters
Nylon Filters
Cellulose Filters
TV/on
Prs-Samnling
Qravimatfy
and Sabs
I
Accsptinc*
Testing
i
i~—
Refrigerated
Storage
Assemble
Rlt«r Packs
*
Traniminal
to Raid
*
Raid Sampling
1
Triramittal to
Laboratory
i
Disassemble
1 1 1
Aceaptanca Accaptanca
Tasting Testing
Atomic Absorption
-------
-------
4.0 SAMPLING AND ANALYSIS STRATEGIES
4.1 General Approach
The preceding sections have identified different methods for PM10 sampling and chemical
analysis. These sections have emphasized that chemical analysis of PM10 samples mu^ be
closely coupled with the appropriate sampling methods and filter handlmg procedSes This
" "** hto SpedfiC »* - be ^ «*• »
The first step is to determine the specific monitoring objectives. Compliance
lST8 aPri0mneilt' "ld C°ntr01 Strategy eval-tionJare the mostTonTon
for PM10 non-attainment areas. Compliance determination requires that PM10 mass
T' 6Ve7 **"* Mfa« a U'S- ^-designated reference or equvS
sampler. As noted in earlier sections, substantial guidance has been given by U S EPA for
compliance monitoring, and this is not repeated here. The important point to remember is that
e T C°m?ianCe m0nit0ring meth0dS iS n0t SUffi*ent to Provide «5£ a^enabfe
,H v ' I0111'6 aPP°rtionment ^d co^ol strategy evaluation require cheS
, so additional measures must be taken when these objectives are to be addressed
The second step is to determine which chemicals need to be measured and at what levels
they are expected. When source apportionment is an objective, it is desirab e to oblat
chemicals winch are present in the sources which are suspected of contributing ^o PM 0 TabS
4-1 identifies several source types which are commonly found in PM10' non attainment area
S?t2? J^ ? ChemiCaIS WhiCh "* lmm t0 be Present fa ^ese 3ourcTimL"i
This table can be used in conjunction with Table 4-2 to determine which methods should be
applied to obtain the needed measurements. metnoas should be
P°tential c°ntributors ^ often be determined from emissions inventory summaries
as that illustrated in Table 4-3. These inventories should include emissions TstinSSsfor
suspended particles, carbon monoxide (CO), sulfur dioxide (SO^, nitrogenoxitoflST^i^
organic compounds (VOCs), and ammonia (NH3), if possible. The" gaseous pre?utors are
needed to assess whether or not secondary aerosol might contribute to
S£T f % C0nf Ct£d to °btain to**** maps ** soa conservation fu^eys PerioS of
illing fertilizing, and grazing might be indicative of elevated emissions from mese activities
Local fire departments, the National Forest Service, the Bureau of Land"mgement and
fire management agencies can often supply information on local burning eveSs
4-1
-------
Source Type
Geological Material
Table 4-1
Typical chemical abundances in source emissions
Dominant
Particle Size
Coarse
Motor Vehicle
Fine
Vegetative Burning
Fine
Residual Oil Combustion
Fine
<0.1%
Cr
Za
~Rb
Sr
Zr
Cr
Ni
Y+
Ca
Mn
Fe
Zn
Br
Rb
Pb
K+
OC
Cl
Ti
Cr
Co
Ga
Se
0.1 to 1%
ci-
NOi
SO^
NHJ
P
S
Cl
Ti
Mn
Ba
La
' NHJ
Si
Cl
Al
Si
P
Ca
Km
Fe
Zn
Br
Pb
NOj
so4-
NHJ
Na*
Na+
NHJ
Zn
Fe
Si
1 to 10% > 10
OC
EC
Al
K
Ca
K
Ca
Fe
S
ci-
N03-
so4-
NHJ
K+
K
Cl
ci-
Ni
OC
EC
V
• «MM^^
Si
OC
EC
OC
EC
S
SO4=
4-2
-------
Source Type
Incinerator
Table 4-1 (continued)
Typical chemical abundances in source emissions
Dominant Chemiral Ahm
Particle Size
Coal Fired Power Plant
Fine
Marine
Coarse
<0.1%
V
Mn
Cu
Ag
Sn
Cl
Cr
Mn
Ga
As
Se
Br
Rb
Zr
Ti
V
Ni
Sr
Zr
Pd
Ag *
Sn
Sb
Pb
0.1 to 1%
K+
Al
Ti
Zn
Hg
. NH4+
P
K
Ti
V
Ni
Zn
Sr
Ba
Pb
K
Ca
Fe
Cu
Zn
Ba
La
Al
Si
1 to 10%
NOj
Na+
EC
Si
S
Ca
Fe
Br
La
Pb
S04~
OC
EC
Al
S
Ca
Fe
NOj
S04
OC
EC
>10?
sor
NH?
OC
Cl
Si
Na+
ci-
Na
Cl
4-3
-------
.g-gj 8 8 8 88888 8888
> vo vo vo vo vo vo vo vo vo
»
-------
vo v
t en
vo ve
en en
vo vo vo vo n
§ss
d d o
.
-------
Table 4-3-
Summary of 1989 emissions inventory in the San Joaquin Valley*
V* '"•-- — —•••••» * vintjt A^UT j i
Soeciesb 1
Source
Stationary Fuel Combustion
(agricultural, oil & gas production,
petroleum refining, other manufacturing,
industrial, electric util., other services
& commerce, residential)
Stationary Waste Burning
(agricultural debris, range and forest
management, incineration)
Stationary Solvent Use
(dry cleaning, degreasing, architectural
coating, asphalt paving, printing, consumer
products, industrial solvent use)
Stationary Petroleum Processing, Storage,
and Transfer
(oil & gas extraction, petroleum refining
and marketing)
Stationary Industrial Processes
(chemical, food, agricultural, mineral and
metal processing, wood and paper
industries)
Stationary Miscellaneous
Processes
(pesticide application, farming, construction
and demolition, road dust, unplanned
fires , waste disposal, natural sources)
Mobile On-Road Vehicles
(light duty passenger, light and medium
duty trucks, heavy duty gas and diesel
trucks, motorcycles, and buses)
County
North San Joaquiif
Fresno
Central San Joaquind
Kern
All
North San Joaquin0
Fresno
Central San Joaquind
Kerfl
All
North San Joaquin0
Fresno
Central San Joaquind
Kern
All
North San Joaquin0
Fresno
Central San Joaqumd
Kern
All
North San. Joaquin6
Fresno
Central San Joaquind
Kern
All
North San Joaquin0
Fresno
Central San Joaquind
Kern
All
North San Joaquin6
Fresno
Central San Joaquind
Kem
All
TOG
2.2
1.0
0.9
33
37.1
16.4
2.5
8.4
2.3
29.6
33.4
24
12.2
15
84.6
8.8
24
3.2
430
466.0
3.6
3.9
0.8
0.4
8.7
74.5
230
19.7
78
402.2
65.1
35
23.9
29
153
ROG
1.2
0.5
0.5
10
12.2
12
1.0
6.1
1.6
20.7
31.6-
22
11.4
13
78.0
4.3
12
1.9
300
318.2
3.2
3.8
0.7
0.3
8.0
29.4
16
17.3
33
95.7
59.6
33
22.5
27
142.1
NO.
17.5
18
5.2
160
200.7
0.3
__
0.3
-
—
—
0.1
0.8
0.9
3.4
5 5
•/ **J
8.9
0.1
0.4
1.1
3.4-
5.0"
99
47
40
56
242
SO. CO
3.5 17.6
8.9 5.6
1.5 8.9
20 . 37
33.9 69.1
109.3
5 4
J.*T
63
15
192.7
0.2
-
0.2
0.1
03 0 ^
V/.J \JfJ
1.4 0.2
1.8 0.5
5.3
i «
i fmj "
0.9
— 0.2
6.8 1.1
9.3
28
75
220
332.3
9.4 460
4.9 230
4.1 174
6.0 200
.24.4 1,064
I
3
0
14
'
6
1
21
I
J
;
0.
24;
14.1
235
290
180
280
985
10.3
' 5'4
4.6
6.7
27.0
4-6
-------
Table 4-3 (continued)
Summary of 1989 emissions inventory in the San Joaquin Valley*
(Annualized Tons/Day)
Source
Other Mobile Sources
(off road vehicles, trams, ships, aircraft,
mobile and utility equipment)
All Sources
County
North San Joaquinc
Fresno
Central San Joaqumd
Kern
All
North San Joaquin6 229
Fresno
Central San Joaquind 80
Kern
All
TOG
24.2
11
10.9
10
56.1
129
130
80 .
fa)
39
ROG
22.9
11
10.2
9.8
53.9
164
99
70
400
733
NO.
33.2
23
21.3
21
98.5
153
95
67
240
555
SO.
3.9
2.3
2.0
2.0
10.2
22.4
18
7.6
30-
78
CO
137
73
51
55
316
734
340
369
530
1,973
PM,n
6.2
=2.8
2.5
2.3
13.8
272
310
196
300
1,078
2 California Air Resources Board, 1991.
b Species:
TOG: Total Organic Gases, compounds reported as equivalent amounts of methane (CH4), containing hydrogen and
one or morc other elements- ™ese include methane>
iC Gases'.comP°'mds reP°rted » equivalent amounts of methane (CH4) including all organic gases
^Vr165 SUCh " methane "d IOW m°leCUlar WdSht hal^nates. ROGs are relatively reactive
and are the most likely precursors of photochemical aerosol. *=•«-" vc
6qUiVaIent aaawas ofNO» mcludinS nitric oxide (NO) and nitrogen dioxide (NO2)
SOX: Sulfur Oxides, reported as equivalent amounts of SO2, including sulfur dioxide (SO,) and sulfur trioxide (SO3).
CO: Carbon Monoxide, a pure species that is reported as equivalent amounts of CO.
°: SSE HM:°' P^idet ta *" ° l° 10 Mm aerodynamic size r^ that are emitted in a liquid or solid phase This
mcludes dust, sand, salt spray, metallic and mineral particles, pollen, smoke, mist, and acid fumes
'• San Joaquin, Stanislaus, Merced, and Madera counties.
d King. and Tulare counties.
4-7
-------
Micromventories are also helpful for identifying potential contributors and the chemical
species which correspond to these contributions (Pace, 1979). Microinventories include detailed
surveys and locations of vacant lots, storage piles, major highways, construction sites, and
industrial operations. These are plotted on a map with notes regarding the visual appearance of
each potential emitter. For example, if several streets near the sampling site are extremely dirty
. this observation is recorded and photographs are taken. Street sweeping locations and schedules
are obtained. Roads in the vicinity of sampling sites are classified with respect to the" type of
traffic on them and whether or not they have sidewalks and paved shoulders.
Expected emissions cycles should be examined to determine sampling periods and
durations. For example, residential woodburning will usually show up on samples taken during
the night whereas agricultural burning will usually show up during the daytime. While these two
source types may be indistinguishable based on their chemical profiles, their diurnal cycles will
provide convincing evidence that one or the other is a major contributor when both activities
occur simultaneously As Table 4-1 shows", particle size is of value in separating one source
from another Particle size fractions, chemical analyses, sampling frequencies, and sample
durations need to be considered because more frequent samples, or samples taken at remote
locations, may require a sequential sampling feature to minimize operator costs. Shorter sample
durations may require a larger flow rate to obtain an adequate sample deposit for analysis. The
types of analyses and size fractions desired affect the number of sampling ports and different
niter media needed.
,*««• ?* ^ ^ IS t0 C3l'Ulate ** expected amount of deP°sit on each filter for each
chemical species and compare it to typical detection limits for the analyses being considered
The references in Appendix A provide typical concentrations which can be compared with
detection limits for the flow rates and filter sizes of different sampling systems. Urban samples
^ 81*, f°r ***** With fl°W rates as low as ~20 10° */min flow rates f<* 24-hour
to obtain an adequate deposit. The analytical laboratory should be involved at the
«** -thods, filter
-
and 2-2 i
fOUrth SteP JS l° apply' Create' adapt' or Purchase the sampling system which
C°St-e,ffeCtive ** reliable means Meeting the monitoring needs T*les£l
several sampler designs which have been applied to PM10 studies Some of
WWCh C3n alS° detennine «« with <* Vo sLdar" in
however, especially those with many contributing sources unknown
1111 " "
The final step is to create a written plan which specifies the study objectives samnlina
locations analysis methods filter media, sampling systen^, sampling frequences ^d dSS
nominal flow rates, methods and schedules for inlet cleaning, calibration and performance
4-8
-------
filter transport and handling procedures, database management system, data analysis methods
and record keeping protocols. A representative flow diagram of sampling and analysis strategies
is shown in Figure 4-1, while Table 44 contains a typical outline for a ftudy plan Such ?S
to car^ out as
hmvi A * Pr0af?n describes an ideal program which may require several
hundred thousand doUars to complete.. Such expenditures are often worthwhile when costly
pollution control decisions must be made, since these decisions may result in tens of millions
of dollars of expenditures. These expenditures cannot always be justified without some pilot
stodies using existing equipment and samples to provide screening analysis. Sometimes these
initial analyses canprovide information which is sufficient to design the desired control strategy
and further measurements are not needed. The following sub-sections provide guidance on whai
can-be done with different sampling and analysis configurations in a step-wise fashion
4.2 Analysis of Archived PM10 Filters from High-Volume Samplers
mrelv t ? f ' J T* **** ** ^ without ** mtent of chemica* analysis can
rarely be used to provide defensible chemical concentrations for source apportionment
Chemical measurements are still useful in a semi-quantitative or qualitative sense to identify'
though not o quantify, the major source types which contribute to high PM10 concenSns
to ^f^me m?rSlte Va?b,mt?' E1Cmenta1' 10n' «* Carbon ^lysis methods can be appHed
to these filters subject to the limitations stated in- Section 3. Archived 20.32 cm x 25 40 cm
quartz-fiber filters should be re-weighed prior to sectioning, and the re-we^ should b^
compared with the final weight which was taken immediately following samplS TOs WU1
" nitrates)
excess 0 ? *%** *?*"* ** th08C Which exhibited PM- concentrations in
excess of 150 Mg/m3 Filters from all sites within the air quality management area on an
exceedance day should be examined, even though the PM10 standard may not be exceeded *
every site. Differences in chemical content among sites, coupled with kn^S£
-------
I Establish Study Objectives |
Examine
Emissions
Inventory
Review
Meteorological
Data
Assemble
Historical Mass
and Chemical Data
Select Sampling Locations
1
Specify Species to
be Measured,
Chemical Analysis
Methods, and
Filter Media
I
Optimize
Sample Durations,
Frequencies, and
Flow Rates
I Select Sampling System
1
1
Specify
Data Management
and Validation
Procedures
Specify
Data Analysis
Methods
Prepare
Program
Plan
Conduct Study
Figure 4-1. Steps in designing a PM10 source apportionment study.
4-10
-------
Table 4-4
Example of program plan outline for PM10 measurement and modeling
1.0 INTRODUCTION
c
1.1 Background
1.2 Objectives
1.3 Overview
2.0 AIR QUALITY IN THE STUDY AREA
2,1
2.2
2.3
2.4
2.5
Emissions
Meteorology
Atmospheric Transformations
Historical PM10 Data
Implications for PM10 Study Design
3.0 DATA ANALYSIS AND MODELING
3.1
3.2
3.3
3.4
3.5
3.6
3.7
3.8
3.9
Data Evaluation -
Descriptive Air Quality Analysis
Descriptive Meteorological Analysis
Source Profile Compilation
Emissions Inventory
Receptor Model Source Apportionments
Trajectory Modeling
Secondary Aerosol Modeling
Case Study Descriptions
4.0 PROPOSED AMBIENT MONITORING NETWORK
4.1
4.2
4.3
Sampling Sites
Sampling Frequency and Duration
Sampling Methods
5.0 EMISSIONS CHARACTERIZATION
5.1
5.2
5.3
5.4
5.5
Emissions Activities and Microinventories
Geological Source Profiles
Motor Vehicle Exhaust Characterization
Residential Wood Combustion Characterization
Other Source Characterization
4-11
-------
'Table 4-4 (continued)
Example of program plan outline for PMW measurement and modeling
6.0 LABORATORY OPERATIONS
6.1 Substrate Preparation
6.2 Gravimetric Analysis
6.3 Light Absorption
6.4 Elemental Analysis
6.5 Carbon Analysis
6.6 Filter Extraction
6.7 Ion Analysis
6.8 Specialized Analysis
7.0 QUALITY ASSURANCE
7.1 Standard Operating Procedures
7.2 Performance Tests
7.3 Quality Audits
7.4 Standard Traceability
8.0 DATA PROCESSING, MANAGEMENT, AND CHAIN-OF-CUSTODY
8.1 Data Base Requirements
8.2 Levels of Data Validation
8.3 Continuous Data Processing
8.4 Substrate Data Processing
9.0 MANAGEMENT, REPORTING, AND SCHEDULE
9.1 Tasks and Responsibilities
9.2 Resource Requirements
9.3 Reports
9.4 Schedule and Milestones
10.0 REFERENCES
4-12
-------
A quick examination of particle sizes on the filter under a reflecting microscope can often
reveal whether or not the particles are truly PM10 or are the result of inlet re-enlin^ent o?
^ge Particle conjunction. A large proportion of particles exceeding 10 microns^lcates
that there may have been a problem with the sampling system, and that the elevated
concentration may not really represent high PM10 levels in me atmosphere at *e time of
4.3 Planned High-Volume PM10 Sampling
tv
amlyses wiU be aPPlied to some or aU of the 20.32 cm x
U8Cd 'm a *&•**** PM10 sampler, the following precaution^
blank concentrations shou^te
the
for h h ons sou
for each chemicd to be quantified. Each box should be labelled when it is received from
vendor and one filter from each box should be submitted to the same chemical analvS
erf WhlCh ^ ^f aPPliCd t0 aU fflters' If «» blank levels ^^SStTrfS
expected concenttations for any of the chemical concentrations to be analyzed the box should
be returned to the manufacturer. Specifications of maximum tolerable S^^SS
agreement will offer the opportunity to obtain replacements at no additional.
W?Ch CSn be mated t0 ** h^votame PM10 sampler should be obtained
f-hiflldBlll0aded USing gl°Ved hands ^ a Sbora^ settmg Each £
should be fo ded ni half with the exposed side inward and stored in a Zip-lock bag The' e bags
Wlth ** C0°
High-Volume and Dichotomous PM10 Sampling
4.4
ooor foe1e,' quartz-fiber filters used ^ high-volume sampling are especially
poor for elemental measurements owing to the penetration of particles into the filter and hi ah
j=g
4-13
-------
reference samplers, compliance can be determined from either sampler. All filter media should
undergo the acceptance testing, handling, and storage procedures described earlier.
4.5 High-Volume or Dichotomous PM10 and Continuous PM10 Sampling
A continuous TEOM or BAM can be operated along with a high-volume or dichotomous
PMI(, sampling system. This configuration is most useful when short-term events, such as fires
or windblown dust, are hypothesized to be major contributors to excessive PM10 concentrations
The dichotomous sampler using Teflon-membrane filters is preferred, since this allows particle
size as well as elements and mass to be measured. When the TEOM is equipped with the bypass
channel, a quartz-fiber filter can be taken simultaneously with the hourly measurements to be
analyzed for ions and carbon. If a high-volume PM10 sampler with a quartz-fiber filter is- used,
^ bypass should use a Teflon-membrane filter for elemental analysis.
4.6 Sequential Filter Sampling
When high PM10 levels are suspected to result from multi-day buildup of a variety of
sources, it is desirable to have daily samples available which can be submitted to analysis
High-volume and dichotomous PM10 sampling can be applied to this task, but this requires
someone to change the filters at midnight every night, or several samplers and a timing
mechanism to switch between them. Manpower and equipment costs can become prohibitive
Many sampling sites have limited space and cannot accommodate a large number, of sampling
systems. In this case, Sequential Filter Samplers (SFSs) using Teflon-membrane filters for mass
and elemental analysis and quartz-fiber filters for ion and carbon analysis are a good choice.
The SFS can also be applied to situations where more than one sample per day is needed to
bracket emissions events with samples amenable to chemical analysis. In this case two to six
samples of four- to twelve-hours duration are taken sequentially and analyzed separately for the
desired chemical species.
4.7 Saturation Sampling
There may be cases where one or more source categories are identified as major
contributors to elevated PM10, but the chemical profiles of specific emitters are too similar to
differentiate them from each other. In this case, the portable survey samplers using Teflon-
membrane filters can be located within and around the suspected emitters (Watson et al 199lb)
If the objective of the study is to characterize fugitive dust sources, mass and elemental' analyses
are sufficient to separate this source category from others by receptor modeling Many past
studies have applied the portable survey sampling approach to characterize the impact of
residential wood combustion. In this case, collocated samplers with Teflon-membrane and
quartz-fiber filters are required for full chemical speciation. The remaining geological source
4-14
-------
t0 Mentify **locations of sPec^ emssions
4.8 Denuder Difference Sampling
In cases where secondary ammonium sulfate and ammonium nitrate are
contnbutors, one or more sites should be operated to obtain precursor TnceSoi of c
acid and ammonia gas (e.g., Chow et al, 1993a). In the extern United Stat? TuTfuric^dd
te aSThm ^ ***** COmP°nents' * «• Cation, denuder meSs can
be applied to obtain accurate measures of the secondary aerosol and the precursor sase^ These
SS? ^ me™ntS ShOUld be accomP^ by collocated tL£^*£'££
hurmdity measures so that equilibrium receptor models (e.g., Watson et. al 1994a) can be
4 o
4-15
-------
-------
5.0 SUMMARY
o r^ ofus?lspended P3*10168 * necessary, along with the application
of receptor models, to apportion ambient concentrations to their sources for the development of
l^TJ^°n^ 'T8- • ^ dOCUment identifies CUirent technology for the sampling and
analysis of PM10 and its chemical constituents on filter deposits.
Particle sampling on filters is the most practical method currently available to
characterize fce sizes and chemical compositions of PM10 and its sub-fractions. Ambient aeroso°
sampling systems consist of a combination of monitoring hardware, filter media, laboratory
SSSl: *£ QP?T8 pr?.cedUreS which m specifically tailored to different monitoring
objectives. No single sampling system can meet all needs, and it is often necessary to adap*
existing sampling components to the specific situation being studied. Examples of successful
°!mter dep°SitS Cann0t be separated from me methods used to obtain
fc ChemCal ""fr*8 requkes strinSent attention to choice of filter media
sample handling, sample storage, and to the sampler used to obtain the filter deposits mS
svst^s ££" 1S Hmtended ^ S°UrCe aPp0rtionment recePtor modeling, sequential samp^g
systems, particle and gas sampling systems with denuders, portable samplers, dichotomous
samplers, or a combination of several samplers may be needed. ""wmous
These
mechanical dev*e used to acquire the sampj The laborato^
analyses to be applied, the type of filters which are amendable to those analyses the mSmum
deposits needed on these filters, the sampling hardware which extracts polXaSs SHE
atmosphere onto the filters, and the procedures which assure the accuracy prcci^on and
validity of the acquired atmospheric concentrations must all be considered
S
improvements which should be incorporated into future plans. Y fy
in
identlfied to provide
5-1
-------
-------
6.0 REFERENCES
Ahfterg M.S and F.C. Adams (1978). "Experimental Comparison of Photon and
Partxcle-Induced X-Ray Emission Analysis of Air Particulate Matter." X-Ray Spectrometry ,
'/' *£ Bourbon» P- Chevin, c- Delaunay, J. Escalassan, and J.D. Lepert (1974) "New
^ Detennmation of Nitrogen Dioxide in Polluted Atmospheres Derived from the Griess-
Saltzmann Method." Water, Air, Soil Pollux., 3:555 (in French).
Ar ' H'L Schiff' G'L Mackay> R'D- Braman'
)-, / ComPffon of T^66 Methods for Measurement of Atmospheric Nitric Acid and
Aerosol Nitrate and Ammonium." Atmos. Environ., 19(2):325-333.
Appel B.RPColodny, and JJ. Wesolowski (1976). "Analysis of Carbonaceous Materials
in Southern California Atmospheric Aerosols." Environ. Sci. Technol., 10:359-363
Appel, B.R., E.M. Hoffer, E.L. Kothny, S.M. Wall, M. Halik, and R.L. Knights (1979)
?3 °98aCe°US Material inS°Uthern California Atmospheric Aerosols-2 " Environ.
Arinc F L. Wielopolski, and R.P. Gardner (1977). "The Linear Least-Squares Analysis o
X-Ray Fluorescence Spectra of Aerosol Samples Using Pure Element Library Standards and
Photon Excitation/ In X-Ry Fluorescence Analysis of Environmental Samptes, T.G. Dz^bay
Ed. Ann Arbor Science Publishers, Ann Arbor, MI, p. 227. ^»ay,
Barnes, B.A., WJ. Roddy, and J.C. Pheasant (1988). "Beta Attenuation Monitoring for PM10 "
fc Transactions, PM1Q: Implementation of Standards, C.V. Mathai and D.H. Stonefield Eds
Air Pollution Control Association, Pittsburgh, PA, pp. 157-170. ^oneneia, fcds.
r ^ M' ^1OT (1,988)- "^ PartiCUlate RecePt0r Modeling * LM Vegas Using
Gaseous and Particulate Source Profiles." In Transactions, PM10: ImplementatioTof
Standards, C.V. Mathai, Ed. Air Pollution Control Association, Pittsburgh, P/, p^ 518 -530
ofd" °iH' LUf ^^ POM' °' Pteinmg' and P' **&* <1979)- '"^e Size Distribution
of the Urban Aerosol in Vienna. " Sci. Tptal Environ. , 13:245-261 .
L-F< P°rter' A-E" ***** «* FJ' Toth <1978)- "Analysis of Air
mxo&zphy: Comparison with Accepted Methods." In Ion
Chromatographic Analysis of Environmental Pollutants, E. Sawicki JD Mulik and F
Wittgenstein, Eds. Ann Arbor Science Publishers, Inc., Ann AtS ? MI ppls-76
6-1
-------
Buzzard, G.H. and J.P. Bell (1980). "Experimental Filtration Efficiencies for Large Pore
Nuclepore Filters." /. Aerosol ScL, 11:435-438.
Cadle, S.H., P.J. Groblicki, and D.P. Stroup (1980a). "An Automated Carbon Analyzer for
Particulate Samples." Anal. Chem., 52:2201-2206.
Cadle, S.H., G.J. Nebel, andR.L. Williams (1980b). "Measurements of Unregulated Emissions
from General Motors' Light-Duty Vehicles." Document 790694, Society of Automotive
Engineers Transactions, 87:2381-2401.
Cadle, S.H. and P.J. Groblicki (1982). "An Evaluation of Methods for the Determination of
Organic and Elemental Carbon in Particulate Samples." In Particulate Carbon: Atmospheric
Life Cycles, G.T. Wolff and R.L. Klimisch, Eds. - Plenum Press, New York, NY, pp. 89-109.
Cahill, T.A. (1980). "Proton Microbes and Particle-Induced X-Ray Analytical Systems " Ann
Rev. Nucl. Particle Sci., 30:211-252.
Cahill, T.A., R.A. Eldred, P.J. Feeney, P.J. Beveridge, and L.K. Wilkinson (1990) "The
Stacked Filter Unit Revisited." In Transactions, Visibility and Fine Panicles, C.V. Mathai Ed
Air & Waste Management Association, Pittsburgh, PA, p. 213.
California Air Resources Board (1991). "Emission Inventory 1989." Technical Support
Division, California Air Resources Board, Sacramento, CA
' ©
o™ 'C- Henderson> RJ- L*. P-K. Hopke, andG.M. Sverdrup
(1989). The Use of CCSEM and Microimaging to Study Source/Receptor Relationships " In
Transactions: Receptor Models in Air Resources Management, J.G. Watson Ed Air& Waste
Management Association, Pittsburgh, PA, pp. 39-58.
Chan, T. and M. Lippmann (1977). "Particle Collection Efficiencies of Sampling Cyclones-
An Empirical Theory." Environ. ScL TechnoL, ll(4):377-386.
Chan, M.C.. K.C. Moon, and J.C. Chow (1990). "PM10 Monitoring in the San Joaquin
Valley." Document AV-FR-89/6121, prepared for San Joaquin Valleywide Air Pollution sLy
Agency and the Western States Petroleum Association by AV Projects, Inc., Monrovia, CA.
MA
: Wa^°n' ^ E; Moore (1980>- Automated Ammonium Analysis Procedure
6000-215., Environmental Research and Technology, Inc.,
6-2
-------
ss .
Document 8086. 1D2, prepared for State of Nevada by Desert Research tattote^So,
Protection Agency by Desert Research Institute, Reno NV.
fs*JW£s ~
Department of Environmental Quality, Portland, OR.
6-3
-------
Chow, J.C., L.C. Pritehett, Z. Lu, B. Hinsvark, and S. Chandra (1989d). "A Neighborhood-
Scale Study of PMjo Source Contributions in Rubidoux, CA, Vol. HI: Chemical Mass Balance
Receptor Modeling Results." DRI Document 8707.1F3, prepared for South Coast Air Quality
Management District by Desert Research Institute, Reno, NV.
Chow, J.C. and L.W. Richards (1990). "San Joaquin Valley Air Quality Study
(SJVAQS)/Atmospheric Utility Signatures -Predictions and Experiment (AUSPEX) Monitoring
and Analysis for Aerosols and Visibility Volume I: Program Plan." DRI Document 8743.IF
Prepared for Pacific Gas and Electric Company, San Francisco, CA, by Desert Research
Institute, Reno, NV.
Chow, J.C., J.G. Watson, J.L. Bowen, C.A. Frazier, A.W. Gertler, B. Hinsvark, and K F
Fung (1990a). "Laboratory Operations Manual for the California Acid Deposition Monitoring
Program: Sampler Pretreatment, Sample Preparation, and Chemical Analysis." DRI Document
8068.1F4, prepared for the California Ah- Resources Board, Sacramento, CA by the Desert
Research Institute, Reno, NV.
Chow, J.C., J.G. Watson, R.T. Egami,- C.A. Frazier, Z. Lu, A. Goodrich and A. Bird (1990b).
"Evaluation of Regenerative-Air Vacuum Street Sweeping on Geological Contributions to PM,
J. Air Waste Manage. Assoc, 40:1134-1142.
Mo-
Chow, J.C., J.G. Watson, D.H. Lowenthal, L.C. Pritehett, and L.W. Richards (1990c) "San
Joaquin Valley Air Quality Study Phase 2: PM10 Modeling and Analysis, Vol. I: Receptor
Modeling Source Apportionment." DRI Document 8929. 1FS prepared for San Joaquin Valley
Air Pollution Study Agency c/o California Air Resources Board by Desert Research Institute
Reno, NV.
Chow, J.C., J.G. Watson, J.L Bowen, C.A. Frazier, A.W. Gertler, and B. Hinsvark (1990d)
Laboratory Operations Manual for the California Acid Deposition Monitoring Program-
Sample Pretreatment, Sampler Preparation, and Chemical Analysis." Final Report DRI
Document 8068. 1F4. Prepared for California Air Resources Board, Sacramento, CA. '
Chow, J.C., J.G. Watson, L.W. Richards, D.L. Haase, C. McDade, D.L. Dietrich D Moon
and C. Sloane (1991a) "The 1989-90 Phoenix PM10 Study, Vol. H: Source Apportionment. :
DRI Document 8931.6F1, prepared for Arizona Department of Environmental Quality by Desert
Research Institute, Reno, NV. y
Chow J.C., J.G. Watson, L.W. Richards, D.L. Haase, C. McDade, D.L. Dietrich D Moon
and C. Sloane (1991b). "The 1989-90 Pilot Tucson PM10 Study, Vol. II: ' Source
Apportionment. DRI Document 8931.8F1, prepared for Arizona Department of Environmental
Quality by Desert Research Institute, Reno, NV.
M' Lowentha1' C'L- Frazier> B.A. Hinsvark, L.C. Pritehett, and
"Wintertime PM10 and PM2.5 Chemical Compositions and Source
w
G. Neuroth (1992a).
6-4
-------
'-
Appomonment in California's San Joa^in
L'W- Richards'
Califomia's
S.D. Ztaan
Aerosol.
Code of Federal Regulations (1988). 40 CFR, Part 50, Appendix J
6-5
-------
Conner, T.L., J.L. Miller, R.D. Willis, R.B. Kellogg, and T.F. Dann (1993). "Source
Apportionment of Fine and Coarse Particles in Southern Ontario, Canada." Paper 93-TP-58.05.
Presented at the 86th Annual Meeting, Denver, CO. Air & Waste Management Association
Pittsburgh, PA.
Cooper, J.A., and J.G. Watson (1979). "Portland Aerosol Characterization Study." Final
Report to the State of Oregon, Department of Environmental Quality, Portland, OR.
Cooper, J.A., J.W. Watson, and JJ. Huntzicker (1979). "Summary of the Portland Aerosol
Characterization Study." Paper 79-24.4. Presented at the 72nd Annual Meeting, Cincinnati,
OH. Air Pollution Control Association, Pittsburgh, PA.
Countess, RJ. (1974). "Production of Aerosol by High Volume Samplers." /. Air Poll
Control Assoc., 24:605. „
Countess, R.J., M. Zeldin, and R.L. Farber (1989). "Strategies of PM10 Compliance in the
South Coast Air Basin: Meteorological and Co-Pollutant.Factors." Presented at the 82nd
Annual Meeting, Anaheim, CA. Air & Waste Management Association, Pittsburgh, PA.
Countess, RJ. (1990). "Inter-Laboratory Analyses of Carbonaceous Aerosol Samples " Aerosol
Sd. TechnoL, 12:114-121.
Countess, RJ. (1991). "Santa Barbara PMi0 Emission Reduction Study." Paper 91-52.5,
presented at the 84th Annual Meeting, Vancouver, British Columbia, Canada. Air & Waste
Management Association, Pittsburgh, PA.
Courtney, W.J., R.W. Shaw, and T.G. Dzubay (1982). "Precision and Accuracy of a
Beta-Gauge for Aerosol Mass Determination." Environ. Sd. TechnoL, 16:236-238.
Coutant, R.W. (1977). "Effect of Environmental Variables on Collection of Atmospheric
Sulfate." Environ. Sd. TechnoL, 11:873-878. -
Criss, J.W. (1976). "Particle Size and Composition Effects in X-Ray Fluorescence Analysis of
Pollution Samples." Anal. Chem., 48:1.
Currie, L.A. (1982). "Contemporary Paniculate Carbon." l& Paniculate Carbon: Atmospheric
Life Cycle, G.T. Wolff and R.L. Klimisch, Eds. Plenum Press, New York, NY, pp. 245-260.
Daisey, J.M., RJ. McCaffrey, andR.A. Gallagher (1981). "Polycyclic Aromatic Hydrocarbons
and Total Extractable Paniculate Organic Matter in the Arctic Aerosol." Atmos Environ
15:1353-1363. . '
Dams, R., J.A. Robbins, K.A. Rahn, and J.W. Winchester (1970). "Non-Destructive Neutron
Activation Analysis of Air Pollution Particulates." Anal. Chem., 42:861.
6-6
-------
Daum, P.H. and D JP. Leahy (1985). "The Brookhaven National Laboratory Filter Pack System
ta Collect™ and Determination of Air Pollux/ Brookhaven
Davis, w. (1992). California Air Resources Board, Sacramento, CA. Personal communication
DeCesar R.T., and J.A. Cooper (1982b). "Evaluation of Multivariate and Chemical Mass
of faeversibte Absoiption
, Lawrence Berkeley Laboratory, Berkeley, CA.
- Blata(1980'- "Mixtureforlmpregnaaonof Air Filters.' Czechoslovakia'
Drane, E.A., D.G. Branton, S.H. Tysinger, and W J Courtnev HQ8^ »r>o^ u
^
6-7
-------
Dzubay, T.G. and R.K. Barbour (1983). "A Method to Improve the Adhesion of Aerosol
Particles on Teflon Filters." JAPCA, 33:692.
Dzubay, T.G. (1986). "Analysis of Aerosol Samples by X-Ray Fluorescence.1
Environmental Protection Agency, Research Triangle Park, NC.
U.S.
Eatough, D.J., N. Aghdaie, M. Cottam, T. Gammon, L.D. Hansen, E.A. Lewis, and R.J.
Farber (1990). "Loss of Semi-volatile Organic Compounds from Particles During Sampling on
Filters." In Transactions, Visibility and Fine Particles, C.V. Mathai, Ed. Air & Waste
Management Association, Pittsburgh, PA, pp. 146-156.
Eatough, p.J. (1993). "Determination of the Size Distribution and Chemical Composition of
Fine Participate Semi-Volatile Organic Compounds Using Diffusion Denuder Technology:
Results of the 1992 Study in Azusa, California." Department of Chemistry, Brigham Young
University, Prove, UT.
Eatough, D.J., A. Wadsworth, D.A. Eatough, J.W. Crawford, L.D. Hansen, and E.A. Lewis
(1993a). "A Multiple-System, Multi-Channel Diffusion Denuder Sampler for the Determination
of Fine-Particulate Organic Material hi the Atmosphere." Atmos. Environ., 27A(8): 1213-1219.
Eatough, D.J., H. Tang, and J. Machir (1993b). "The Particle Size Distribution and Chemical
Composition of Semi-Volatile Organic Compounds Lost from Atmospheric Fine Particles During
Sampling." Paper 93-RA-l 10.04. Presented at the 86th Annual Meeting, Denver, CO. Air &
Waste Management Association, Pittsburgh, PA.
Eldred, R.A., T.A. Cahill, L.K. Wilkinson, P.J. Feeney, J.C. Chow, and W.C. Malm (1990).
"Measurement of Fine Particles and Their Components in the NPS/IMPROVE Network." In
Transactions, Visibility and Fine Particles, C.V. Mathai, Ed. Air & Waste Management
Association, Pittsburgh, PA, pp. 187-196.
Eldred, R.A. (1993). Persona.l Communication. Crocker Nuclear Laboratory University of
California, Davis, CA.
Engelbrecht, D.R., T.A. Cahill, and PJ. Feeney (1980). "Electrostatic Effects on Gravimetric
Analysis of Membrane Filters." /. Air Poll Control Assoc., 30:391-392.
Evans, J.S. and P.B. Ryan (1983). "Statistical Uncertainties in Aerosol Mass Concentrations
Measured by Virtual Impactors." Aerosol Sci. TechnoL, 2:531-536.
Fairley, D., R. De Mandel, M. Rothenberg, and T. Perardi (1992). "Results from the 1991-92
Pilot Study of Wintertime PM10 hi the San Francisco Bay Area." Document BAAQMD TM
92002. Bay Area Air Quality Management District, Planning and Research Division San
Francisco, CA.
6-8
-------
Coupled Plasma-°ptical
Federal Register (1982). "Reference Method for the Determination of Suspended Particulate
Meth°d> " 40 CF* *« 50.-
Federal Register (1983). "Reference Method for the Determination of Suspended Particulate
Mattery the Atmosphere (High-Volume Method) - 40 CFR Part 50." Federal
Federal Register (1987a). "Revisions to the National Ambient Air Quality Standards for
Peculate Matter: 40 CFR parts 51 and 52. " Federal Register, 52:24634 JulyT
•-»-. * *
l tePlementta8 »«*- Patticulate Matter Standards:
51 and 52. Federal Register, 52:24672, July 1.
Fusitive
40
: 40 CFR
Federal Register (1987f). "Rules and Regulations." Federal Register, 52:29383, August 7.
Federal Register (1987g). "Rules and Regulations." Federal Register, 52:29383, August 7.
. "Reference Method for the Determination of Particle Matter as PM
!.' Federal Register, 52:24664 July 1.
for Mtw PM
'°
for A* Quaiity
6-9
-------
Feeney, P.J., T.A. Cahffl, J. Olivera, and R. Guidara (1984). "Gravimetric Determination of
Mass on Lightly Loaded Membrane Paters." /. Air Poll. Control Assoc., 34:367-378.
Perm, M. (1979). "Method for Determination of Atmospheric Ammonia." Atmos. Environ. ,
13:1385-1393.
Perm. M. (1986). "A NaCO3-Coated Denuder and Filter for Determination of Gaseous HNO
in the Atmosphere. " Atmos. Environ. , 26: 1 193-1201 .
Fernandez, P. J. (1989). "Atomic Absorption Spectroscopy . " In Methods of Air Sampling and
Analysis, 3rd Ed., J.P. Lodge, Jr., Ed. Lewis Publishers, Chelsea, MI, pp. 143-150.
Fitz, D., M. Chan, G. Cass, D. Lawson, and L. Ashbaugh (1989). "A Multi-Component Size-
Classifying Aerosol and Gas Sampler for Ambient Air Monitoring. " Presented at 82nd Annual
Meeting, Anaheim, CA. Air & Waste Management Asspciation, Pittsburgh, PA.
Forrest, J. and L. Newman (1973). "Sampling and Analysis of Atmospheric Sulfur Compounds
for Isotope Ratio Studies." Atmos. Environ., 7:561-573.
Fujita, E.M. and J.F. Collins (1989). "Quality Assurance for the Southern California Air
Quality Study. " Presented at 82nd Annual Meeting, Anaheim, CA. Air & Waste Management
Association, Pittsburgh, PA.
Fung, K.K., S.L. Heisler, A. Price, B.V. Nuesca, and P.K. Mueller (1979). "Comparison of
Ion Chromatography and Automated Wet Chemical Methods for Analysis of Sulfate and Nitrate
in Ambient ^articulate Filter Samples." In Ion Chromatographic Analysis of Environmental
Pollutants, Vol. 2, E. Sawicki and J.D. Mulik, Eds. Ann Arbor Science Publishers, Inc Ann
Arbor, MI, pp. 203-209. ''
SSP/A?' (1988)' 'IArtifacts 'm me Sampling of Ambient Organic Aerosols. " Presented at 1988
EPA/APCA Symposium on Measurement of Toxic and Related Air Pollutants, Raleigh NC
Air Pollution Control Association, Pittsburgh, PA. . '
Fung, K.K (1990). "Paniculate Carbon Speciation by MnO2 Oxidation." Aerosol Sci
Tecnnol., 12:122-127.
^", D
-------
J' (1974)' "Solvent Section in Entrance of Particulate Matter." Atmos. Environ.
'
-15o2.
' PJ' Li°y' LA- Co°Per> J'G- Watson> and G.R.
D™S* of Source Apportionment Studies. • Atmos. Environ. ,
'AL(19f 0)* "P!p.ical lamination of a Method for Determination of Nitrogen Dioxide
m the Atmosphere by Using Triethanolamine Filter Paper." Taiki Osen Gakkaishi, 15:334 (in
Japanese).
Extraction "d 0*a"fc Carbon Determination in Atmospheric
16 Ext^Cti0n:°rganic S^ ^^ (OE-OCA) Tec Unique."
Grosjean D^(1980) "Comments at the Second Chemical Congress of the North American
6 ^ ChemiCal C°ngreSS °f ^ North ^^^ Continent Las
d n m? AH> S?^eW (1989)' "Paramete^tion of the Formation Potential of
Secondary Organic Aerosols." Atmos. Environ., 23(8): 1733-1747.
A*«».
Harman, J.N (1989). "Inductively Coupled Plasma Emission Spectroscopy . " In Methods of Air
Sampling and Analysis, 3rd ed., J.P. Lodge, Jr., Ed. Lewis Publishers, Chelsea, MI, pp 88-92.
AAL (1f?)' , nileasurement of L^t Absorption and Elemental Carbon in
Atoosphenc Aerosol Samples from Remote Locations." In Particulate Carbon, Atmospheric
Life Cycles, G.T. Wolff and R.L. Klimisch, Eds. Plenum Press, New York, NY, pp37\ .377
Heisler S.L R.C. Henry, and J. Collins (1980a). "The Nature of the Denver Haze in
November and December of 1978." Presented at 73rd Annual Meeting, Montreal Quebec
Canada. Air Pollution Control Association, Pittsburgh, PA. iviomreai, Quebec,
Heisler, S.L R.C. Henry, J.G. Watson, and G.M. Hidy (1980b). "The 1978 Denver Winter
Haze Study " Document P5417-1, prepared for Motor Vehicle Manufacturer's Association of
the Umted States by Environmental Research and Technology, Inc., wtSSe v
Vancouver, British Columbia, Canada. Ai
of
6-11
-------
Hering, S.V., R.C. Flagan, and S.K. Friedlander (1979a). "Design and Evaluation of New
Low-Pressure Impactor-L" Environ. Sci. Technol., 12:667-673.
Hering, S.V., S.K. Friedlander, JJ. CoUins, and L.W. Richards (1979b). "Design and
Evaluation of a Low Pressure Impactor-H." Environ. Sci. Technol., 13:184-188.
Hering, S.V. and S.K. Friedlander (1982). "Origins of Aerosol Sulfur Size Distributions in the
Los Angeles Basin." Atmos. Environ., 16:2647-2656.
Hering, S.V., D.R. Lawson, I. Allegrini, A. Febo, C. Perrino, M. Pdssanzini, I.E. Sickles H
K.G. Anlauf, A. Wiebe, B.R. Appel, W. John, J. Ondo, S. Wall, R.S. Braman, R. Sutton'
G.R. Cass, P.A. Solomon, D.J. Eatough, N.L. Eatough, E.G. Ellis, D. Grosjean, B B Hicks'
J.D Womack, J. Horrocks, K.T. Knapp, T.G. Ellstad, R.J. Paur, W.J. Mitchell, M. Pleasant'
E. Peake, A. MacLean, W,R. Pierson, W. Brachaczek, H.I. Schiff, G.L Mackay, C W Spicer'
D.H. Stedman, A.M. Winer, H.W. Biermann, and E.G. Tuazon (1.988). "The Nitric Acid
Shootout: Field Comparison of Measurement Methods." Atmos. Environ,, 22:1519-1539.
Hering, S.V. (1989). "Inertial and Gravitational Collectors." In Air Sampling Instruments for
Evaluation of Atmospheric Contaminants, 7th ed., S.V. Hering, Ed. American Conference of
Governmental Industrial Hygienists, Cincinnati, OH, pp. 337-385.
Hering S.V B.R. Appel, W. Cheng, F. Salaymeh, S.H. Cadle, P.A. Mulawa, T.A. Cahill
R-A-Eldred M-Surovik, D. Fitz, I.E. Howes, K.T. Knapp, L. Stockburger, B. J. Turpin, JJ.
Huntzicker, X.-Q. Zhang, and P.H. McMurry (1990). "Comparison of Sampling Methods for
Carbonaceous Aerosols in Ambient Air." Aerosol Sci. Technol. 12:200-213.
Hering, C.V J.C. Chow, and S. Chandra (1993). "Component Testing for a Two-Week
Sampler for Fine Particle Ions and Gaseous Acids." Presented at the American Association for
Aerosol Research Twelfth Annual Meeting, Oak Brook, IL.
Houck J.E.J.C. Chow, and M.S. Ahuja (1989). "The Chemical and Size Characterization of
Participate Material Originating from Geological Sources in California." In Transactions
Receptor Models in Air Resources Management, J.G. Watson, Ed. Air Pollution Control
Association, Pittsburgh, PA, pp. 322-334.
Houck J E., J.A. Cooper, and E.R. Larson (1982a). "Dilution Sampling for Chemical
OrSr^r^TS™^'" PaPer82-61M-2 Presented at the 75th Annual Meeting, New
Orleans, LA. Air & Waste Management Association, Pittsburgh, PA.
aS/'^/;^ C™Pf,'cCA- F^ier'R' DeCesar> J'F- M<*an, D. Maughan, and J. Roberts
(1982b). Receptor Model Source Apportionment of Lead in Their Airshed with Lead Smelters "
ied'° C0"tem!""my POlUtti°" Pr°M™- ** Po»-ta
6-12
-------
Huntzicker J.J., R.L. Johnson, J.J. Shah, and R.A. Gary (1982). "Analysis of Organic and
Elemental Carbon in Ambient Aerosol by a Thennal-Optical Method. " In Paniculate Carbon
Atmospheric Life Cycles, G.I. Wolff and R.L. Klimisch, Eds. Plenum Press, New York NY'
pp. 79-88. ' '
Husar, R.B. (1974). "Atmospheric Participate Mass Monitoring with a Beta Radiation
Detector." Atmos. Environ., 8:183-188. *vauuiuuu
Illinois Environmental Protection Agency (1991). "1990 Illinois Annual Air Quality Report "
Illinois Environmental Protection Agency, Springfield, IL. '
Jaklevic J M., B.W. Loo, and F.S. Goulding (1977). "Photon-Induced X-Ray Fluorescence
Analysis Using Energy-Dispersive Detection and Dichotomous Sampler. " InX-Ray Fluorescence
Analysis of Environmental Samples, 2nd ed. , T.G. Dzubay , Ed. Ann Arbor Science Publishers
Ann Arbor, MI. • '
c ' F'Sl.GouMmg' Md B'W- Loo (1981). "A Beta-Gauge Method
Applied to Aerosol Samples." Environ. Sci. TechnoL, 15:680-686.
Japar, S.M. and W.W. Brachaczek (1984). "Artifact Sulfate Formation from SO2 on Nylon
Filters." Atmos. Environ., 18: 2479-2482.
Japar, SMA.C. Szkarlat, R.A. Gorse, Jr., E.K. Heyerdahl, R.L. Johnson, J.A. Rau, and J J
Huntzicker (1984). Comparison of Solvent Extraction and Thermal-Optical Carbon Analvsis
TechnoL,
f°r S
ve Sampling of Ambient Air."
io
. 'C- Wang (1986)' "Dry Deposition of Acidic Gases
ic Berkeley C ^ Lab°rat°ry' CaBfcndl1 Department of Health
•John, W S.M. Wall> md JL Qndo (198g) ,,A New Method for
Aerosol Measurement Using the Dichotomous Sampler." Atmos. Environ., 22:1627^1635
oh M' TWa11' LL' A0nd°',^d W' Winklmayr (1990). "Modes in the Size Distributions
of Atmospheric Inorganic Aerosol." Atmos. Environ., 24A: 2349-2359.
6-13
-------
Jdrn, W. and H.-C. Wang (1991). "Laboratory Testing Method for PM10 Samplers: Lowered
Effectiveness from Particle Loading." Aerosol ScL TechnoL, 14:93-101.
John, W., W. Winklmayr, and H.C. Wang (1991). "Particle Deagglomeration and
Reentrainment rn a PM10 Sampler." Aerosol Sci. TechnoL, 14:165-176.
Johnson, D.A. and D.H.F. Atkins (1975). "An Airborne System for the Sampling and Analysis
of Sulfur Dioxide and Atmospheric Aerosols." Atmos. Environ., 9:825-829.
Johnson, R.L. and J.J. Huntzicker (1979). "Analysis of Volatilizable and Elemental Carbon in
Ambient Aerosols." In. Proceedings, Carbonaceous Particles in the Atmosphere, T Novakov
Ed. Document #LBL-9037, Lawrence Berkeley Laboratory, Berkeley, CA, pp. 10-13.
Johnson,^R.L., JJ. Shah, and J.J. Huntzicker (1980). "Analysis of Organic, Elemental and
Carbonate Carbon in Ambient Aerosols. " In Sampling and Analysis of Toxic Organic* in the
Atmosphere. American Society for Test and Materials, p. 111.
Johnson, R.L. (1981). "Development and Evaluation of a Thermal/Optical Method for the
Analysis of Carbonaceous Aerosol." Masters Thesis, Oregon Graduate Center, Beaverton, OR.
Johnson RL.JJ Shah, R.A. Gary, and J.J. Huntzicker (1981). "An Automated
Thermal-Optical Method for the Analysis of Carbonaceous Aerosol. " In ACS Symposium Series
#167: Atmospheric Aerosol, Source/Air Quality Relationships, E.S. Macias and P K Hooke
Eds. Plenum Press, New York, NY, pp. 223-233. ' '
Kelly J.T. (1991). "Evaluation of Comparability between Portable Saturation Monitors and
°^ -Pa^late/Lead Monitors-" Project Report, Environmental Services Division,
, Region
Kevex Corporation (1986). "Kevex XRF ToolBox Reference Manual. " Document 71 80-5060a
ivevex Corporation. '
Kim, B.M., R. Lewis, H. Hogo, and J.C. Chow (1992). "Source Apportionment by Chemical
Mass Balance: A Comparison Between Measured Source Profiles and SAFER Model Estimated
r^i ?re™ I^^' PMl° Standards "* Nontraditional Paniculate Source
Controls J C Chow and D.M. Ono, Eds. Air & Waste Management Association, Pittsburgh,
•*••*»•» pp. 14o~lo2.
A-H- n T -• E"eStad (1986)' "P°llutant SamPler for Measurements of
Atmospheric Acidic Dry Deposition." Environ. Sci. TechnoL, 20(6):633-673.
6-14
-------
Koutrakis, P., J.M. Wolfson, J.L. Slater, M. Brauer, and J.D. Spengler (1988) "Evaluation
m to Conect Acidic Aeroso's '
m Spengler' GJ- Keeler, and J.L. Slater
P T Str°ng Addity L08868 Due to Interactions of Collected
Particles: Results from Laboratory and Field Studies. " Presented at the 84th Annual McetinT
Vancouver, British Columbia, Canada. Air & Waste Management Association,pSburgh ?!'
'D- Spenglef' GJ' Keeler' and J-L- Slater
Pc P r Str°ng Addity L08868 Due to Interactions of Collected
Particles: Results from Laboratory and Field Studies.'" Annas. Environ,, 26A(6): 987-995
Kufaeja, 'V.P and J.L. Bove (1976). "Determination of Free Carbon Collected on
High-Volume Glass Fiber Filter." Environ. Sci. Technol., 10:187-189. collectecl on
Kusko B. T.A. Cahill, R.A. Eldred, Y. Matsuda, and H. Miyabe (1989) "Nondestructive
by Forward
for
' N' Maykut (1992)' "Weekly Composite Sampling of
and Trace Elemental Analysis." In Transactions, PM^andards ^Nontradol
Paniculate Source Controls, J.C. Chow and D.M. Ono, Eds Air & Waste ManSemen
Association, Pittsburgh, PA, pp. 39-50. • Management
Lee, K W. and M. Ramamurthi (1993). "Filter Collection." In Aerosol Measurement-
K' wmeke
«-*»•—
n
6-15
-------
Liffienfeld, P. (1979). "GCA's Model APM-1 Ambient Paniculate Monitor-Field Applications
and Results." Presented at 72nd Annual Meeting, Cincinnati, OH. Air Pollution Control
Association, Pittsburgh, PA.
Lin, C.I., M. Baker, and RJ. Charlson (1973). "Absorption Coefficient of Atmospheric
Aerosol: A Method for Measurement." Appl Opt., 12:1356.
Lippmann, M. (1989). "Sampling Aerosols by Filtration." In Air Sampling Instruments for
Evaluation of Atmospheric Contaminants, 7th ed., S.V. Hering, Ed. American Conference of
Governmental Industrial Hygienists, Cincinnati, OH, pp. 305-336.
Liu, B.Y.H. and K.W. Lee (1976). "Efficiency of Membrane and Nuclepore Filters for
Submicrometer Aerosols." Environ. Sci. TechnoL, 10:345-350.
Lowenthal, D.L. (1991). "Final Report on CMB Modelling for the Ohio EPA PM10 Project."
Prepared for Pacific Environmental Services by Desert Research Institute, Reno, NV.
Lowenthal, D.L., J.C. Chow, J.G. Watson, C.A. Frazier, and L.C. Pritchett (1991). "Puerto
Rico CMB Source Apportionment." DRI Document 8629.IF, prepared for E.H. Pechan and
Associates by Desert Research Institute, Reno, NV.
Lynch, A.J., N.R. McQuaker, and D.I. Bicun (1980). "ICP/HES Analysis and the Composition
of Airborne and Soil Materials in the Vicinity of a Lead/Zinc Smelter Complex " / Air Poll
Control Assoc., 30:257-259. .
Macias, E.S. and R.B. Husar (1976). "Atmospheric Particulate Mass Measurement with Beta
Attenuation Mass Monitor." Environ. Sci. TechnoL, 10:904-907.
Macias, E.S., R. Delumyea, L.C. Chu, H.R. Appleman, C.D. Radcliffe, and L. Staley (1979)
The Determination, Speciation, and Behaviour of Particulate Carbon." In Proceedings
Carbonaceous Particles in the Atmosphere, T. Novakov, Ed. Document LBL-9037 Lawrence
Berkeley Laboratory, Berkeley, CA, p. 70.
Malissa, H. (1979). "Some Analytical Approaches to the Chemical Characterization of
Carbonaceous Particulates." In Proceedings, Carbonaceous Particles in the Atmosphere T
Novakov, Ed. Document LBL-9037, Lawrence Berkeley Laboratory, Berkeley, CA, p. 3.
Marple, V.A., B.Y.H. Liu,'and G.A. Kuhlmey (1981). "A Uniform Deposit Impactor " J
Aerosol Sci., 12:333-337.
McCarthy, R. and C.E. Moore (1952). "Determination of Free Carbon in Atmospheric Dust "
Anal; Chem., 24:411.
6-16
-------
McDow S.R. and JJ. Huntzicker (1990). "Vapor Adsorption Artifact in the Sampling of
Organic Aerosol: Face Velocity Effects." Atmos. Environ., 24A:2563-2572.
McFarland, A.R C.A. Ortiz, and R. W. Bertch (1978). "Particle CoUection Characteristics of
a Single-Stage Dichotomous Sampler." Environ. Sci. Technol., 12:679-682. ciensucs or
McFarland A.R.C A. Ortiz, and C.E. Rodes (1980). "Characterization of Sampling Systems
A Size Specific Particulate standarl
McFarland, A R and C.A. Ortiz (1984a). "Characterization of Sierra-Andersen Model
McFarland, A.R. and C.A. Ortiz (1984b). 'Wind Tunnel Characterization of
SamplOTs-" Texas A&M *
TP
'11- "* C'A- Orflz (1984c)' "Characterization of Sierra-Andersen PM Inlet
A&M *" Collie
McFarland, A.R. and C.A. Ortiz. 1987. Aerosol sampling characteristics of the Sierra
llb PMl° Uet' TeMS **" ^ ^ Repon °S
ML
N'R,' RD' Khickner- «"« N.C. Gok (1979). "Calibration of an Inductive*
mC " Spectt0meter for to *-!»* of Environmental M™"
Analysis. • MikrocHim
S3.
6-17
-------
Mueller, P.K...R.W. Mosely, and L.B. Pierce (1971). "Carbonate and Non-Carbonate Carbon
in Atmospheric Particulates. " In Proceedings, Second International Clean Air Congress
Academic Press, New York, NY.
Mueller, P.K., B.V. Mendoza, J.C. Collins, and E.S. Wilgus (1978). "Application of Ion
Chromatography to the Analysis of Anions Extracted from Airborne Paniculate Matter " In Ion
Chromatographic Analysis of Environmental Pollutants, E. Sawicki, J.D Mulik and E
Wittgenstein, Eds. Ann Arbor Science Publishers, Inc., Ann Arbor, MI, pp. 77-86.
Mueller, P.K., G.R. ffilst, G.M. Hidy, T.F. Lavery, and J.G. Watson (1981). "EPRI Sulfate
Regional Experiment: Results and Implications." Document EA-2077-SY-LD, Electric Power
Research Institute, Palo Alto, CA.
Mueller, P.K., K.K. Fung, S.lT. Heisler, D. Grosjean, and G.M. Hidy (1982) "Atmospheric
Paniculate Carbon Observations in Urban and Rural Areas of the United States " In Paniculate
CarboKAtmospheric Life Cycles, G.T. Wolff and R.L. Klimisch, Eds. Plenum Press, New
X OiJ£9 iN X 9 PJP* J^O"~J /U.
Mueller, P.K., G.M. Hidy, R.L. Baskett, K.K. Fung, R.C. Henry, T.F. Lavery N J Nordi
A.C. Llc-yd JW .Thrasher, K.K. Warren, and J.G. Watson (1983). "Sulfate 'Regional
Experiment (SURE): Report of Findings. " Document EA-1901, Electric Power Research
Institute, Palo Alto, CA.
M!f £-f' ?f: *£ C.'E- McDade (1986)' HThe SCENES Measurement of Aerosol Properties
and Visual Air Quality in the Southwestern U.S." Paper #86-17.3, presented at 79th Annual
Meeting, Minneapolis, MN. Air Pollution Control Association, Pittsburgh, PA.
Mueller, P.K., D.A. Hansen, and J.G. Watson (1986). "SCENES: An Overview of the
Sub-Regional Cooperative Electric Utility, Department of Defense, National Park Service and
Environmental Protection Agency Study on Visibility. " Electric Power Research Institute, Palo
Muhlbaier J.L and RL. Williams (1982). "Fireplaces, Furnaces and Vehicles as Emission
S nTr8 ^r^1^031™11-" ^Particulate C<*rton, Atmospheric Life Cycles, G.T. Wotff
and R.L. Klumsch, Eds. Plenum Press, New York, NY, pp. 185-205.
™
Sulfate and
. SaWicki (1976>- "Ion Chromatographic Analysis
in Ambient Aerosols." Environ. Sci. TechnoL, 9(7): 653-663.
Mulik J.D R Puckett, E. Sawicki, and D. Williams (1977). "Ion Chromatographv - A New
Analytical Technic^e for the Assay of Sulfate and Nitrate in Ambient Aerosol? "In Methods
t. Document 464, National Bureau of Standard?
6-18
-------
Characterization of Aerosols." In Nature Air
2— :
Ah TT (i971)' "Detenninati<>n of Trace Concentration of Ammonia in the
Atmosphere Using Pyndine-Pyrazolone Reagent." Atmos. Environ., 5:621-62™
Olin J.G. (1978). A New Virtual Impactor (Dichotomous Sampler) for Fine Particle Air
Momtonng., Presented at 71st Annual Meeting. Air Pollution ContL ^
Olin, J.G and R R. Bonn (1983). "A New PM10 Medium Flow Sampler " Presented at 76th
Annual Meeting, Atlanta, GA. Air Pollution Control Association, Pi^burgh PA
Oregon Department of Environmental Quality
Repon.' Oregon Department of Environmemal
"Oreion Air
ry; SaTem ! OR
ioon
**>
^
, U.S. Environmental Protection Agency, Research Triangle Park, NC
Ooo u ' Applying ^ ValidatinS «* CMB Model "
450/4-87-010, U.S. Environmental Protection Agency, Research Triangle Park NC
6-19
-------
Parkes, L, LJ. Rabbitt, and MJ. Hamshire (1979). "Live Peak-Stripping During X-Ray
Energy-Dispersive Analysis." Anal. Chem., 46(12): 1830.
Patashnick, H. and E.G. Rupprecht (1990). "Continuous PM10 Measurements Using the Tapered
Element Oscillating Microbalance." Presented at 83rd Annual Meeting. Air & Waste
Management Association, Pittsburgh, PA.
Patashnick, H. and E.G. Rupprecht (1991). "Continuous PM10 Measurements Using the Tapered
Element Oscillating Microbalance." J. Air Waste Manage. Assoc., 41:1079-1083.
Patterson, R.K. (1973). "Automated Pregl-Dumas Technique for Determining Total Carbon,
Hydrogen and Nitrogen hi Atmospheric Aerosols." Anal. Chem., 45:605-609.
Perldn-Elmer (1982). "Analytical Methods for Atomic Absorption Spectrophotometry " Perkin-
Elmer, Norwalk, CT.
Perry, W.H. (1989). "Sequential and Tape Samplers ~ Unattended Sampling." In Air Sampling
Instruments for Evaluation of Atmospheric Contaminants, 7th ed., S.V. Bering, Ed. American
Conference of Governmental Industrial Hygienists, Cincinnati, OH, pp. 291-303.
Pimenta, J.A. and G.R. Wood (1980). "Determination of Free and Total Carbon in Suspended
Air Particulate Matter." Environ. Sci. TechnoL, 14:556-561.
Pyen, G.S. and M.J. Fishman (1979). "Determination of Anions in Pore Waters from Cores."
In Ion Chromatography Analysis of Environmental Pollutants, J.D. Mulik and E. Sawicki, Eds
Ann Arbor Science Publishers, Inc., Ann Arbor, MI, pp. 235-244.
Raabe, O.G., D.A. Braaten, R.L. Axelbaum, S.V. Teague, and T.A. Cahill (1988)
"Calibration Studies of the DRUM Impactor." J. Aerosol Sci., 19:183-195.
Ranweiler, L.E. and J.L. Moyers (1974). "Atomic Absorption Procedure for Analysis of Metals
in Atmospheric Particulate Matter." Environ. Sci. TechnoL, 8:152-156.
Rau, J.A. (1986). "Residential Wood Combustion Aerosol Characterization as a Function of
Size and Source Apportionment Using Chemical Mass Balance Modeling." Ph.D Dissertation
Oregon Graduate Center, Beaverton, OR.
Rich, -W., J.A. TUlotson, and R.C. Chang (1978). "Ion Chromatography: An Analytical
Perspective." In Ion Chromatographic Analysis of Environmental Pollutants, E. Sawicki J D
Mulik, and E. Wittgenstein, Eds. Ann Arbor Science Publishers, Inc., Ann Arbor, MI, pp.
X /v<£>7*
6-20
-------
Rogers, C F. and J.G. Watson (1984). Potential Causes of Elevated PMm and PM
Concentrat,ons m the Inhalable Paniculate Network, Document EPA-450/4-??? PreZei for
- NC>"
'"a«-^^^^
Rogge, W.F L.M. Hildemann, M.A. Mazurek, G.R. Cass, and B.R T Simoneit fl993a^
Dust: Roads as Sources and Sinks." Environ. Sci. Technol., 27:1892-1904
Rosen H., A.D.A. Hansen, L. Gundel, andT. Novakov (1978). "Identification of the Ctoticallv
Absorbing Component in Urban Aerosols. " Appl Opt, , 17(24):3859-386L '
' R-L> D°d' L'A- Gunde1' ^ T' Nov^ov (1982) "Graphitic
WoId^r^ f16^" ID Pam'CK/^ Carb™' ^osphe^
, G.I. Wolff and R.L. Klimisch, Eds. Plenum Press, New York, NY, pp 273-294
cZ^
Conference of Governmental IndusMal HwtadSTSffi OK pp
Rupprecht, E., M. Meyer, and H Patashnick- ^QQ'7^
SeSTEas a Tof °r ^^SL'Su
Presented at European Aerosol Conference, Oxford, U.K.
Russ, J.C. (1977). "Processing of Energy-Dispersive X-Ray Spectra." X-Ray Spectrometry ,
Cation
Schweiss, J. (1991). EPA Region X. Personal communication.
6-21
-------
*
Shah, JJ. (1981). "Measurements of Carbonaceous Aerosol Across the U.S.: Sources and
Role in Visibility Degradation." Ph.D. Dissertation, Oregon Graduate Center, Beaverton, OR.
Shah, JJ. and J.A. Rau (1991). "Carbonaceous Methods Comparison Study: Interlaboratory
Round Robin Interpretation of Results." Prepared for California Air Resources Board by G,
Environmental, Inc., Portland, OR.
Shendrikar, A.D., and J.P. Lodge, Jr. (1975). "Microdetermination of Ammonia by the Ring
Over Technique and Its Application to Air Pollution Studies." Atmos. Environ., 9:431-435.
Shimp, D.R. (1988). "Field Comparison of Beta Attenuation PM10 Sampler and High-Volume
PM10 Sampler." In Transactions, PM10: Implementation of Standards, C.V. Mathai and D.H.
Stonefield, Eds. Air Pollution Control Association, Pittsburgh, PA, pp. 171-178.
Skidmore, L." and J.C. Chow (1992). "PM10 Air Quality Assessment for the Jefferson County,
Ohio Air Quality Control Region," In Transactions, PM10 Standards and Nontraditional
Paniculate Source Controls, J.C. Chow and D.M. Ono, Eds. Air & Waste Management
Association, Pittsburgh, PA, pp. 1016-1031.
Sloane, C.S., J.G. Watson, J.C. Chow, L.C. Pritchett and L.W. Richards (1991). Size-
Segregated Fine Particle Measurements by Chemical Species and Their Impact on Visibility
Impairment hi Denver. Atmos. Environ., 25A, 1013-1024.
Small, H., T.S. Stevens, and W.C. Bauman (1975). "Novel Ion Exchange Chromatographic
Method Using Conductimetric Detection." Anal. Chem., 47:1801-1809.
Small, H. (1978). "An Introduction to Ion Chromatography." Ion Chromatographic Analysis
of Environmental Pollutants, E. Sawicki, J.D. Mulik, and E. Wittgenstein, Eds. Ann Arbor
Science Publishers, Inc., Ann Arbor, MI, pp. 11-21.
Smith, T.B., W. White, J. Anderson, and S. Marsh (1975). "The Chemistry, Dispersion and
Transport of Air Pollutants Emitted from Fossil Fuel Power Plants in California." Report
prepared for California Air Resources Board, Sacramento, CA.
Solomon, P.A., T. Fall, L. Salmon, P. Lin, F. Vasquez, and G.R. Cass (1988). "Acquisition
of Acid Vapor and Aerosol Concentration Data for Use hi Dry Deposition Studies in the South
Coast Air Basin." Vol. H. Environmental Quality Laboratory, California Institute of
Technology, Pasadena, CA.
Solomon, P.A., T. Fall, L. Salmon, G.R. Cass, H.A. Gray, and A. Davison (1989). "Chemical
Characteristics of PM10 Aerosols Collected in the Los Angeles Area." J. Air Poll Control
Assoc., 39:154-163.
6-22
-------
M.A. Mason, and WJ. Courtney (1982)
^- M?rlenny' T'G-
Stevens R.K.,RJ.Paur,I.Allegruni,F.DeSantis,A.Febo,C.Perrino M Possanzini IT w
Cox E.E. Estes, H.R. Turnes, and I.E. Sickles, '
.
, U.S. Environmental
Research Triangle Park, NC pp.
6-23
-------
Sutherland, J.L. and P.S. Bhardwaja (1987). "Composition of the Aerosol in Northern Arizona
and Southern Utah." In Transactions, Visibility Protection, Research and Policy Aspects, P.S.
Bhardwaja; Ed. Air Pollution Control Association, Pittsburgh, PA, p. 373.
Tang, H., E.A. Lewis, DJ. Eatough, R.M. Burton, and RJ. Farber (1994). "Determination
of the Particle Size Distribution and Chemical Composition of Semi-Volatile Organic
Compounds in Atmospheric Fine Particles." Atmos. Environ., in press.
Tanner, R.L., J.S. Gaffney, and~M.F. Phillips (1982). "Determination of Organic and
Elemental Carbon in Atmospheric Aerosol Samples by Thermal Evolution " Anal Chem
54:1627-1630.
Tanner, R.L., A.W. Gertler, E.M. Fujita, and J.C. Chow (1993). "Atmospheric Organic
Acids: A Review. " Submitted to Atmos. Environ.
•
Technicon Instruments Corporation (1987). "Preliminary Operation Manual for the Technicon
TRAACS 800 System." Document DSM-0005-00.3, Technicon Instruments Corporation
Tarrytown, NY. .
Tejada, S.B., R.B. Zweidinger, I.E. Sigsby, Jr., andR.L. Bradow (1978). "Modifications of
an Ion Chromatograph for Automated Routine Analysis: Applications to Mobile Source
Emissions." In/o/z Chromatographic Analysis of Environmental Pollutants, E. Sawicki, J D
Mulik, and E. Wittgenstein, Eds.^ Ann Arbor Science Publishers, Inc., Ann Arbor, MI, pp.
Thurston, G.D., H, Ozkaynak, and A. Schatz (1984). "A Chemical Characterization and Source
Apportionment of the IP Network Fine Paniculate Data. " Paper 84-58.6. Presented at the 77th
Annual Meeting, San Francisco, CA. Ah- Pollution Control Association, Pittsburgh, PA.
Thurston, D.G., I.E. Gorczynski, Jr., J. Currie and D. He (1992). "A Multi-Year Study of Air
Pollution and Respiratory Hospital Admissions in Three New York State Metropolitan Areas-
Results for 1988 and 1989 Summers." J. Exposure Anal. Environmental Epidemiology, 2: 429-
^
Tombach, I.H., D.W. Allard, R.L. Drake, and R.C. Lewis (1987). "Western Regional Air
Quality Studies. Visibility and Air Quality Measurements: 1981-1982." Report #EA-4903
prepared for Electric Power Research Institute by AeroVironment, Inc., Monrovia, CA.
U.S. Environmental Protection Agency (1976). "Laboratory Procedures for the Analysis of
Ammonia in Particulates Collected by Means of HI-VOL Samplers-Techmcon Autoanalyzer H
Procedures. Analytical Chemistry Branch, Research Triangle Park, NC.
cnT Protection Agencv <1987a)- ™10 SIP Development Guidelines." EPA
450/2-86-001, U.S. Environmental Protection Agency, Research Triangle Park, NC.
6-24
-------
U.S. Environmental Protection Agency (1987b). "Protocol for Reconciling Differences Anton*
™'^'^
U.S. Government Printing Office (1991). "Clean Air Act Amendments of 1990 " Conference
Report to Accompany S. 1630, House of Representatives, Superintendent* ScumW US
Government Printing Office, Washington, D.C. Documents. U.S.
VanOsdell D W and F.L. Chen (1990). "Wind tunnel test report no. 28- Test of
Beaverton, OR. University Microfilms International, Ann Arbor, ML waauate ^enter'
°f Inhalable Particu'ate Batter
Environmental Protection Agency, Research Triangle
as:
Wateon J.G, J C. Chow, R.T. Egami, C.A. Frazier, A. Goodrich, and C Ralph a98&n
6-25
-------
Program Plan." DRI Document 8810.1F1, prepared for the 1987-J
Cloud Study, Inc., Denver, CO.
Metro Denver Brown
Watson, J.G., J.C. Chow, L.W. Richards, W.D. Neff, S.R. Andersen, D.L. Dietrich, I.E.
Houck, and I. Olmez (1988c). "The 1987-88 Metro Denver Brown Cloud Study. Volume H:
Measurements." DRI Document 8810.1F2, prepared for the 1987-88 Metro Denver Brown
Cloud Study, Inc., Denver, CO.
- Watson, J.G., J.C. Chow, L.W. Richards, W.D. Neff, S.R. Andersen, D.L. Dietrich JE
Houck, and I. Olmez (1988d). "The 1987-88 Metro Denver Brown Cloud Study. Volume IE-
Data Interpretation." DRI Document 8810.1F3, prepared for the 1987-88 Metro Denver Brown
Cloud Study, Inc., Denver, CO.
Watson, J.G., J.L. Bowen, J.C. Chow, C.F. Rogers, M.G. Ruby, M.J. Rood, andR.T. Egami
(1989a). "Method 501: High Volume Measurement of Size Classified Suspended Particulate
Matter." In Methods of Air Sampling and Analysis, 3rd ed., J.P. Lodge, Ed. Lewis
Publishers, Inc., Chelsea, MI, pp. 427-439.
Watson, J.G., P.J. Lioy, and P.K. Mueller (1989b). "The Measurement Process: Precision,
Accuracy, and Validity." In Air Sampling Instruments for Evaluation of Atmospheric
Contaminants, 7th ed., S.V. Hering, Ed. American Conference of Governmental Industrial
Hygienists, Cincinnati, OH, pp. 51-57.
Watson J.G., N.F. Robinson, J.C. Chow, R.C. Henry, B.M. Kim, T.G. Pace, EX. Meyer and
Q. Nguyen (1990a). "The USEPA/DRI Chemical Mass Balance Receptor Model, CMB 7.0 "
Environ, Software, 5:38-49.
Watson, J.G., J.C. Chow, R.T. Egami, J.L. Bowen, C.A. Frazier, A.W. Gertler, K.F. Fung
(1990b). "Program Plan for the California Acid Deposition Monitoring Program." Final
Report, DRI Document 8068.1F1, prepared for the California Air Resources Board, Sacramento
CA by the Desert Research Institute, Reno, NV.
Watson, J.G, J.C. Chow, L.W. Richards, D.L. Haase, C. McDade, D.L. Dietrich D Moon
L. Chinkin, and C. Sloane (1990c). "The 1989-90 Phoenix PM10 Study, Vol. I: Program
Plan." DRI Document 8931.2F, prepared for Arizona Department of Environmental Quality bv
Desert Research Institute, Reno, NV.
Watson, J.G, J.C. Chow, L.W. Richards, D.L. Haase, D.L. Dietrich, D. Moon, L. Chinkin
and C. Sloane (1990d). "The 1989-90 Pilot Tucson PM10 Study, Vol. I: Program Plan " DRI
Document 8931.4F, prepared for Arizona Department of Environmental Quality by Desert
Research Institute, Reno, NV.
6-26
-------
Wateon, J.G., J.C. Chow, and T.G. Pace (1991a).
"Chemical Mass Balance." In Receptor
U.S. Environment Protectiongency, Region by D««
Watson J.G., J.C. Chow, L.W. Richards, D.L. Haase, C. McDade, D L Dietrich D Moon
and C. 810^(19910. Tie 1989-90 Phoenix Urban Haze Study Votoe £' £e Apport
of L,^tExnncnon to Sources. Final Report, DRI Document 8931.5FL Prepared
Department of Envrronmental Quality, Phoenix, AZ, by Desert Research IrSte,
Watson J.G., J.C. Chow, R.T. Egami, J.L. Bowen, C.A. Frazier A W Gertler D H
Lowenthal, and K..K. Fung (199!*. 'Measurement of Dry Deposition 'pLSSTte te
Cahfomia Acid Deposition Monitoring Program." DRI Document 8068.2F1 prepared for
California Air Resources Board by Desert Research Institute, Reno, NV.
(1993)' "Amt>ient
In
Measurement-
Watson, J.G., J.C. Chow, F. Lurmann, and S. Musarra (1994a). 'Ammonium Nitrate Nitric
Acid, Ammoma Eqmhbnum, in Wintertime Phoenix, AZ.' /. Air Was,, Manag^'soc. ta
6-27
-------
Wedding, J.B., A.R. McFarland, and I.E. Cennak (1977). "Large Particle Collection
Characteristics of Ambient Aerosol Samplers." Environ. Sci. Technol., 4:387.
Wedding, J.B., M. Weigand, W. John, and S. Wall (1980). "Sampling Effectiveness of the Inlet
to Dichotomous Sampler." Environ. Sci. Technol., 14:1367-1370.
Wedding, J.B., M.A. Weigand, and T.C. Carney (1982). "A PM10 Cutpoint Inlet for the
Dichotomous Sampler." Environ. Sci. Technol., 16(9):602-606.
Wedding, J.B. and T.C. Carney, (1983). "A Quantitative Technique for Determining the Impact
of Non-ideal Ambient Sampler Inlets on the Collected Mass." Atmos. Environ., 17:873.
Wedding, J.B., M.A. Weigand, M.W. Ligoke, and R. Baumgardner (1983) "Wedding
Ambient Aerosol Sampling-Inlet for an Intermediate Flow Rate (4 cfm) Sampler " Environ Sci
Technol., 17(7): 379-3 83.
Wedding, J.B. (1985). "Errors in Sampling Ambient Concentrations Employing Setpoint
Temperature Compensated Mass Flow Transducers." Atmos. Environ., 19:1219-1222.
Wedding, J.B., and M.A. Weigand (1985). "The Wedding Ambient Aerosol Sampling Inlet
(D50 - 10 iao) for the High Volume Sampler." Atmos. Environ., 19:535-538.
Wedding, J.B., M.A. Weigand, Y.J. Kim, D.L. Swift, and J.P. Lodge (1987). "A Critical
How Device for Accurate PM10 Sampling and Correct Indication of PM10 Dosage to the
Thoracic Region of the Respiratory Tract." J. Air Poll. Control Assoc., 37:254-258.
Weiss, R.E., A.P. Waggoner, R. Charlson, D.L. Thorsell, J.S. Hall, and L.A Riley (1979)
Studies of the Optical, Physical, and Chemical Properties of Light Absorbing Aerosols " In
Proceedings: Conference on Carbonaceous Panicles in the Atmosphere T Novakov Ed
Document LBL-9037, Lawrence Berkeley Laboratory, Berkeley, CA, p. 257.
Whitby, K.T., R.B. Husar, and B.Y.H. Liu (1972). "The Aerosol Size Distribution of Los
Angeles Smog." J. Colloid Interface Sci., 39:177-179.
Wffley, J.D. and C.A. Wilson (1993). "Formic and Acetic Acids in Atmospheric Condensate
in Wilmington, North Carolina." J. Atmos. Chem., 16(2): 123-133.
Witz S. M.M Smith, and A.B. Moore, Jr. (1983). "Comparative Performance of Glass Fiber
Hi-Vol Filters." /. Air Poll. Control Assoc., 33:988-991.
Witz, S R.W. Eden, M.W. Wadley, C. Dunwoody, R.P. Papa, andK.J. Torre (1990). "Rapid
Loss of Paniculate Nitrate, Chloride and Ammonium on Quartz Fiber Filters During Storage "
J. Air Poll. Control Assoc., 40:53-61.
6-28
-------
Wolff, G.T., PJ. Groblicki, S.H. Cadle, and RJ. Countess (1982). Tarticulate Carbon at
Various Locations ui the United States." In Paniculate Carbon: Atmospheric Life Cycle, G.I
Wolff and R.L. Klumsch, Eds. Plenum Press, New York, NY, pp. 297-315.
™ > ?'R StrouP> «* P-E- Korsog (1991). "A Characterization of
the Principal PM10 Species in Claremont (Summer) and Long Beach (Fall) During SCAO
-------
-------
APPENDIX A
SUMMARY OF PM10 STUDIES AND DATA BASES
A-l
-------
on m
"3
S' 111
ea 6- 13
s
1
o.2S-5|
1 = 2 8i|
Sit i£i 52. ^ a 2
A-2
-------
fl«^
S ^3 M* rrj
s
S f2 - ^ e
1 « * £ !
SO S _ ^
2
.
? 2
y a u O
S o*1*) .co
•c
"O
«
1
t
4)
CO
£
i
111
\o
&
« S ra -a
«s s a >•
5SSf
a*
3
. &s£
T»- > O\ ,.
es S -< .5
§••2
•a & o
2 i §:
3 g,
3 55
^.
CO
"i -"
a «
2 §
1*2
2 O
cu ^i-
A-3
-------
I
S
I
1
I
e
Jjf *1
1
.
I
5 fc>|o£
7 8 a,o\
5 Sjf2
I
n-l A,
~ »*
§ ^
« y|
3 ?
A &
« 5-
13 <2
-•a
Jl
.2
— <3 C
•§ o. S,
s|-§
•o
u
2l
u . "x
llfi
« ^
-ri rt
13 ^- U
ll
I -a
en o
.
S I* '§,
SS C3
S g £
«-i CO « •-<
•a
u
'B
l^-ei
5> 2 O *2
o, *^r &4 JQ
sg^^
A-4
-------
•o
o
.
«N
:
JS
.
-a
-a
a
o!
03
O
-Illo
o • "9 > « o .a
Sz u 3) .-I S *3
« S t_ « ••• «
1 J o 'g « 2
|s &^|a
2 ^ *o ^ dt ^
^ o E ™ 2>n
5 > « S>S ""
S J3 73 •§ 5 2
c «( .—
3j «^ »^^ ••
2 S W 2
C co ,.; 'B
^
2
ON
CM
O
g
1
i
>
a o „
.g ^ eo
I'! I
a*
o
c
A-5
-------
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverie before completing) '
1. REPORT NO.
EPA-452/R-94-009
2.
I. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
-Guidelines For PM-10 Sampling and Analysis
Applicable to Receptor Modeling
S. REPORT DATE
March 1994
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Dr. Judith C. Chow and Dr. John G. Watson
I. PERFORMING ORGANIZATION REPORT NO
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Desert Research Institute
P.O. Box 60220
Reno, NV 89506
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
CR816826-02-01
12. SPONSORING AGENCY NAME AND ADDRESS
U.S. Environmental Protection Agency
Office of Air and Radiation
Office of Air Quality Planning and Standards
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
Air Quality Management Division Research Triangle Parl|, NC 27711
15. SUPPLEMENTARY NOTES
EPA contacts: Breda M. Phillips and Thompson G. Pace, Program Development Section
Sulfur Dioxide/Particulate Matter Programs Branch _
16. ABSTRACT
Chemical characterization of^Suspended particles is necessary, along with
the application of receptor models, to apportion ambient concentrations
to their sources for the development of'emission reduction strategies.
This document identifies current technology for the sampling and analysis
of PM-10 and its chemical constituents on filter deposits.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lOENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Croup
Particulate Matter
PM-10
sampling methods
chemical analysis
filter analysis
receptor modeling
18. DISTRIBUTION STATEMENT
Release unlimited
19. SECUFUTY CLASS JTJiit Report)
unciassTndd
21. NO. OF PAGES
149
20. SECURITY CLASS (Thispage)
unclassified
22. PRICE
EPA Form 2220-1 (R*v. 4-77) PREVIOUS EDITION 19 OBSOLETE
-------
-------