-------
the eight major urban areas studied were suspect because the dichoto-
mous sampler PMjs exceeded the hivol sampler TSP by more than the data
flagging criteria adopted for the IP Network (U.S. EPA, 1980; Watson et
al., 1981). These criteria, applied by EPA/EMSl, flag simultaneous
measurement sets for which the ratio of PMj5 to hivol mass con-
centrations exceeds 1.1. Such ratios do not invalidate the data points
because it is impossible to determine which sample is in error with the
available information. For this study, it is assumed that the hivol
data derive from the older and more established measurement device, and
that a PM15/HIVOL ratio exceeding 1.1 probably indicates a faulty PM15
measurement.
Another type of measurement discrepancy involved out-of-bounds
coarse/fine mass ratios. In this case, the IP Network flagging cri-
teria identify coarse/fine ratios less than 0.3 or greater than 1.3.
This criterion is not applied stringently here, but three cases are
classified as anomalous: one with a coarse/fine ratio of 0.05 (El Paso,
4/29/82), one with a coarse/fine ratio of 0.07 (Philadelphia, 3/10/80),
and finally a case with a coarse/fine ratio equal to 12.5 (El Paso,
12/11/79). *
As noted earlier, additional hypotheses could be advanced. It will
be seen in the next section, however, that these five simple hypotheses,
individually and in combinations, are often supported by IP Network
data.
37
-------
SECTION 5
SUPPORT FOR HYPOTHESES
Detailed case studies for each site-day are presented in Appendix A.
These case-studies include the ambient chemical data and a summary of
the meteorological situation. Their results are summarized in this sec-
tion for each of the hypotheses to determine whether or not it has
general support. Unfortunately, all data were not available for all
site-days, and the same set of samples is not drawn from to support
every hypothesis.
INDUSTRIAL SOURCES (Hypothesis 1)
Thirty-six site-days had a full set of chemical concentrations,
though three of these were suspect for one reason or another. Sixteen
of the remaining 33 cases showed a marked influence of some industrial
activity. All of these sites are located in cities where the indicated
industrial activity is known to take place. All of the sites in
Buffalo, NY, Cleveland, OH, Philadelphia, PA, Pittsburgh, PA, and
Youngstown, OH, are classified as Center City-Industrial in Table 3-1.
Only Bakersfield is 'Center City-Commercial.
Buffalo, Cleveland and Pittsburgh contain major steel mills within a
mile of the sampling sites, and ambient concentrations of iron, manga-
nese and zinc were often elevated above the values in Table 4-1 by a
factor of two or more.
38
-------
The coarse iron concentrations reached values as high as 12.3 yg/m3
in Cleveland on 4/4/81. Fine iron concentrations reached 8.1 yg/m at
the same site on 7/20/79. Similar results were found for the high site-
days in Buffalo and Pittsburgh.
In Philadelphia, the coarse and fine manganese concentrations
reached 6.9 and 0.9 yg/m respectively at the T and A Pet site on
11/20/79. A nearby minerals handling facility is a likely source.
Copper and zinc were elevated at nearby sites and the site surveys note
the presence of a copper smelter nearby.
Bakersfield attained one of the highest fine sulfate concentrations
in the network on 1/10/81, 45 yg/m . Even though this site is
classified as Center City-Commercial it is known that oil fields
surround the city of Bakersfield and that a substantial amount of
sulfur-containing gases are emitted which could be the precursors to
sulfate.
In none of the cases studied is the chemical species indicating the
presence of a given source of a sufficient concentration to greatly
influence the PM^ mass concentration. In fact, even if all of the chem-
i
ical species measured at a IP Network site were summed, they would
account for far less than half of the corresponding PM]^ values. If
steel "mills, smelters, and mineral handling facilities contribute only
the species which are measured, such as Fe, Cu, and Mnป then they are
39
-------
not major causes of high PMj5 concentrations. If these chemical con-
centrations are also associated with other, unmeasured species, then the
contributions of industrial sources to PM^ could be much greater.
All of the Center City-Industrial sampling sites identified in
Table 3-1 which had chemical concentrations were found to have some
industrial influences. Only one which is not so classified,
Bakersfield, shows a significant industrial influence, and this
influence is apparently not due to industrial activities within the
city.
NON-INDUSTRIAL SOURCES (Hypothesis 2)
The non-industrial sources include resuspended geological material
and road dust (which may indeed be industrial in origin, but is con-
sidered separately here because it cannot be distinguished from its non-
industrial counterpart), automobile exhaust, construction activities,
heating and burning. Of the 33 valid site-days for which chemical spe-
cies were measured, 18 showed significantly elevated chemical con-
centrations indicative of these non-industrial sources.
Geological material appears to be a contributor at P.S. #26 in
Buffalo, Bakersfield, Rubidoux, and Fresno where very high Al and Si
levels were measured. Coarse silicon and aluminum reached levels of 24
3
and 9 yg/m , respectively, in "Bakersfield on 11/17/80, which would make
suspended dust a major contributor to the 183 yg/m PMjs concentration
observed on that day. High speed Santa Ana winds are recorded for that
period which probably raised the dust.
40
-------
Elevated chloride levels sometimes accompany the higher aluminum and
silicon concentrations, particularly during winter months. Hartford and
Youngstown both exhibited higher than normal chloride levels on 1/22/81
and 2/15/81, respectively. The weather summaries for both cases show
snow on the ground and it is known that roadways in these eastern
cities are salted and sanded during snowfall. The chloride could result
from traffic resuspension.
Motor vehicle exhaust is indicated by elevated Br and Pb con-
centrations with Br/Pb ratios in the range of 0.2 to 0.4. This
situation is observed in Cleveland, at the T and A Pet and Presbyterian
Home sites in Philadelphia, and in El Paso, but not to a great extent at
other sites. One of the highest cases occurred at the T and A Pet site
on 11/20/79 when PM^ lead reached 2.4 pg/m3 and bromine reached 0.6
pg/m . If one assumes that lead constitutes approximately 20% (e.g.
Watson, 1979) or less of the mass of particulate motor vehicle exhaust,
these levels imply a significant contribution to the 173 pg/m
concentration observed on that date.
Calcium concentrations were elevated in the coarse fraction for a
number of site-days,* and the levels reached are rarely consistent with
those expected from geological material. The case in El Paso was
offered as an example in Section 4, and owing to a detailed site survey,
it could be explained by nearby construction. The Ca source is not so
obvious at Wilmuth Pump in Buffalo, NY, on 4/4/81, in Bakersfield on
11/17/80, and in Rubidoux on 8/7/80. For example, calcium contributes 27
41
-------
yg/m3 to the 145 yg/m3 PMjs concentration at Wilmuth Pump. Since
calcium is a non-reportable species (as defined in Section 1), this may
be a measurement anomaly, but its levels at other sites seem so con-
sistent with normal geological material that it is difficult to believe
the errors in its measurement can be so large. The El Paso case lends
credence to the effects of nearby construction, and it may be that such
activities periodically take place but are not adequately recorded.
Elevated vanadium and nickel levels are present at the T and A Pet,
NE Transfer, and Presbyterian Home sites in Philadelphia, PA, indicating
a potential source of residual oil combustion. All of these occurred on
the same day, 11/20/79, a day on which the weather reports show higher
than . normal temperatures, but it was still cold enough to require
heating. Stagnant conditions were also present, as will be discussed
below.
One clear-cut case of vegetative burning contributions occurred in
Bakersfield on 11/17/80. In this case, high speed Santa Ana winds
fanned fires in southern California which destroyed much grassland and
over 100 homes. Potassium in PMj5 reached 3.7 yg/m in Bakersfield and
4
chloride was also elevated on this day. Both potassium and chloride are
known to be products of vegetative burning (Watson, 1979). Though
these species were elevated at other sites, notably Cleveland on 9/12/80
and 4/4/81 and Wilmuth Pump on 6/15/81 where the fine potassium con-
centrations reached 2.3 yg/m , vegetative burning in these communities
has not been reported in other studies.
42
-------
The classifications of these sites where non-industrial sources
contribute more than their typical share to the PM^ are industrial as
well as non-industrial. P.S. #26, Cleveland, T and A Pet, NE Transfer
and Youngstown, all classified as Center City-Industrial, show signifi-
cant non-industrial contributions. Several of these non-industrial
tracer concentrations are elevated on the same days for which industrial
source tracers are elevated, demonstrating that the industrial sources
cannot be singled out as the sole causes of high PMj5 concentrations.
Center City-Commercial sites with elevated non-industrial contributions
are Bakersfield and Hartford. Presbyterian Home is Suburban-Industrial,
Rubidoux is Rural-Commercial, El Paso is Center City-Commercial and
Fresno is Suburban-Commercial.
The hypothesis that non-industrial sources are significant
contributors to high PM]^ concentrations is supported by the chemical
concentrations and the site-types at which they occur for the majority
of the 33 cases.
REGIONAL SCALE SECONDARY PARTICLES (Hypothesis 3)
<
The first identifier of a regional-scale secondary particle event is
an elevated concentration of sulfate and/or nitrate at the sampling
site. " The second identifier is a simultaneous elevated value at a
sampling site which is still within the region, but which may be several
43
-------
hundred miles away. The final identifier is a synoptic weather system
with warm moist air and high pressure which homogenous!y covers a large
region.
Unfortunately, not all of this information was available for the
high sulfate and nitrate concentrations contained in the 33 valid data
sets with chemical species. Chemical concentrations in the IP Network
were not uniformly measured on the same days at all sites. Complicating
this was an inability to acquire weather data from every site which
showed an elevated concentration. Thus, only seven out of 33 cases
might support the notion of a regional-scale secondary particle event
with sulfate or nitrate concentrations more than double the maximum
averages listed in Table 4-1. Several other cases with lower con-
centrations showed high sulfate or nitrate values, but they were less
than twice the maximum averages. The absence of sulfate and nitrate
information from other sites on the same days precludes a complete eva-
luation of this hyposthesis.
The most pronounced event occurred on 11/20/79 in Philadelphia, PA.
Here, fine sulfate values exceeded 30 yg/m at the T and A Pet,
1
Presbyterian Home, and NE Transfer sites. Fine nitrate concentrations
reached 9 pg/m at NE Transfer. Sulfate and nitrate values from other
eastern cities were not available on this date to confirm its regional
nature. The weather maps show a large high pressure system which had
persisted for three days with unseasonably warm weather. There is no
question that these secondary species were major contributors to the
44
-------
1/2, 152 and 146 yg/m3 PM15 coicentretlons at the T and A Pet, NE
7.-ar;fer, and P~esbyterii^ Ho-ne s-'t'ปs, resrsctively, especially when the
unrr.ei? j"ed catic'T *iz'n es ' cropsn lor and ammonium, associated with
the sulfate and ni: -~:e comnoj^ds are considered.
P.S. 126 in Buffalc experienced similar and high sulfate on 9/18/79
and 4/4/81. Some of the elevaced sulnte may be of local or sub-
reg'oral origin ir these cases, as nearly sites in Ironton, PA, and
Cleveland, OH, s^oป *"'re iuHste concentrsttons of 5 yg/m and 8
in i/c/si. -. -.."-it2 3nc -": ~:te mfcsarements were available from
- '6* s tes or, - "9.
Western s't-::, c. not usu?'. } exhibit pronounced regional-scale phe-
-omer.c owinq -: * - ccri:le> " opraphy (e.g. Flocchini et al . , 1981).
*s already -. . . e hie '"ste concentration at Bakersfield was
possibly due :,', i'~5 sjL-^ej on=i conversion of emissions from nearby
inGusi-ial so, r~es. Ccrresponcing readings at sites which are exposed
to v^e sin:- me* :. r;1 oclvir " "''"uaiions, such as Fresno, were not
Secondary aerosj. products cc^ ba nejor contributors to high
levels, but the information from the IP Network and other sources used
i". this study is insufficient to distinguish between regional-scale pro-
cesses a''d local or sub-recional sources.
45
-------
INVERSIONS (Hypothesis 4)
Vertical temperature soundings were available for 27 of the 36 site-
days with chemical speciation. Of these, 24 corresponded with the 33
site-days for which no measurement anomalies were suspected. These
inversions were nearly always accompanied by low wind speeds and often
occurred at the end of a high pressure system which had persisted for
two or three days.
Inversions and stagnant conditions do not cause high pollutant con-
centrations. They do provide situations which are conducive to an accu-
mulation of pollutants. These conditions occur at all site types in
both the eastern and western U.S.
Subsidence or radiation inversions were observed on the OOOOZ soun-
dings for eighteen of the 24 cases with complete and valid data, making
this hypothesis the most completely supported of the five. Since these
soundings were taken during the afternoon on or evening of the sampled
day, they were probably more persistent than short-term radiation inver-
sions which would have been present only during early morning hours.
4
MEASUREMENT ANOMALIES (Hypothesis 5)
The potential always exists for a specific measurement to be
unrepresentative of reality, and the number of cases supporting this
hypothesis provides a rough estimate of the proportion of high PM^s
concentrations which may result from an inadequate measurement process.
The IP Network is particularly amenable to the identification of these
46
-------
cases owing to the largs number of simi;T:#ieous ns&suremerrts taken at
each site which req-Ji--- en internal cnr-S^stency w'th each other. Tป-
o^; of the ~ ~ty h: - ?M'5 m?:. Jir^ment' ปia^t foun.-:' -, c havfc o?r,Dinet :r;*
of 1) a ""' c:rce':" Mon c-eet^r vhsr- tHs PKvc :ป.?C2ntrEr- r., 2} e
coe"se to f",r.e ccricentratior rstic whicn Is unlikely to be ot med frcm
typical particle size distributions, 3^ 3} chen,i.:al t " :eatration
levels which are .=- c-rder of macnituoe higher or low-: t , nase t>pi-
ceV.* fojnd in ar^-'cnt aerosol sarrp'ies (see Teble 4-1 for c :i*nt cnemi-
cel c:r c 2:it~3tion "ieveH).
TS?' -vas "iess "-^a"- PM-sc in sav" .;asss, tie n.os": o^vijus of wMr.h
is ti-s El PS:-3 cess, desr-ibed in Section 4, in whichViu 400 ug/ra PMjj
3
ex'.-^tded the irซ- -jg/rr." TSP by nearly a '*s-cii3r -of four,
A hi :; "' .' /.arjo/fine rati^ v reeson by Jtse1f t<3 -ajc'" . 3
-.!-.. vclu-?- ' trXc'^Ifi, this -'',: w, s 12.5 in ฃ1 Paso on 12?-'Ti/?9ป
J-JT. :;he coerse a"1,urnnum, silicon and ca'ciuro values, while riot excep-
tic-elly hia-'% Q%:r!orst"ate a substantial coarse contribution from gaclo-
cict'-'i ^Ete-'i". t;-' concentrcticns for ti.V'ate, nitrate.* ??::' the
geological a^-v.ia a~e cerie^all.v lov> wltli r-:.->ect to th-e v?lues M
Table 4-1. In th^ case, the da",a are cons".i'"j-- valid. T-r's is ncrt
tie case *or tre Presbyterian Home sits or 3.-" 1/8C end a '.T^asurameiKt
anomaly is assumed.
The chemical species concentrations at the Wilmuth Pun? site cs
?.'?M1 do not support the 3.1 coa-r-e/fine ratid meas^-ecl toe^-e, Kost af
t'i Cv/arse concent rations are rr.u-;h too low tc account for the ssars-e
47
-------
mass. A better example is the case of Portland, OR, on 10/12/79 which
exhibits a 43 yg/m aluminum concentration. Though aluminum pot lines
are located east of Portland, Watson (1979) never found them to be major
contributors in downtown Portland. Similar high aluminum levels have
been found at other Oregon sites in Portland, Deschutes County, and
Eugene. The high aluminum concentrations may result from contamination
of the samples.
The small 37 mm ringed Teflon filters used for PM^5 sampling are
much more susceptible to measurement anomalies than the large 8 x 10"
hivol filters simply because a small gain in mass translates into a much
larger gain in ambient concentration. Even minor contamination must be
avoided and it is not always possible to do so.
48
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SECTION 6
SUMMARY, CONCLUSIONS AND RECOMMENDATIONS
This report has attempted to identify the potential causes of ele-
vated PMjQ concentrations from measurements available in the IP Network
Data Base and meteorological measurements from the National Weather
Service. The number of PM^Q measurements was found to be insufficient
to meet the study objectives, but a high correlation was found between
elevated PM^ and PM^Q concentrations at sites where simultaneous
measurements were taken. High PM^ concentrations were then used as
surrogates for PMjQ.
Five causes of elevated PM^ concentrations were advanced: 1) local
industrial source emissions, 2) local non-industrial source emissions,
3) regional-scale secondary aerosol events, 4) subsidence and radiation
inversions and air mass stagnation, and 5) measurement anomalies.
Support for the first hypothesis was found in 16 of 33 cases (48%),
nearly all of which occurred at industrial site types. The second
hypothesis was supported in 18 out of 33 cases (55%) and included
industrial, commercial, residential and agricultural site types. The
regional-scale nature of the third hypothesis was difficult to support
owing to inadequate data, though major secondary aerosol events were
identified in 7 of 33 (21%) of the cases. Inversions and stagnation
were observed in 18 of 24 (75%)-. Measurement anomalies occurred in ten
of 50 (20%) cases. These anomalous measurements were not considered as
support for the other four hypotheses even though the PMj5 data were not
necessarily invalid.
49
-------
The conclusions drawn from this study are:
e Though industrial sites often exhibit elevated local industrial
source contributions, these are often accompanied by elevated
non-industrial and secondary aerosol contributions. Thus, local
industrial sources are not the sole cause of elevated PM^5 con-
centrations.
ซ Most elevated PM^5 episodes are accompanied by adverse weather
conditions, such as temperature inversions and persistent
stagnation. Since these meteorological events are bound to
occur from time to time in most urban areas, the only way to
lower PM}5 levels is to reduce emissions.
9 Secondary aerosol is a potentially major contributor to PM^,
and its origin may or may not be within the region in which the
samples are taken. Gaseous as well as particulate emissions
reductions may be required to reduce elevated PM^ con-
centrations.
o A significant potential for the erroneous measurements of high
PM^ exists, probably owing to the very small samples and flow
rates of the dichotomous sampler. A small filter weight gain
due to contamination can translate into a large increase in the
computed ambient concentration.
The IP Network data base is a rich source of information on the
size-classified concentrations of suspended particulate matter and its
chemical composition. This qualitative examination of the potential
cause of elevated PM^ levels, and through them the PM10 levels, found
in the data base provokes several recommendations for improving its
<
utility and analyzing it further. Three recommendations pertain to the
enhancement of the data base itself:
ซ A comprehensive guide to the data base should be written. This
guide would include a. description of all the reports, their
contents, the meanings of flags and symbols, and the criteria
for quality control, sample analysis selection, and data
validation. While this study adds new insights to those found
earlier by Watson et al. (1981), these references do not ade-
quately unify the necessary information.
ซ A sample selection strategy for chemical analysis needs to be
formulated and applied. Evaluation of regional-scale events
50
-------
was hampered by the lack of simultaneous chemical speciation
from samples at nearby sites. Similarly, some of the highest
PM}5 concentrations in the network were not submitted to che-
mical analyses, thereby hindering the interpretation of those
high values. Presumably these samples are still archived and
chemical analyses can still be performed. Several of these
should be selected and analyzed in future studies.
o Site surveys and urban emissions summaries of all IP Network
sites need to be compiled. The examination of elevated PM^
concentrations with respect to Hypotheses 1 and 2 was hampered
in many cases by the lack of site surveys and the source
distribution maps similar to those presented in Watson et al.
(1981). These would enhance the utility of the IP Network data
base immeasurably.
Three recommendations pertain the further analysis of IP Network data:
ซ The non-reportable data listing classified by elements should
be examined to identify days on which individual source-types
are large contributors, and the PMj5 mass should be examined
for these days to see if it is generally high. For example,
PM^5 vanadium reached a near network high of 1.06 yg/m in
Hartford, CT, on 10/31/81, which may be indicative of a large
contribution from residual oil combustion. PM}5 was only 41
ug/m on this date, which by no means approaches a maximum.
There may be many incidences when a source-type, as indicated
by a trace element, reaches its maximum contribution, yet the
overall PM|$ mass concentration is well within normal bounds.
The occurrence of meteorological regimes needs to be iden-
tified. Days on which they occur need to be examined for ele-
vated PMj5 concentrations. Several patterns of temperature
soundings and synoptic weather maps have been found to
correspond with elevated concentrations. If the meteorological
conditions they represent are truly causal factors, then for
each such c%se the PM^ concentration should be above average.
1980 to 1982 weather maps need to be examined and classified
for these cases and the concentrations for days on which they
occur can be drawn from the data base.
o Source contributions need to be quantified by receptor modeling
methods. Some local -source samples might be taken for chemi-
cal mass balance analyses. Factor analysis and linear
regression models might also be tested for creating site-
specific source composition matrices.
51
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REFERENCES
Chow, J.C., V. Shortell, J. Collins, J.G. Watson, T.G. Pace and B.
Burton, 1981: A Neighborhood Scale Study of Inhalable and Fine
Suspended Particulate Matter Source Contributions to an Industrial
Area in Philadelphia. Presented at the 74th Annual Meeting of the
Air Pollution Control Association, Philadelphia, PA.
Chow, J.C., J.G. Watson, J.J. Shah and T.G. Pace, 1982: Source
Contributions to Inhalable Particulate Matter in Major U.S. Cities.
Presented at the 75th Annual Meeting of the Air Pollution Control
Association, New Orleans, LA.
Cooper, J.A., J.G. Watson, and J.J. Huntzicker, 1979: Summary of the
Portland Aerosol Characterization Study. Presented at the 72nd
Annual Meeting of the Air Pollution Control Association, Cincinatti,
OH.
Environmental Reporter, 1983: EPA to Propose Particulate Standard
Representing Relaxation of 18 Percent. Environmental Reporter, 13,
1787. :~
Feder'al Register, 1984: Proposed Revisions to National Ambient Air
Quality Standards for Particulate Matter to Control Particles 10
Micrometers or Less. Federal Register, 49 FR 10408, March 20, 1984.
Flocchini, R.G., T.A. Cahill, M.L. Pitchford, R.A. Eldred, P.J. Feeney,
and L.L. Ashbaugh, 1981: Characterization of Particles in the Arid
West. Atmospheric Environment, 15, 2017.
Graf, J.L. and R.G. Draftz, 1979: Total Suspended Particulates
Non-Attainment Study for Cleveland, OH. Prepared for EPA Region V
by the Illinois Institute of Technology Research Institute, Chicago,
IL.
Hidy, G.M. et all, 1975: Summary of the California Aerosol
Characterization Experiment. Journal of the Air Pollution Control
Association, 25, 1106.
King, R.B., J.S. Fordyce, A.C. Antoine, H.F. Leibecki, H.E. Neustadter,
and S.M. Sidik, 1976: Elemental Composition of Airborne
Particulates and Source -Identification: An Extensive One Year
Survey. Journal of the Air Pollution Control Association, 26, 1073.
Liu, B.Y.H. and D.Y.H Pui, 1981: Aerosol Sampling Inlets and Inhalable
Particles. Atmospheric Environment, 15, 584.
52
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Mueller, P.K., G.M. Hidy, R.L. Baskett, K.K. Fung, R.C. Henry, T.F.
Lavery, N.J. Lordi, A.C. Lloyd, J.W. Thrasher, K.K. Warren, and J.G.
Watson, 1983: Sulfate Regional Experiment (SURE): Report of
Findings. Report EA-1901, Electric Power Research Institute, Palo
Alto, CA.
Rodes, C.E., 1979: Protocol for Establishment of a Nationwide
Inhalable Particulate Network. USEPA/EMSL Report, Research
Triangle Park, NC.
Shaw, R.W., R.K. Stevens, C.W. Lewis, and J.H. Chance, 1981: Comparison
of Aerosol Sampler Inlets. Presented at the 74th Annual Meeting of
the Air Pollution Control Association, Philadelphia, PA.
Suggs, J.C., and R.M. Burton, 1983: Spatial Characteristics of
Inhalable Particles in the Philadelphia Metropolitan Area. Journal
of the Air Pollution Control Association, 33, 668.
Trijonis, J., 1983: Development and Application of
Inhalable and Fine Particle Concentrations
Atmospheric Environment, 17, 999-1008.
J y -3
Estimating
Hi-Vol Data.
Methods for
from Routine
USEPA, 1980:
Assurance
Inhalable Particulate Network Operations and Quality
Manual
U.S. Environmental Protection Agency
Environmental Monitoring Systems Laboratory, Research Triangle Park.
Watson, J.G, 1979: Chemical Element Balance Receptor Model
for Assessing the Sources of Fine and Total Suspended
Matter in Portland, Oregon. Ph.D. Dissertation, Oregon Graduate
Center, Beaverton, OR.
Methodology
Particulate
Watson, J.G., J.C. Chow
Particulate Matter
Triangle Park, NC.
and, J.J. Shah,
Measurements.
1981: Analysis of Inhalable
EPA-450/4-81-035, Research
Watson, J.G., J.C. Chow, J.J. Shah, and T.G. Pace, 1983: The Effect of
Sampling Inlets on the IP and TSP Concentration Ratios. Journal of
the Air Polluticfo Control Association. 33, 114.
Yocom, J.E., E.T. Brookman, R.C. Westman, and O.P. Ambardar, 1981:
Determining the Contributions of Traditional and Nontraditional
Sources of Particulate Matter. Journal of the Air Pollution
Control Association, 31, 17.
53
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APPENDIX A
CASE STUDIES OF ELEVATED PM15 CONCENTRATIONS
Each of the 50 cases specified in Table 3-1 is examined in detail
in this Appendix. The size-specific mass and chemical data have been
grouped by urban area in Tables A-2 to A-ll. Detection limits for the
chemical species as a function of year are presented in Table A-l for
comparison against the values in the subsequent tables. The caveat that
Al , Si, Cl, K, Ca, and Ni are not normally reported by EPA, owing to
lack of interlaboratory comparability, is repeated here.
Also reported in Tables A-2 to A-ll are the coarse to fine mass
ratios and the temperature/pressure correction factors. After examina-
tion of the various data reports, it was found that these factors were
applied to fine mass concentrations in all cases, but they did not
appear to have been applied to all coarse mass concentrations. The fac-
tors were applied to sulfate and nitrate values, but to none of the ele-
mental concentrations. To maintain a consistent picture, the values
reported in Tables A-2 to A-ll have riot been corrected by these factors.
In all cases, these factors do not differ from unity by more than a few
percent and the adjdstments are well within the routine data uncertain-
ties of 5 to 10%. They have been listed to establish comparability of
the values listed here with those presently in the IP Network data
base.
54
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TABLE A-l
DETECTION LIMITS FOR SELECTED
ELEMENTS QUANTIFIED BY X-RAY FLUORESCENCE
Detection Limit, yg/ms
Element
Al*
Si*
pa
Sa
Cia
Ka
Caa
V
Mn
Fe
Ni
Cu
Zn
Br
Pb .
1979
0.210
0.060
0.035
0.025
0.055
0.025
0.030
0.015
0.010
0.010
0.005
0.005
0.'005
0^001
0.010
1980
0.250
0.070
0.040
0.030
0.065
0.030
0.030
0.015
0.010
0.010
0.005
0.005
0.005
0.002
0.010
1981
0.140
0.040
0.020
0.020
0.040
0.020
0.020
0.010
0.010
0.010
0.005
0.005
0.005
0.005
0.005
1982
0.140
0.040
0.020
0.020
0.040
0.020
0.050
0.020
0.020
0.020
0.005
0.005
0.005
0.005
0.010
a These elemental concentrations are not normally reported by EPA
because interlaboaratory comparisons for their values have
demonstrated ambiguous results.
55
-------
TABLE A-2
SITE-DAY DESCRIPTIONS FOR
BIRMINGHAM, AL: NORTH BIRMINGHAM
O 1 1 C.
DAY
Observable
HIVOL mass
SSI mass
PMic mass
COARSE-15 mass
FINE-15 mass
Alb C
F
F
Fe C
F
S04 C
. F
N03 C
F
V C
F
Ni C
F
Clb C
F
8r C
F
Pb C
F
Kb C
F
Mn C i
F
Zn C '
F
Cu C
F
Cab C
F
COARSE/FINE
HIVOL Correction
SSI Correction
COARSE and FINE
7/14/80
236
157
134
79
54
No
II
If
11
tt
tt
II
M
n
..
tt
it
it
tt
il
tt
H
H
II
It
It
It
II
II
II
ft
II
It
II
1
1
1
1
.9
.4
.4
.9
.5
data
It
If
M
rr
it
ti
tt
it
n
ti
M
It
It
M
If
tt
It
If
ft
11
tt
II
tl
II
It
M
II
It
II
.47
.010
.010
.013
12/5/80 8/26/81
277.
214.
164.
90.
7}.
3
0
5
7
8
No data
II
tt
n
tt
tt
n
it
ii
ii
ii
ti
ซ
n
it
it
11
ii
n
n
n
ii
it
M
tt
11
if
tt
n
it
i.
0.
0.
0.
11
II
It
tl
n
it
ti
it
n
ii
n
tt
it
ti
n
it
ii
ti
tt
ti
n
ii
n
n
n
ti
ft
ii
it
23
978
990
984
178
141
112
51
61
No
H
II
11
tt
n
i
25
0
0
11
It
II
tl
tf
fl
"
If
ft
It
tt
II
II
II
It
II
If
H
ft
11
0
1
1
1
.2
.4
.9
.8
.1
data
II
tl
II
tt
II
.3
.0
.78
.29
II
If
II
II
II
II
II
11
H
If
It
It
It
M
II
It
It
If
H
It
.85
.020
.020
.013
5/5/82
305.
214.
182.
118.
63.
4
7
3
6
7
No data
tt
tt
tl
It
tl
1
ft
tt
II
It
tl
tt
tl
II
II
n
11
ft
it
ti
M
n
it
11
it
tt
it
if
n
i.
i.
i.
i.
II
11
tl
If
II
II
II
ft
tt
II
It
11
II
II
It
II
It
tt
II
II
11
II
If
II
It
II
II
11
tl
86
020
020
013
Correction
All concentrations are in
b. These concentrations are not normally reported by EPA owing to lack
of comparability between Analysis laboratories
56
-------
TABLE A-3
SITE-DAY DESCRIPTIONS FOR
BUFFALO, NY: P.S. 26
J A 1 l_
DAY
Observable
HIVOL mass
SS I mass
PM^ mass
COARSE-15 mass
FINE-15 mass
Alb C
F
Sib c
F
Fe C
F
S04 C
F
NOj C
F
V C
F
Ni C
F
Clb C
F
Br C
F
Pb C
F
Kb C
F
Mn C '
F
Zn C
F
Cu C
F
Cab C
F
COARSE/FINE
HIVOL Correction
SSI Correction
COARSE and FINE
Correction
9/18/79
153.2
No data
143.1
71.3
71.8
2.14
0.30
5.07
0.55
6.17
1.11
2.77
30.30
2.70
1.91
0.015
0.015
0.017
0.009
0.54
0.13
0.024
0.077
0.15
0.41
0.48
0.64
0.32
0.081
0.21
0.25
0.41
0.020
6.70
0.37
0.99
1.002
1.02
1.005
r.D.
1/4/81
28.2
No data
148.9
64.9
84.0
No data
II II
II tl
M tl
II tl
tl It
If II
II "It
II M
II II
II II
tl II
II It
II II
fl It
M M
II It
II It
It II
II II
II tl
tt tl
If II
II tl
II M
II M
II II
It It
tl tt
II II
II It
0.944
0.964
0.970
4/4/81
No data
No data
142.0
38.6
103.4
3.30
4.91
2.03
2.57
2.30
5.14
2.13
18.7
0.56
0.81
0.010
0.010
0.008
0.020
0.33
1.10
0.008
0.084
0.045
0.86
0.22
1.45
0.11
0.18
0.031
0.21
0.010
0.048
2.70
3.60
0.37
0.980
1.002
1.005
6/15/81
No data
123.6
130.2
52.2
78.0
14.24
6.24
2.16
2.16
1.93
2.19
2.35
15.7
0.55
2.60
0.010
0.010
0.005
0.010
0.31
0.70
0.009
0.081
0.067
0.51
0.21
0.72
0.032
0.073
0.044
0.21
0.024
0.032
1.11
1.02
0.67
0.980
1.002
1.005
a. All concentrations are in yg/m-'
b. These concentrations are not normally reported by EPA owing to lack
of comparability between analysis laboratories
57
-------
TABLE A-3 (continued)
SITE-DAY DESCRIPTIONS TOR
BUFFALO, NY: BIG SISTER AND WILMUTH PUMP
31 ic. Dig o later
DAY 8/7/80
Observable
HIVOL mass 60.0
SSI mass No data
PM15 mass 129.5
COARSE-15 mass 80.0
FINE-IS mass 49.5
Alb C No data
Sib C ซ ซ
F " "
Fe C " "
C- MM
50^ C " "
f* II II
N03 C " "
r M n
V C " "
F " "
Ni" C " "
r M ii
C1b c .. ..
C II II
Br C " "
C II II
Pb C " "
C II II
Kฐ C " "
p M II
Mn C4 " "
F. " "
Zn C " "
F " "
Cu C " "
C II II
Cab C - "
F " "
COARSE/FINE 1.61
HIVOL Correction 1.002
SSI Correction No data
COARSE and FINE 1.005
5/22/81 6/15/81
177.0
168.1
187.2
136.5
50.7
3.22
0.44
9.92
1.10
10.84
5.55
2.25
9.31
3.69
2.13
0.014
0.010
0.020
0.013
1.41
0.79
0.019
0.089
0.18
0.94
0.90
3.29
0.39
0.14
0.12
0.83
0.018
0.043
26.5
2.46
2.69
0.980
1.002
1.005
No data
163.5
144.9
94.2
50.7
2.42
0.65
4.51
1.48
5.55
7.05
3.9
16.0
2.94
0.93 '
0.010
0.010
0.016
0.015
1.2
0.39
0-.015
0.035
0.23
0.63
0.58
2.29
0.10
0.17
0.29
2.00
0.012
0.047
25.1
1.75
1.85
0.980
1.002
1.005
7/9/81
No data
209.0
198.2
149.6
48.6
0.14
No data
0.040
No data
0.010
No Data
4.7
13.5
1.B8
1.10
0.22
No data
5.10
No data
0.040
No data
0.050
No data
0.007
No data
0.020
No data
0.62
No data
3.25
No data
0.26
No data
0.047
No data
3.12
0.980
1.002
1.005
Correction
a. All concentrations are in yq/m-5
b. These concentrations are not normally reported by EPA owing to lack
of comparability between analysis laboratories
58
-------
TABLE A-4
SITE-DAY DESCRIPTIONS FOR
CLEVELAND, OH: BIDOULPH 4 54th
JAIL.
DAY
Observable
HIVOL mass
SSI mass
PM^j mass
COARSE-15
FINE-15 mass
Alb C
F
Sib C
F
Fe C
F
S04 c
F
NOj C
F
V C
F
Nib C
F
Clb C
F
Br C
F
Pb C
F
Kb C
F ,
Mn C
F
Zn C
F
Cu C
F
Cab C
F
COARSE/FINE
HIVOL Correction
SSI Correction
COARSE and FINE
Correction
7/20/79
No data
No data
175.7
96.0
79.7
4.12
0.21
9.68
8.74
8.13
1.15
2.90
18.52
2.88
0.16
0.17
0.15
0.21
0.19
2.17
0.30
0.043
0.11
0.52
2.00
1.01
1.08
0.26
0.063
0.49
1.13
0.076
0.093
8.87
0.58
1.20
1.001
No data
No data
9/6/79
223.6
No data
144.9
100.3
44.6
3.19
0.22
18.73
1.16
4.51
0.42
1.34
17.82
3.80
0.55
0.15
0.15
0.010
0.006
0.70
0.090
0.031
0.038
0.16
0.42
1.09
0.22
0.12
0.024
0.14
0.10
0.032
0.018
*7.51
0.40
2.25
1.001
No data
No data
11/5/79 9/12/80 4/4/81
227.3
No data
140.2
72.5
67.7
2.79
0.33
8.04
0.76
5.36
1.25
.1.92
15.90
1.22
1.20
0.15
0.15
0.019
0.018
1.30
5.26
0.055
0.33
0.42
1.34
0.72
1.32
0.19
0.092
1.05
1.10
0.050
0.065
6.37
0.54
1.07
0.955
No data
No data
191.2
134.0
123.2
67.7
55.5
3.45
0.37
6.98
1.21
4.29
0.57
1.28
12.84
2.67
0.42
0.02
0.02
0.02
0.01
2.00
1.79
0.03
0.10
0.17
0.62
0.82
2.25
0.17
0.05
0.35
0.39
0.07
0.07
6.24
0.58
1.22
0.991
1.001
1.008
186.2
No data
135.8
82.5
53.3
2.74
0.48
7.43
1.18
12.30
5.14
3.01
8.06
0.79
0.90
0.01
0.01
0.03
0.02
0.93
1.19
0.01
0.04
0.80
0.64
0.74
2.07
0.43
0.33
1.30
2.51
0.03
0.06
7.37
.89
1.55
0.991
1.001
1.008
8/26/81
196.1
143.5
223.4
23.1
200.3
No data
II H
H H
tl H
n ซ
W H
n ft
Mr II
MI n
M n
Hป n
M II
i it
n
a it
M It
it n
n *
n n
1* H
II M
it 11
n ti
it n
n n
n H
n n
it ii
n it
it n
it n
10/13/81
299.6
170.1
131.9
92.5
39.4 -
2.45
0.26
8.10
0.49
5.53
1.47
2.31
6.79
1.31
0.78
0.01
0.01
0.01
0.01
1.84
2.47
0.01
0.07
0.11
0.55
0.68
1.33
0.19
0.11
0.36
0.71
0.04
0.05
9.35
0.53
2.35
0.955
0.955
0.974
a. All concentrations are in yg/m
b. These concentrations are not normally reported by EPA owing to lack
of comparability between analysis laboratories
59
-------
TABLE A-5
SITE-DAY DESCRIPTIONS FOR
PHILADELPHIA, PA: T & A PET SHOP, ME TRANSFER,
AND BRIDESBURG RECREATION CENTER
SITE
DAY
Observable
HIVOL mass
SSI mass
PMi c mass
COARSE-15 mass
FINE-15 mass
Alb C
F
Sib C
F
Fe C
F
S04 C
F
NOj C
F
V C
F
Ni' C
F
Clb C
F
Br C
F
Pb C
F
Kb C
Mn C
F
Zn C
F
Cu C
F
Cab C
F
COARSE/FINE
HIVOL Correction
SSI Correction
COARSE and FINE
Correction
T & A Pet
11/20/79
192.4
No data
173.0
64.2
108.8
2.90
0.81
6.39
0.99
4.38
0.90
4.2
35.0
1.94
6.22
0.14
0.15
0.05
0.11
0.83
0.48
0.11
0.45
0.59
1.82
0.62
0.44
6.9
0.90
No data
ti 11
0.10
0.06
2.6
0.49
0.59
No data
No data
0.965
Bridesburg
12/5/79
176.5
No data
124.8
77.3
47.5
3.04
0.49
4.73
0.45
1.80
0.33
0.8
7.2
1.13
3.75
0.02
0.02
0.01
0.02
0.49
2.38
0.02
0.17
0.15
0.56
0.47
0.28
0.04
0.02
0.22
0.26
0.04
0.21
1.66
0.34
1.64
No data
No data
0.965
Recreation
12/11/79
173.7
No data
126.9
67.0
59.9
2.92
0.45
5.67
0.59
2.16
0.33
2.0
10.9
1.09
4.81
0.02
0.06
0.02
0.04
0.72
1.44
0.04
0.22
0.22
0.76
0.50
0.27
0.04
0.01
0.79
0.93
0.14
0.61
2.15
0.35
1.12
No data
No data
0.965
NE Transfer
11/20/79
180.2
No data
151.8
45.2
106.3
3.15
0.63
6.46
0.79
2.90
0.78
4.6
31.3
0.52
9.22
0.05
0.10
0.04
0.10
0.55
0.40
0.07
0.27
0.34
1.26
0.59
0.31
0.06
0.05
0.30
0.50
0.07
0.05
2.87
0.49
0.42
No data
No data
0.965
a. All concentrations are in
b. These concentrations are not normally reported by EPA owing to lack
of comparability between analysis laboratories
60
-------
TABLE A-5 (continued)
SITE-DAY DESCRIPTIONS FOR
PHILADELPHIA, PA: ALLEGHENY AND PRESBYTERIAN HOME
7' ! C.
DAY
Cbs'?r-. ab le
K! . X mass
S S fT'B S 3
pvu . mass
CO"3>SE-15 mass
F i ("> 1 5 mass
VD c
r
S'" C
F
Fa C
r
C-v Q
" a
r
>.. c
r
v C
T
v: :
r
C.:' C
F
8- C
F
Pb C
F
n w
F
t*n C
c
In C
F
Cu C
r
Ceb C
F
COA;-.SE/FINE
HI J'OL Correction
SSI Correction
COARSE and FINE
Correction
11/20/79
195.2
167.2
134.0
51.9
82.1
No data
n it
n n
n ii
n n
it n
M II
II It
II tl
II II
II It
II II
II II
n ti
n n
n it
!ป II
n n
ii it
it it
11 M
II II
11 II
11 It
It tl
It It
II II
II tl
It II
II II
0.63
0.947
0.947
0.965
11/20/79
161.5
No data
146.3
43.1
112.2
2.88
0.68
5.36
0.98
2.45
0.82
3.4
35.0
0.47
2.61
0.16
0.13
0.05
0.10
0.28
0.40
0.10
0.32
0.42
1.70
0.45
0.55
0.04
0.05
0.16
0.38
0.03
0.06
1.54
0.34
0.30
0.947
No data
0.965
3/10/80
No data
No data
136.4
8.9
127.5
0,89
0.27
1.91
0.21
0.67
0.18
1.03
4.06
0.79
1,29
0.02
0.02
0.01
0.02
0.14
0.35
0.02
0.11
0,13
0.60
0.17
0.19
0.01
0.01
0.05
0.11
0.01
0.02
1.58
0.28
0.07
0.947
No data
0.965
a. All concentrations are in q/m
b. These concentrations are not normally reported by EPA owinq to lack
of comparability between analysis laboratories
61
-------
TABLE A-6
SITE-DAY DESCRIPTIONS FOR
PITTSBURGH, PA, HARTFORD, CT, CHICAGO, IL
IRON TON, OH, AND YOUNGS TOWN, OH
oi ii-
DAY
Observables
HIVOL mass
SS I mass
PMi c mass
COARSE-15 mass
FINE-15 mass
Alb C
F
Sib C
F
Fe C
F
S04 C
F
N03 C
F
V C
F
Ni C
F
Clb C
F
Br C
F
Pb C
F
Kb C
F *
Mn C
F
Zn C
F
Cu C
F
Cab C
F
COARSE/FINE
HIVOL Correction
SSI Correction
COARSE and FINE
--riLtsDurgn - nartrorg uru.(.ayu -irum-un
10/30/80 5/22/81 1/22/81 2/3/81 4/4/81
364.1 228.7
No data No data
183.6 137.5
59.5 79.4
124.1 58.1
No data No data
" " 0.67
" " No data
11 " 0.89
" " 7.24
11 " 4 . 83
" " 2.9
" " 16.3
" " 1.008
" " 0.29
" " 0.018
11 " 0.010
" " 0.042
" " 0.024
" " No data
" " 0 . 66
11 " 0.030
" " 0.17
" " 0.24
" " 1.008
" " 0.76
" " 0.87
" " 0.45
" " 0.37
" " 0.35
" " 1.300
" " 0.066
" " - 0.10
" " 7.09
" " 0.80
0.48 1.37
0.974 0.992
No data No data
0.980 1.016
212.6
154.0
126.4
65.4
61.0
3.26
0.54
9.53
0.52
2.26
0.21
0.6
11.1
1.22
1.32
0.035
0.067
0.042
0.034
9.81
0.300
0.060
0.35
0.29
1.10
0.76
0.44
0.049
0.024
0.094
0.23
0.039
0.071
1.61
0.37
1.08
0.938
0.938
0.962
209.4
No data
120.1
61.9
58.2
No data
n n
ii n
it ii
n if
ซ n
tt n
n ซ
II M
ti tt
ii ii
i n
i n
n M
it ti
n n
n ti
n tt
it it
tl n
it n
ti n
ii tt
11 it
i tl
it if
it ii
H It
II It
II II
1.06
0.962
0.952
0.970
175.9
121.4
123.7
75.3
48. 4
2.65
0.14
8.00
0.073
5.65
0.053
0.89
4.7
1.87
1.96
0.010
0.010
0.008
0.005
0.30
0.040
0.008
1.03
0.038
0.050
0.71
0.22
0.23
0.010
0.093
0.005
0.013
0.005
6.27
0.02
1.56
1.004
1.004
1.012
2/15/81
210.7
173.9
127.3
56.3
71.0
2.74
0.44
5.95
0.53
3.51
0.80
1.6 .
13.2
0.88
1.72
0.010
0.010
0.011
0.012
7.43
3.66
0.047
0.31
0.22
0.79
0.40
0.50
0.081
0.051
0.121
0.43
0.019
0.025
4.82
0.33
0.79
0.997
0.944
0.978
Correction
a. All concentrations are in yg/nr
b. These concentrations are not normally reported by EPA owing to lack
of comparability between analysis laboratories
62
-------
TABLE A-7
SITE-DAY DESCRIPTIONS FOR
PHOENIX, AZ: ROOSEVELT ST.
ji 11-
DAY
Observable
HIVOL mass
SSI mass
PM^j mass
COARSE-15 mass
FINE-15 mass
Alb C
F
Sib c
F
Fe C
F
S04 C
F
N03 C
F
V C
F
Nik C
F
Clb C
F
Br C
F
Pb C
F
Kb C
F
Mn C '
F
Zn C
F
Cu C
F
Pb C
F
COARSE/FINE
HIVOL Correction
SSI Correction
COARSE and FINE
Correction
noose ven
6/21/81
92.1
54.3
145.8
39.0
106.8
No data
It It
II It
II II
II 41
ซ ft
II II
II 11
11 II
n it
it n
n n
n n
H 11
n 11
H II
tt tt
II HI
ti ti
it it
it it
M II
It M
tt 11
II II
II II
n ti
ii it
II -. **
II If
0.37
1.054
1.054
1.032
t Ji.. -
11/6/81
157.9
115.7
107.6
77.2
30.4
0.140
0.140
0.054
0.040
0.083
0.037
0.5
0.06
0.91
0.42 .
0.010
0.010
0.005
0.005
0.046
0.040
0.56
0.58
0.005
0.005
0.066
0.10
0.010
0.010
0.005
0.005
0.005
0.005
2.39
0.39
2.56
1.028
1.028
1.003
a. All concentrations are in jjg/m
b. These concentrations are not normally reported by EPA owing to lack
of comparability between analysis laboratories
63
-------
TABLE A-B
SITE-DAY DESCRIPTIONS TOR
BAKERSFIEID, CA: CHESTER AVE.
Oi 1 C.
DAY
Observable
HI VOL mass
SSI mass
PMi c mass
COARSE-15 mass
FINE-15 mass
Alb C
F
Sib C
F
Fe C
F
S04 C
F'
N03 C
F
V C
F
Ni C
F
Clb C
F
Br C
F
Pb C
F
Kb C
F
Mn C *
F
Zn C
F
Cu C
F
Cab C
F
COARSE/FINE
HIVOL Correction
SSI Correction
COARSE and FINE
Correction
11/17/80
234.0
213.1
183.1
110.3
72.8
8.83
0.73
23.88
1.028
5.41
0.44
0.81
9.0
2.62
6.76
0.010
0.065
0.025
0.17
0.52
0.25
0.11
0.63
0.46
0.25
2.61
1.07
0.11
0.016
0.076
0.047
0.022
0.023
4.sr
0.48
1.52
0.968
0.968
0.986
-i.nesi.er
12/23/80
230.3
217.7
196.8
54.2
142.6
4.18
0.42
11.59
0.43
2.43
0.17
2.20
21.10
1.28
46.0
0.010
0.044
0.016
0.013
0.081
0.48
0.064
0.51
0.32
0.15
1.22
0.19
0.046
0.010
0.049
0.050
0.016
0.013
1.91
0.18
0.38
0.968
0.968
0.986
ซ ve .
1/10/81
202.3
183.9
176.3
52.6
123.7
0.14
0.14
0.04
0.04
0.064
0.064
12.05
44.65
1.01
13.78 '
0.01
0.01
0.005
0.005
0,04
0.04
0.31
2.28
0.12
0.005
0.028
0.046
0.01
0.01
0.005
0.005
0.005
0.005
0.02
0.02
0.42
0.968
0.968
0.986
2/3/81
132.6
143.3
128.3
33.5
94.8
0.14
0.14
0.14
0.14
0.057
0.064
1.52
13.45
1.16
25.70
0.01
O.Q1
0.005
0.005
O.Q4
0.04
0.37
2.87
0.028
0.005
0.042
0.038
0.01
0.01
0.005
0.005
0.005
0.005
0.02
0.02
0.35
0.968
0.968
0.986
a. All concentrations are in yg/ra
b. These concentrations are not normally reported by EPA owing to lack
of comparability between analysis laboratories
64
-------
TABLE A-9
SITE-DAY DESCRIPTIONS FOR
RUBIDOUX, CA: RUBIDOUX
SITE
DAY
^ซ
Observables
HI VOL mass
SS I mass
PMj^ mass
COARSE-15 mass
FINE-15 mass
Alb C
C
Sib C
F
Fe C
F
S04 C
F
N03 C
F
V. C
F
Ni~ C
F
Clb C
F
fir C
F
Pb C
F
Kb C
F
Mn C
F
Zn C
F
Cu C
F
ซ. K -.
Cab C
F
COARSE/FINE
HIVOL Correction
SSI Correction
COARSE and FINE
B k.
10/12/79
_ .
195.7
No data
157.3
53.3
104.9
3.83
0.35
10.68
0.57
2.90
0.21
2.42
9.25
8.39
20.01
0.015
0.015
0.015
0.019
1.24
0.24
0.092
0.24
0.29
1.16
1.59
0.18
40.066
0.010
* 0.075
0.057
0.079
0.018
7.47
0.33
0.51
0.985
0.985
0.988
10/24/79
221.8
No data
171.0
67.6
103.4
0.31
0.35
0.33
0.55
0.036
0.27
0.70
6.68
3.58
37.05
0.015
0.015
0.005
0.017
0.055
0,24
0.001
0.30
0.010
1.57
0.16
0.10
0.010
0.019
0.005
0.068
0.005
0.025
Q..14
0.39
0.65
0.985
0.985
0.988
6/20/80 8/7/80
210.0
182.3
156.0
87.0
69.0
3.92
0.32
10.34
0.49
2.90
0.21
1.87
9.58
8.58
15.41
0.015
0.015
0.008
0.016
0.65
0.14
0.032
0.077
0.16
0.51
1.64
0.14
0.059
0.010
0.051
0.039
0.025
0.023
5.94
0.26
1.27
0.992
0.992
0.995
^^^^"^^^M
263.6
214.4
162.3'
103.7
58.6
4.91
0.35
13.07
0.53
3.73
0.28
1.54
9.72
0.42
2.79
0.015
0.015
0.013
0.019
0.58
0.13
0.048
0.13
0.20
0.78
1.93
0.18
0.081
0.011
0.069
0.057
0.035
0.046
10.16
0.56
1.75
0.992
0.992
0.995
5/22/81
No data
128.7
125.6
81.1
44.5
3,88
0.23
10.44
0.29
2.60
0.13
1.18
4.92
6.84
9.21
0.010
0.010
0.007
0.005
1.42
0.098
0.033
0.080
0.10
0.32
1.46
0.088
0.053
0.010
0.044
0.023
0.019
10.010
4.15
0.39
1.82
No data
No data
0.995
2/22/82
No data
No data
217.0
53.2
163.8
No data
M ซ
n ii
ii ii
n n
n n
n ซi
n n
n ti
n n
il u
II M
n 11
n n
n n
M n
u n
il ti
n n
n ii
n n
II M
n n
ii n
11 11
M II
ii M
n n
it ii
ii n
n n
n n
n n
11 ii
Correction
a. All concentrations are in yg/nr
b. These concentrations are not normally reported by EPA owing to lack
of comparability between analysis laboratories
65
-------
TABLE A-10
SITE-DAY DESCRIPTIONS FOR
EL PASO, TX: TILLMAN HEALTH
AND EL PASO COUNTY
SITE Tillman Health El Paso County
DAY 11/29/79 12/11/79 4/29/82
Observable
HIVOL mass
SSI mass
PMi c mass
COARSE-15 mass
FINE-15 mass
Alb C
F
F
Fe C
F
S04 .C
F
NOj C
F
V C
F
Ni C
F
Clb C
F
Br C
F
Pb C
F
Kb C
F 4
Mn C
F '
Zn C
F
Cu C
F
Cab C
F
COARSE/FINE
HIVOL Correction
SSI Correction
COARSE and FINE
Correction
206.3
147.3
126.0
81.4
44.6
3.82
0.60
9.79
0.68
1.74
0.17
1.46
3.21
1.24
0.77
0.015
0.015
0.008
0.005
0.54
1.63
0.11
0.43
0.54
1.59
0.92
0.50
0.074
0.011
0.11
0.10
0.064
0.039
14.13
1.21
1.82
1.043
1.043
1.042
217.6
No data
130.9
120.7
10.2
3.40
0.45
8.59
0.61
1.15
0.14
0.87
1.30
0.30
1.36
0.015
0.015
0.006
0.005
0.32
0.11
0.010
0.044
0.039
0.15
0.98
0.45
0.029
0.010
0.029
0.015
0.11
0.014
5.59
0.76
12.5
1.043
1.043
1.042
104.2
No data
399.6
19.1
380.5
No data
n n
ซ it
it it
ti n
it it
it n
If H
it it
it it
H it
it it
ti it
ii n
it n
it it
it it
it it
it it
ti it
it ti
it n
tt n
ii ii
n ซ
tt ti
it ii
it tt
ti ปt
n it
0.05
1.145
No data
0.076
a. All concentrations are in yg/m'
b. These concentrations are not normally reported by EPA owing to lack
of comparability between analysi-s laboratories
66
-------
TABLE A-ll
SITE-DAY DESCRIPTIONS FOR
FRESNO, CA, SAN JOSE, CA, AND PORTLAND, OR
Jl 1 U
DAY
Observable
HIVOL mass
SSI mass
PM^j mass
COARSE-15 mass
FINE-15 mass
Alb C
F
Sib C
F
Fe C
F
S04 C
F
N03 C
F
V C
F
Ni C
F
Clb C
F
Br C
F
Pb C
F
Kb C
F
Mn C *
F
Zn C
F
Cu C
F
Cab C
F
COARSE/FINE
HIVOL Correction
SSI Correction
COARSE and FINE
Correction
r resno -----
12/11/80
166.2
138.9
123.5
47.9
75.6
3.87
0.25
12.27
0.35
2.21
0.10
1.15
6.44
0.42
28.61
0.010
0.010
0.013
0.025
0.092
0.10
0.005
0.030
0.024
0.12
1.053
0.22
0.030
0.010
0.025
0.016
0.19
0.028
1.87"
0.34
0.63
0.974
0.974
0.982
--sari .Jose
10/30/80
109.9
No data
120.1
47.0
73.1
2.75
0.54
9.22
0.61
2.23
0.30
0.63
4.02
1.53
13.75
0.015
0.015
0.011
0.013
0.17
0.25
0.087
0.47
0.35
1.59
0.66
0.62
0.042
0.011
0.066
0.12
0.031
0.065
1.92
0.39
0.64
0.975
No data
0.979
-rortiana
10/12/79
No data
No data
207.0
115.6
91.2
42.87
7.79
4..09
0ซ74
1..72
0.67
0.58
12 ..19
0.72
4.47
0.015
0.023
0.017
0.042
0.32
0.67
0.065
0.47
0.22
1.48
0.25
0.53
0.066
0.12
0.061
0.13
0.088
0.087
1.42
0.30
1.27
No data
No data
0.969
a. All concentrations are in yg/m
b. These concentrations are not
normally reported
by EPA owing to lack
of comparability between analysis laboratories
67
-------
The site-days have been arbitrarily divided into eastern and western
sites because consistent differences were observed in both the meteor-
ology and in the chemical character of samples taken in these sections of
the country. Urban-scale subsets have been formed within these two
geographical regions.
Each case study contains a general description of the aggregate
information acquired for the specific urban-scale subset. These
descriptions provide the basis for the support of the five hypotheses as
described in Sections 4 and 5. In the several cases where data are
inconclusive or inadequate to support or refute the hypotheses, the spe-
cific limitations are delineated so that future measurements may make up
for present shortcomings.
EASTERN SITES
Birmingham, AL (4 Site-Days)
The Birmingham data set in Table A-2 contains no dichotomous sampler
chemical or elemental information.
Since TSP is larger than PMjs, the ambient particle size distribu-
<
tion extended well beyond 15 ym to larger sizes. The HIVOL/PMis ratio,
for example, ranges from 1.6 to about 1.8, being at its lowest value on
8/16/8'! when the PM^ coarse/fine ratio reaches its minimum of 0.85. In
all cases, the coarse mode appears to be a major, if not the dominant,
component of the PM^. This is consistent with local or neighborhood-
scale sources. Industrial sources such as coke ovens, lime kilns, lead
68
-------
and c'uminuffi smelters, '"on and stee'ซ foundries, blast fcrnaoss. and
cem-,t plants, a;~e locate, in Blrralrtgncra, ~:nd a founds. ;s locatsa 1/4
Tile east :" the sits. ' - effects c* :-:i^ indust~"i :.ij^ces tป-*r-r.t
:e cscerta-"- '.< the ab: ce of enemies species, ;M- : -:rly fe .s
an indicato" r tne founorv.
A vacant lot of unssecified nature is situated ^n the block
southeast of the sampling site and the preponderance of course partscles
could result from some ac*..\-ity end an appropriate surface v^iicti wauld
allow suspension of coars: : ~~ :-.clss on ell four occasioss,
IT; Cent-_'vilie, AL, abouz 4D miles scwtn-
aopear arcuate * .r dust rSusjxปcrs'iOT
.11 of the Sinr.ingham days were 6 IHets.
Wind so.?, -neasureme'
west of r ">:riingham3 do
hov;ever. ' j^^ace wind:
four c2.:-k ihov;a broad
L-ce iTidt- for e:
a st2~1onarv *.
case;"., the 5CG tnb v'ndr;
3/26/81.
]y
.ssure regions : uit generally hrve 3v?ฃn on
. one or two days preceding sa-:h case,
Irawn over ceit"*.^ M on T/14/SC. LT a"!l
. =ry light, for ^vr.ple, 2 knr*. i , 35ฐ on
Chemical data are VIE, _tent to icent'i \ secondary Da-tide epi-
sodes. The weatrier maps ae '"-Hy indicate sluggish clrctflatians in the
vicinity of Pirminghcrr., witr- so-at^easter!y and southwesterly winds, not
conducive t<. sjlfate traispc"";" *ron the major sulfate pradactno regions
vj tr.e nort -r-d east of /'!: a for thess -leys.
69
-------
Though the circulation is sluggish, the available OOOOZ soundings on
7/14/80 and 8/26/81 show only weak inversions at about 800 mb, and it is
not clear that these were either subsidence inversions or major barriers
to vertical mixing.
Data validation checks give no cause for rejection of the data for
these days. Owing to lack of chemical and meteorological data these
cases neither support not refute any of the hypotheses.
Buffalo, NY (8 Site-Days)
Fe is the most likely contribution from steel mills close to P.S.
#26 and Wilmuth Pump. Fe can also result from resuspension of earth's
crustal material, but Watson (1979) summarizes a large selection of
literature which indicates that the Fe/Si ratio for the total tro-
pospheric background aerosol composition is usually considerably, less
than 1.0. These ratios are nearly equal to or greater than 1.0, and in
several cases greater than 2.0, in both the fine and coarse samples,
with the exception of 7/9/81 at Wilmuth Pump. For the Buffalo cases,
the Fe concentration ranges from .01 yg/m to 10.8 yg/m . The inter-
mediate values for ?e range from about 2 to about 6 yg/m in the coarse
fraction and usually exceed the coarse Si concentration by 10% to 20%.
Fine Fe concentrations range from 1.11 yg/m to 7.05 yg/m . Fe is
enriched in Buffalo, especially in the fine fraction, and the nearby
steel industry is a likely source. Local soils may have become
enriched in Fe due to the long-term operation of iron and steel mills in
70
-------
Buffalo. Resuspension of these soils may contribute to the high, coarse
Fe concentrations. This doesn't explain the elevated Fe concentrations
in the fi."ปe "''action where resuspended dust is less of a contributor.
Mn is ; a product of iron and steel processing. Watson et al.
.531) fojf-i :? Network average coarse and fine Mn concentrations to be
3
in the .01 *D .03 yg/m range. For these site days Mn ranges from .03,
* 3 '
to 0.52 ye/; . Intermediate values are in the 0.1 to 0.3 yg/m range
for ;.\v;h cocas'3 and fine fractions showing substantial enrichment. The
K; c-;j^se/fi'ฃ ratio is greater than 1.0 when the Fe coarse/fine ratio
fr i". grec~2- than one. It is less than 1.0 when the same is true for
Fe, i tnough tne absolute magnitudes of Fe and Mn do not show a clear
correlation. Chough Mn is a minor component of the particles generated
r.v -ic.-y type; " iron and steel processes, the Mn values further support
; - -, jothe:. . chat iron and steel plants contribute to Buffalo's high
r-:- ".-gs.
High coa~"? Ca concentrations were found at the Wilmuth Pump site on
6/'5/c: (2".i j.]/m3), on 5/22/81 (26.5 yg/m3), and at P.S. #26 on
9'Id/ 9 (6./ ur, 'i ). Since Ca is a non-reportable chemical species, its
hi nh -./alcies may be caused by a measurement anomaly.
The P.S. i'26 site is close to both a freeway and a railroad, but it
i; net clear tnat these have contributed in an important way. Pb con-
centrations, for example, are not excessive at P.S. #26.
S'j-fate values exceed nitrate, with the maximum value being
: 3 ug/m3 in t'le fine fraction at P.S. #26 on 9/18/79. Most fine
71
-------
sulfate concentrations are in the range of 10 to 15 yg/m , however, with
coarse values considerably less. Watson et al. (1981) cite an average
fine sulfate concentration of about 8 yg/m for urban-industrial IP
Network sites, and these values are not appreciably greater than Watson
et al. values.
High PMi5 levels were observed at both the P.S. #26 and Wilmuth Pump
sites on 6/15/81, implying that one or more contributions were espe-
cially significant on that day or a subregional phenomenon resulted in
high particluate matter loadings over the greater Buffalo area. The
regional-scale contributions are not well supported because 6/15/81 did
not emerge as a high site-day at any other eastern urban site.
Upper air soundings were available for all cases except 5/22/81. In
the case of 6/15/81, high pressure at the surface was retreating as a
warm front slowly advanced from the southwest. The sounding is very
nearly wet-adiabatic from 850 mb up to 500 mb, suggesting the presence
of an extensive cloud layer. The OOOOZ surface wind was 12 knots at
240ฐ. The 9/18/79 sounding (OOOOZ) shows more evidence of an inversion,
with its top at about 780 mb. The 9/18/79 surface map shows high
pressure retreating *as a cold front approaches from the northwest.
The 4/4/81 sounding at OOOOZ shows a pronounced inversion very close
to the surface (about 970 mb or 355 m). Surface winds were 6 knots at
220ฐ, but were much stronger and from the same direction aloft.
Conditions had been dry for several days, and on 4/4/81 the surface map
shows a low pressure system over the Great Lakes, approaching Buffalo
72
-------
from the west and causing rain by 4/5/Si. 4/4/51 v.-es also a high site-
day at Cleve";::" and Ironton, 0^-',. an-d wil" be d-ls^ssed shortly.
;ฃ 7/9 St. an: -: shows ~ -*eak ^^ve'^'c -,* 945 - 656 m) and a
muc?' more D '.;ec' c i-s ' i wrr;- 700-:',"-'' r-: ' -:~. ฃc: the surface
wine is s:g. -'.rant, 14 knots froa 250ฐ ct 00002.. "'n-.= receding days
show surfac'. r^gh preis.;re retredti^c ss -a cold frcnt approaches from
the northw-r bringinc ncderate a^wnts of or&r nta:*on by 7/10/81.
No ?r.;r ic was a -/all able for 5/22/8i; but zle surface map indi-
cates tha:. nsre haa been no prsctc"tr;'Trt -"or s^ie-'al days. On
b/?2/8i. r<;r-fa:e hign pressure vas center*-1 : -- southern Ohio, and a
jtjticnery front is shown tc the north of " ^ t'cat Lakes,
With the ,'D$sio'1e exception of Wi" T- Push's h^chest site-day,
S/'-7'?!, all ' '^ :ซ-.' cases seer ty - -
and s-jr^ace ! ..r, ; e^>:-ure leading uj t
concentration day, otten v.-it!i preclr -'lioa by the next day. Par-
ticulate matt?" DV3r Buffalo co-J7d bo _" optd! du^--c stagnant conditions
;ปrior to fr- ; ?1 massages. Tn--- rac . " : fee^sr ;?rticuTorly difficult
.. :. cla-ify \'"3:' one considers t^ t 54" ^1,07 .ปf-*re "*ten sigriificant,
ai'-.c SCTS so"; o" d'cti^c trans"1 .'"u K. " "s?., .?ป.. as chet observed in
SURE (Mueller and Hid\ -it n: . , 1^:3 K . -t be - -ed r-vit.
At the Big Sister site on 8; 7/8Q, : s PH^:*. ! /OL ratio was 2.16, at
P.S. A'2o on 1/4/81, tr.e highest cay ~-Z'~ this sit?, the PMjc/HIVOL ratio
w>c :.. 28. At tr.e Wiln-utn Pump ?--.e mi 5'22/Sl, the PM^r/HIVOL ratio was
. . )5 and these case?, support Hyr; "tr-es -.1 '. kt tv.ซ P.S. #26 site on
- several deys of dry weather
front?"- approach on the high
-------
6/15/81, no HIVOL values are given, but the PM^ exceeds the SSI value
by 5%. Though this is within EPA/EMSL criteria for acceptance, it is
not a common finding in the IP Network.
Cleveland, OH (7 Site-Days)
No site survey and no nearby radiosonde soundings were available for
Cleveland.
Graf and Draftz (1979) examined microscopic TSP compositions at nine
sites in the greater Cleveland area during 1977. One of the sites was
the same as the Cleveland site identified for the present study. Graf
and Draftz present a list of 24 Cleveland emissions sources, estimates
of their 1977 emissions, and a map showing their location with respect
to the sampling sites. Two Republic Steel facilities, a DuPont plant,
and the Lorain Cuyahoga Works of U.S. Steel are within one mile of the
sampling site. Graf and Draftz note, with respect to their 1977 survey
of the APC HQ site, "Emissions from iron industries were also the pri-
mary cause of elevated TSP levels recorded at this site."
King et al. (1976), also studying the Cleveland urban area, did
not analyze their results with the degree of spatial resolution given by
Graf and Draftz. They contrasted urban and suburban measurements. Some
of the relevant conclusions of these authors are that 1) Pb sources in
Cleveland are predominantly automotive, 2) there appears to be a local
industrial source of Br, and 3) that V, Mn, and Fe concentrations are
consistent with those expected from coal combustion.
74
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In the Cleveland measurements from Table A-4, coarse Si and Fe con-
centrations are elevated, but the Fe/Si ratio is less than 1.0, except
on 4/4/81. The Fe may originate from geological material. On 4/4/81, it
appears that a regional event took place, because that date is also a
high day at Ironton, OH, and Buffalo, NY. However, the Fe concentration
was not remarkably high at Buffalo on 4/4/81 (2.30 yg/m in coarse and
5.14 yg/m in the fine), nor was it an especially high value at Ironton
3 3
(5.65 yg/m in the coarse, and 0.053 yg/m in the fine). Neither coarse
nor fine Fe were regionally distributed on 4/4/81.
Coarse Ca is in the 6 to 9 yg/m range. Fine Ca is much lower,
ranging from 0.4 to 0.9 yg/m . Calcium-containing cement and calcium
sulfate aggregate particles (from iron melting operations) are noted in
the microscopic analyses of Graf and Draftz as a very minor component of
their samples.
Both Graf and Draftz, and King et al. note evidence of local sources
of vehicular traffic emissions, including diesel exhaust, Br, Pb, and
rubber tire fragments. Modest levels of Br and Pb are found in the pre-
sent data, however, the Br/Pb ratios are often substantially less than
the 0.2 to 0.3 value commonly accepted for aged auto exhaust, and
another source of Pb may be of importance.
Sulfate levels in Cleveland range from 6.8 to 18.5 yg/m in the fine
fraction with coarse values being considerably less. To check the
possibility that a regional-scale event was involved in the highest two
75
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cases, 18.5 yg/m3 on 7/19/79 and 17.8 yg/m3 on 9/6/79, sulfate con-
centrations at three nearby cities were checked: Akron, OH, Chicago,
IL, and Buffalo, NY. For two reasons, either that IP measurements had
not started yet or that no chemical data were given, Buffalo and Chicago
had no information to contribute. At Akron, however, fine sulfate
levels were 20.9 yg/m3 on 7/29/79 and 13.7 yg/m3 on 9/6/79. Graf and
Draftz also found high sulfate readings in a large proportion of their
Cleveland samples, and they comment on the difficulty of separating
regional-scale events from local phenomena when there are so many coal
emission sources close to Cleveland.
Only the 500 mb weather maps were examined for Cleveland. No soun-
dings were available.
On 7/20/79 weak surface high pressure was centered very nearly over
Cleveland. The previous three days had been dry, and a stationary .front
lay along the Atlantic coast on 7/18 and 7/19. On 9/6/79 a low pressure
system had moved north along the Atlantic coast causing rain in PA and
NY, while a cold front lay to the west. There had been a cold frontal
passage on 9/3 with significant rain followed by temporary clearing on
9/5. On 11/5/79 surface high pressure was centered over PA. A frontal
passage on 11/2 had brought rain, with partial clearing on 11/3 and
11/4.
On 9/12/80, a cold front was approaching Cleveland from the north,
displacing surface high pressure centered over eastern OH on 9/11.
Apparently light rain fell at Cleveland by 9/13.
76
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On 4/4/81, the simultaneous high day at Cleveland, Ironton, and
Buffalo, a large surface low pressure system was centered over Wisconsin
and was moving rapidly northeastward, pushing surface high pressure out
to sea. Winds at the surface and aloft were southwesterly and rela-
tively strong, and surface isobars would fall parallel to a line joining
Cleveland and Buffalo on the map. Record high temperatures had been
recorded over the Great Lakes on 4/2/81.
On 10/13/81, extensive surface high pressure was centered over
Montreal, while a cold front approached the western side of the Great
Lakes. Conditions had been dry in Cleveland for two days. One day
later, on 10/14/81, the situation seemed similar to 4/4/81, with moder-
ately packed isobars sandwiched between a cold front approaching the
Great Lakes and surface high pressure lying along the New England
coast.
Regional sulfate events on 7/10/79 and 9/6/79 may have enhanced the
relatively stagnant conditions in the advance of frontal positions on
those days. The situation on 4/4/81 was quite different, with a
vigorous storm and heavy rain approaching. The dry conditions preceding
the cases of 7/20/7^ and 10/13/81 may have enhanced the resuspension of
particulate matter earlier deposited at the surface, though Al and Si
concentrations for these two days are not elevated with respect to the
other Cleveland site-days.
-------
On the highest day of the set of seven, the PM15 mass exceeded the
HIVOL by 14%. The PM^ data have been rejected on that day as the
PM15/HIVOL ratio exceeds the EPA/EMSL criterion of 1.1.
Philadelphia, PA (9 Site-Days)
The greater Philadelphia area has at one time or another included
fourteen IP Network sites. Many of these operated only on a temporary
basis during 1979 and 1980.
Neighborhood-scale sources include unpaved roads, a copper smelter,
grain loading and mineral handling facilities, a coke oven, and a chemi-
cal plant. Three of the sampling sites, T and A Pet, Bridesburg
Recreation, and ME Transfer, are located within about a one mile radius
near the confluence of the Delaware River and Tacony Creek in the
Bridesburg industrial area. Urban-scale sources include a broad range
of industrial activities, such as copper, lead, and aluminum smelting,
iron and steel foundries, coke ovens, blast furnaces, chemical plants,
. incinerators, refineries, feed and grain handling, mineral handling, and
heavy vehicular traffic.
On 11/20/79, the' Fe/Si ratios, as well as the magnitudes of Fe con-
3
centrations (ranging from 2.5 to 4.4 ug/m in the coarse, and much less
in the fine mode) were similar to those expected from geological
material. Al was in the vicinity of 3 ug/m in the coarse mode, and much
less in the fine mode. The 11/20/79 Br/Pb ratios in both coarse and
fine modes are probably indicative only of auto exhaust, as they range
78
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from 0.19 to 0.25. Cu reached a maximum value of only 0.1 yg/m in the
coarse fraction at the T and A Pet site on 11/20/79. The 11/20/79
coarse and fine Ca concentrations are characteristic of geological ori-
gins, being in the ranges of 1.5 to 2.9 yg/m and 0.3 yg/m to 0.5
yg/m , respectively. On the highest site-day of the set, coarse Mn
reached 6.9 yg/m3 and fine Mn was 0.9 yg/m3 on 11/20/79 at the T and A
Pet site. On other days these concentrations were less than 0.05 u9/m3,
and in the absence of simultaneously high Fe readings, which would Indi-
cate iron and steel processing, -this reading may have resulted from a
mineral handling operation.
In the 12/5/79 and 12/11/79 cases, the above observations for the Fe
concentration, the Fe/Si ratio, the Br/Pb ratio, and the Ca con-
centration still apply. Fine Cu reached 0.2 yg/m on 12/5/79 and 0.6
yg/m on 12/11/79. Possibly smelting operations are the source, but
this does not explain the 50 - 60 yg/m fine mass concentrations on
those dates.
The Br/Pb ratios cited above indicate a vehicular traffic contribu-
tion to the Philadelphia readings. The sum of Br and Pb coarse and fine
contributions is 2 tfo 3 yg/m , and presumably carbonaceous material is
also present from the same source. Coarse Al and Ca contributions are
not high enough to indicate substantial re-entrainment of either crustal
or construction particles.
The three available fine sulfate readings on 11/20/79 were all high,
ranging from 31.4 to 35.0 yg/m . A very high fine nitrate value for an
79
-------
eastern station, 9.2 yg/m at the NE Transfer site, was observed on this
date, and the minimum value for the date was 2.5 yg/m (fine mode) at
Presbyterian Home. Sulfate and nitrate concentrations in nearby Ohio
and New York were not measured on 11/20/79 (they were measured on
11/17/79). The meteorological circumstances makes these high sulfate
readings appear to be regional.
At the recommendation of the National Climatic Data Center, the Fort
Totten, NY, soundings were used for Philadelphia cases. On 11/20/79,
the OOOOZ sounding shows inversions at 944 mb (695) and 934 mb (1716 M).
A warm front was approaching, with cloud decks above 750 mb. Winds up
to 850 mb were less than 10 knots at OOOOZ; the surface wind was 2 knots
out of 110ฐ. High pressure had been a feature of the surface map for at
least three days, with dry and unseasonably warm weather.
On 12/5/79 temperatures were much cooler than 11/20/79, and the
OOOOZ sounding shows an inversion at 810 mb (1850 m). The surface wind
was 8 knots out of 300ฐ. Conditions were cool and dry. Surface high
pressure on 12/3 gave way as a low pressure system passed to the north
of the Great Lakes on 12/5 and 12/6/79.
4
The 12/11/79 the sounding is very hard to interpret, as it shows a
series of inversions all the way up to 500 mb. A stationary front had
been shown on the 12/10 surface map, lying along the northern border of
PA, but by 12/11 the flow was strictly southwesterly as a cold front
approached the Midwest. The surface wind (at Fort Totten) was 4 knots
out of 200ฐ.
30
-------
In summary, conditions were clearly stagnant prior to the 11/20/79
cases, and may also have been stagnant prior to 12/5/79. Both sets of
soundings show inversions which tended to confine particulate matter
from surface sources to the layer below 850 mb. On 11/20/79 the
material may have been confined to an even shallower layer. Clear skies
and stagnant, inverted atmospheric conditions clearly enhanced the
regional secondary particle episode hypothesized for 11/20/79.
On 10/21/79 at the Bridesburg Recreation Center site the PM^/HIVOL
ratios were 2.27 and 1.11, respectively, and these data are suspect
because they exceed the EPA/EMSL acceptance ratio of 1.10. On 3/10/80
at the Presbyterian Home site the fine/coarse ratio was 14.33. On this
site .day, none of the supporting data can explain the extremely high
PM}5 fine mass total of 127.5 yg/m , and furthermore, windy and rainy
weather prevailed. In this case it is apparent that an erroneous PMj5
fine mass reading has caused a false high site-day identification.
Pittsburgh, PA (2 Site-Days)
The highest day for Pittsburgh, 10/30/80, is included, although no
i
elemental or chemical information could be found. Some of the highest
total mass readings in this data base occurred at the nearby
Aval on", PA, site, for example 634.3 yg/m on 2/4/82 and 431.6 yg/m on
12/6/81. As no supporting chemical, SSI or HIVOL information are
available for Avalon, these cases have not been analyzed. Their very
magnitudes render them suspect.
81
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Surrounding neighborhood-scale land use is predominantly residential
and light commercial. A railroad and the Jones and Laughlin Steel
Corp. are located to the west of the site. No urban scale source sum-
mary could be found.
On 5/22/81, which was also a high day at Wilmuth Pump, NY, coarse
Al and Si concentrations are missing. The coarse Fe concentration was
3 3
7.2 yg/m while Mn was elevated at 0.45 and 0.37 yg/m in the coarse and
fine fractions, respectively. The fine Fe/Si ratio was 5.45, possibly
indicating iron and steel processing as a source. The Br/Pb ratio was
0.13 for the coarse mode and 0.17 for the fine mode, possibly indicating
a source of Pb apart from vehicular traffic, as these values are below
the typical auto exhaust ratios of 0.2 to 0.3. K and Zn were elevated,
especially in the fine mode (0.9 and 1.3 yg/m in coarse and fine,
respectively), without an obvious urban source to which they can be
attributed. The site survey indicates substantial nearby vehicular
traffic (more than 30,000 cars per day), but it does not indicate "dust
visibly re-entrained". No construction is indicated which would
explain the elevated Ca readings.
< 3
The fine sulfate was 16.3 yg/m on 5/22/81. Fine sulfate on the
same day at Buffalo (Wilmuth Pump), NY, was 9.3 yg/m3; Buffalo, NY,
(P.S. #28), 12.2 yg/m3; Philadelphia, PA, (500 S. Broad), 5.4 ug/m3; and
Philadelphia, PA, (Presbyterian Home), 6.2 yg/m3. The case of 5/22/81
does not seem to involve a major, if any, regional sulfate episode.
82
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The 5/22/81 Pittsburgh sounding shows a very high inversion at
650 mb (3688 m). Surface winds were 6 knots out of 310ฐ, with high
pressure on the surface map centered over southern Ohio. Generally, it
was the driest week statewide since the end of January, 1981.
In the case of 10/30/81, the highest day at Pittsburgh, no sounding
was obtained, but the maps show high pressure at the surface centered
over Pittsburgh. Some precipitation had fallen two to three days before
10/30, but on 10/30 a record low temperature was recorded at Harrisburg,
PA, and a wide spread frost was reported. It is likely that a
Pittsburgh sounding, if one were available for this day, would show evi-
dence of a radiation inversion close to the surface, given the clear
skies and reports of cold temperatures.
On 5/22/81, the strong high pressure over the eastern states pro-
bably was the regional factor causing high readings at both Pittsburgh
and Buffalo. On 10/30/80, clear skies and high pressure may have
resulted in meteorological factors inhibiting the removal and dilution
of surface-originating particulate matter, as well as increased demands
for residential heating with resultant emissions.
No significant violations of the EPA/EMSL validation criteria are
apparent.
83
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Hartford, CT (1 Site-Day)
Though the PM^ concentration on 1/22/81 of 126 yg/m3 is not one of
the highest in the network, this site-day is important in that it repre-
sents an eastern city apart from the large industrial centers, such as
Buffalo and Philadelphia.
The chemical data for Hartford on 1/22/81 do not show highly ele-
vated concentrations of Fe, Vn, Ni , Br, Pb, Mn, Zn, and Cu, with the
possible exception of fine Zn at 0.2 yg/m . The Br/Pb ratio is indica-
tive of auto exhaust, at 0.21 in the coarse and 0.32 in the fine frac-
tions. Si is high, at 9.5 pg/m in the coarse mode, while coarse Al and
Fe concentrations are 3.3 and 2.3 yg/m , respectively. Coarse Cl shows
one of the highest concentrations seen in this study, at 9.8 yg/m , and
K is noteworthy at 0.8 and 0.4 yg/m in the coarse and fine fractions,
respectively. Fine sulfate is slightly elevated at 11.1 yg/m .
Industrial sources do not appear to be major contributors.
This case may involve the coldest surface temperature of all of the
present 50 site days, with a low of 8ฐF and a high of 36ฐF reported at
Hartford airport on 1/22. Furthermore, 1.1 inches of snow had fallen on
*
1/16, a trace on 1/17, and a trace remained on the ground on 1/22.
Therefore, it seems plausible that both the elevated coarse Cl and the
elevated coarse Si could be the result of road sanding and salting
operations. There is some substantial local source of coarse particles,
as the HIVOL mass is 212.6 yg/m3 while the FINE-15 is 61.0 yg/m3.
84
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Also, it is possible that some of the elevated Cl and most of the ele-
vated K are a result of residential heating in the form of wood
burning.
Evidence for regional-scale events is lacking in the 2 typical fine
3
sulfate and nitrate values of 11.1 and 1.32 yg/m , respectively.
A radiosonde sounding from Albany, NY, for OOOOZ on 1/22/81 shows a
cold surface temperature (18ฐF) and the lowest of many inversions at 850
to 900 mb (1414 to 962 m). The OOOOZ surface wind at Albany was 4 knots
out of 30ฐ, and is characteristic of the wind speed and direction at all
levels up to 900 mb. The map shows surface high pressure on 1/21, with
a cold front and precipitation approaching from the west on 1/22. This
appears to be a clear case of a low, radiation-caused inversion with
surface high pressure.
Chicago, IL (1 Site-Day)
The PM}5 coarse/fine ratio is 1.06 and does not suggest a dominant
contribution from either size mode. No data are available from the
other IP Network site in Chicago for this date.
In the absence oฅ a sounding, it is still possible to infer the for-
mation of a low-level inversion as skies cleared following a frontal
passage on 2/2/81. The high and low temperatures recorded at Chicago
O'Hare Airport on 2/3 were 10aF and -5ฐF, and a trace of snow remained
on the ground from the 2.3 inches that fell on 2/1 and 2/2. The
pressure was rising at Chicago on 2/3, but it appears to be only a short
interlude between storms.
35
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In the absence of other data, it appears that a radiation inversion
contributed substantially to this one-time appearance of Chicago on the
list of high IP Network site-days.
Ironton, OH (1 Site-Day)
Al, Si, and Fe concentrations were not elevated on 4/4/81 in
Ironton, and their ratios are consistent with those of geological
material. Zn and Cu concentrations were at typical levels. Coarse Ca
was elevated at 6.27 yg/m , as were coarse K and Mn at 0.71 and 0.23
ug/m .
These elements were compared to the masses and the relative
fine/coarse proportions at Buffalo and Cleveland on 4/4/81, but the only
apparent similarity is with the Ca at Cleveland.
The Ironton Br/Pb ratio for the coarse mode waa 0.21, well within
the auto exhaust range; however, fine Br was 1.03 ug/m , causing a very
unusual Br/Pb fine ratio of 21.0. There is no source information to
explain this Br concentration.
As in several previous cases, it is plausible that the elevated
coarse Ca derives fr*om local construction. On the other hand, Ironton
on 4/4/81 was between storms (in fact, precipitation probably started
at Ironton on 4/4/81), and surface conditions probably were not dry
enough to encourage resuspension of dust. The elevated K reading may be
an indication of residential heating by wood burning, a hypothesis
strengthened by the slightly elevated coarse Cl mass of 0.3 yg/m .
86
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The very modest sulfate and nitrate levels for this case do not sup-
port the idea of a regional-scale phenomenon.
The weather summary for Ironton is similar to that of Cleveland and
Buffalo, showing the imminent approach of a front and southwesterly
flow. The Huntington and Buffalo soundings are similar from 960 mb on
up. The Ironton temperatures were warmer than those in Buffalo, but they
were basically dry-adiabatic from 960 mb up to 770 mb. The Buffalo
sounding shows a very shallow inversion near the surface, which is not
present on the Huntington sounding. Both show some weak inversion
structure in the 700 to 750 mb layer, 2500 to 3000 m MSL at Huntington.
Again, what is most noteworthy in the meteorology of .all three sites is
that -heavy rain fell over the states of OH and NY on 4/4/81, following
record high temperatures over the Great Lakes on 4/2/81. Despite signi-
ficant prefrental southwesterly winds (Huntington OOOOZ surface wind was
6 knots at 220ฐ, increasing to 25 knots, 207ฐ, at 850 mb), the rapid
approach of the front on 4/4/81 seems to have involved a PM^5 enhance-
ment mechanism at Ironton, as well as in Cleveland and Buffalo.
4
Youngstown, OH (1 Site-Day)
This date comes less than one month after the Hartford, CT, case of
1/22/81 and the Chicago, IL, case of 2/3/81.
Coarse Al, Si, and Fe concentrations suggest a slightly elevated
crustal contribution. A check of the HIVOL/PM^ ratio, 1.66, confirms
that large concentrations were present in the coarse and larger fraction
87
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of the particle size distribution. K and Zn were slightly elevated.
Coarse Cl and Ca were high at 7.3 and 4.8 yg/m , respectively. The
coarse Br/Pb ratio, 0.21, is indicative of auto exhaust. The fine
ratio, 0.39, is near the maximum value attributable to unaged auto
exhaust.
The elevated Cl concentrations may again indicate road salting. On
2/15/81 about one inch of snow still remained on the ground at
Youngstown following a 3 inch snowfall on 2/11. Road sanding may also
have contributed to the coarse Al, Si, and Fe concentrations. No infor-
mation is available to suggest whether or not the coarse Ca mass origi-
nated in a local non-industrial, or for that matter, an industrial
source.
Regional sulfate episodes are relatively rare in winter. The
Youngstown data show an appreciable fine sulfate concentration, 13.4
yg/m , but this value is not in the regional-scale episode category and
local coal combustion is probably a simpler explanation.
Intense high pressure formed over the northeastern states on 2/12
and 2/13, following a storm on 2/11. Conditions remained dry, and the
high pressure remained over the area until 2/15, when a stationary front
is shown on the surface map to the north of the Great Lakes and over NY.
A warming trend was in effect at Youngstown from 2/12 to 2/15; on 2/15
the high was 50ฐF and the low was 22ฐF. It is likely that a sounding at
Youngstown would have shown a radiation inversion and/or a subsidence
inversion. The clear skies, high pressure and probable inversion almost
88
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certainly made the difference in placing this case on the list of 50
high site-days.
WESTERN SITES
Phoenix, AZ (2 Site-Days)
During the first examination of the quarterly summaries, this site,
Roosevelt St., provided four possible site days. The second examination
provided two more. None of the first four cases were found to have chem-
ical data. The case of 11/6/81, with its very marginal PM^ total mass
of 107.6 yg/m , was retained because chemical data were found. Although
elements are lacking, and the PM^/HIVOL ratio is suspect, the highest
day for Phoenix, 6/21/81, is also included in order to round out the
profile of this urban area.
The sampling instruments are located on top of a building (County
Health Department Complex) which contains a large parking garage and is
adjacent to an outdoor parking lot. Vacant lots, residential areas, and
a hospital are within a 0.25 mile radius of the sampling location. On
the urban-scale, industry in the form of mineral and feed and grain
handling, cement works, blast furnaces, and rock crushing are noted.
On 11/6/81 the PM^5 coarse/fine mass ratio was 2.56, exceeding the
EPA/EMSL criterion which flags any data for which this ratio exceed 1.3.
However, the simultaneous HIVOt measurement was 157.9 pg/m . Since it
exceeded the PM^ total mass value by 47% and the SSI value by 36%,
there was evidently a large proportion of coarse material on 11/6/81.
89
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In addition, Watson et al. (1981) point out that this criterion is
empirical and "...it is possible, though unlikely, that these limits are
exceeded under ambient conditions." With this caveat, the case of
11/6/81 will be further analyzed.
For a case where such a large fraction of the mass is apparently in
the coarse mode, the crustal species show concentrations barely above
background levels. Ca is not even shown in Table 5-7 because the non-
reportable data indicated its mass to be at the background level of 0.02
vg/m in both size ranges. There is no evidence of Phoenix's rock
crushing or cement industry in these data. Three unusual elements do
show elevated levels in the 1 to 2 yg/m mass range P, Ba, and Rb.
These non-rsportable elements, measured by x-ray fluorescence, are not
in excess of detection limits on any other site-day in this study, and
their source is not obvious. The difficulty of extracting non-
reportable data is an obstacle to checking other Phoenix measurements
for these elements and that check has not been made.
The appreciable nearby vehicular traffic, as well as the starting
and stopping of engines in the adjacent parking facilities, might cause
Pb to be elevated. 4 But the values of 0.005 yg/m for both size ranges
are below detection"limits. Br is slightly elevated, giving resultant
and rather unbelievable Br/Pb ratios in excess of 100.00.
No support for regional-sc-ale sulfate or nitrate episodes follows
from the very low levels measured for these species.
90
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The nearest radiosonde data relevent to Phoenix is the sounding from
Winslow, roughly 25 miles NNE. On 11/6/81, a broad high presssure
region is shown at the surface from New Mexico and Texas to North Dakota
and Iowa. Surface trajectories would bring air from southern Texas and
the Gulf Coast into Arizona. The high temperature at Phoenix was
87ฐF, the low was 60ฐ, and the OOOOZ Winslow sounding indicates a dry
adiabatic atmosphere without inversions up to 550 mb. The OOOOZ Winslow
surface wind was 4 knots out of 10ฐ, with 10 knots at the 700 mb level.
The meteorological picture, then, is one of possible stagnation, as high
pressure is shown on the surface for the preceding two days. The sub-
sidence inversion was apparently very high at 540 mb., and there is no
evidence of a radiation inversion. Although one may have been present at
Phoenix, the nighttime low of 60ฐF makes this unlikely.
The meteorological situation on 6/21/81 may have allowed advection
of material into the Phoenix area from some other location. The simpler
explanation seems to be measurement anomaly. The PM^s mass exceeds the
HIVOL by 58%, and the SSI by 169% on 6/21/81.
1
Bakersfield, CA (4 Site-Days)
All four cases in Bakersfield occurred in the winter period,
November 1980 to February 1981. Soundings were available for three of
the cases, from Vandenburg, CA, roughly 125 miles SW of Bakersfield on
the California coast.
91
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The first day, 11/17/80, shows relatively low sulfate and nitrate
levels and a fine/coarse ratio of 0.66, while the last three days show
much higher sulfate and nitrate levels and fine/coarse ratios between
2.0 and 3.0.
The crustal components, Al, Si, and Fe, were elevated on 11/17/80
and were less so on 12/23/80. Fine Cl, fine Br, and coarse Pb con-
centrations were higher than normal on both days, and K was elevated in
both modes on 11/17/80 as was coarse Ca at 4.5 ^g/m on 11/17/80.
The fine sulfate concentrations of the four Bakersfield cases range
from 9 to 45 pg/m . The latter is one of the highest sulfate values of
all the 50 site-days. The likely precursor of this sulfate is sulfur
gases from the pumping and handling of oil in the southern California
oil fields. Though the Cl, Br, Pb, K, and Ca concentrations cannot be
attributed to a specific industry, the simplest explanation of the
sulfate concentrations is an oil industry source.
Non-industrial sources are involved in the 1980 cases. The elevated
coarse crustal species probably resulted from re-entrained dust, perhaps
from the vacant lot on the corner SW of the sampler. The coarse Br/Pb
ratios on 11/17/80 *and 12/23/80 are indicative of auto exhaust at 0.24
and 0.20 respectively, but as noted above, fine Br was elevated with
respect to Pb on these days, and the Br/Pb ratios were too high for auto
exhaust at 2.48 and 3.34. Fine Br concentrations are, in fact, elevated
for all four cases. The fine Br concentration of 2.9 yg/m on 2/3/81 is
92
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the highest observed in the 50 cases. Site surveys indicate no Br
sources in Bakersfield and this species is not expected from oil extrac-
tion, Coarse Ca is also elevated for the two 1980 cases (no data are
available for the two 1981 cases) and may indicate nearby construction
work.
It is unlikely that sulfate is transported from distant sources
since sulfur emissions in other parts of California are lower than they
are in the San Ooaquin Valley. The four Bakersfield cases show
elevated fine nitrate concentrations, reaching a maximum of 46 yg/m
on 12/23/80. By comparison, the highest nitrate concentration of the
si< Rubidoux cases to be discussed below is 37 pg/m in the fine frac-
tion. This may be a Southern California regional event. A fine nitrate
concentration of 33 yg/m3 from the SSI at Fresno on 12/11/80 is
noteworthy, but data from 12/23/80 were not found in a search of most
southern California sampling sites.
The Vandenburg OOOOZ soundings from 12/23/80 and 2/3/81 show promi-
nent, low-level inversions from 950 mb to 1000 mb. The 11/17/80
.ounding was taken as a weak cold front approached and it is harder to
characterize. On 12^23/80 and 2/3/81, high pressure is shown on the 500
mb naps over the west coast, and the resultant inversions may be a
result, of subsidence.
11/17/80 may be different from the other three cases. The crustal
contribution on this date was noted earlier, and it is probably related
tc the fact that over 100 homes were destroyed in southern California by
93
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fires fanned by strong "Santa Ana" easterly winds on 11/16/80. The high
potassium concentrations, 2.61 pg/m in the coarse fraction and 1.07
yg/m in the fine fraction, confirm this source. The three later cases
all involve strong upper level ridging which blocked storms, kept preci-
pitation away, and, at least in the case of 12/23/80, led to markedly
warm temperatures compared to averages. These conditions are consistent
with the high sulfate and nitrate readings noted above.
Rubidoux, CA (6 Site-Days)
The prevailing opinion is that air pollution is usually worse in
this area than in other parts of the Los Angeles basin because westerly
surface winds tend to move particulate matter toward the eastern side of
the valley where the confluence of two mountain ranges, together with
frequent subsidence inversions, restrict its removal.
To round out the case studies at Rubidoux, the highest PM^ reading
on 2/22/82 is also included, although no elemental or chemical infor-
mation is available for that day and there is an indication of erroneous
data.
The site survey' for Rubidoux shows a well-traveled, paved street,
vacant land, and residential areas in the surrounding 0.25 mile radius.
An urban-scale source characterization was not available. Atmospheric
soundings from Vandenburg and San Diego, CA, were plotted and applied to
the analysis of these cases.
The site-days tend to cluster toward the end of the work week (3
on Friday, 1 on Thursday, and 1 on Wednesday), and, as will be discussed
94
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belc-A, three o* tne cases occurred the di/ before fronts passed through
the no"the-rn pert of Ce'ifornic.
'": on 'I- . ./'? v/cs H-.' at 0.34 an - ug/rc" vi the coarse and fine
modes, res:?" ve-" . ;; -v&s e" :/ an- .'is'1/ ';> on 10/24/79, but on
a
the other days *'t was significantly n :*.-' at ^ to 10 yg/m . K was
moderately elevated at 1.5 to 2.0 yg/m3 ia the coarse mode on all days
except 10/24/79.
Crustel components cc" -r-ibuted ซnoderately and consistently on all
days except 10/24/75, with coarse Al/Si/Fe in tne rough proportions of
4/:.l/3 (yg/m"). Substantial coerse Ca was seen on all days except
lD/^/73 and nrsy indicate construction s^ewhere nearby, or possibly
industrial ceoent .-ctivity. C1 was sllgfccly e'e\3ted in a few cases,
and p^ohab '/ crio-' -. ~.i r -/re sea^ast Most : the Br/Pb ratios,
especially '.n t^e : _e mooe, were in tnซ 0.2 to 0.3 range, indicative
of auto exhaust. " : 10/24/79 data are eraomalous with a coarse Br/Pb
ratio of C.I.
A-ot^nd ฃ5% of ^a ^5 mass or, 10/12 /'79 ard 10/24/79 can be
accounttc for by t; c -jlfjte and nitrite coซCฃ'it<~3t-;ons; lesser contri-
i
b'Jtionj were found :- otr,er da>jF. In this "aspect, 10/24/79 is again
ano^c1 cut in that r: ?-cws the second highest fine nitrate concentration
of th-j 50 cases, .:? v9/^ . Sulfate and nitrate may not be regionally
d':stT" 7uted. "JUT; !n at least two of the cases they account for large
'-actions of the :;*'':-,. O-'ner s?co;idary aerosols ir.a.y be present, which
fi-^Kt account for a najor part f' the f'M-, 5.
-------
The San Diego and Vandenburg soundings show subsidence inversions in
the 700 to 900 mb interval on all five days. One must regard these soun-
dings with the important caveat that strong on- or off-shore winds may
be active below the subsidence inversions.
All cases involve high pressure and dry weather over southern
California. Warmer than average temperatures were noted for 10/12/79,
6/20/80, and 8/7/80. On this last day the high was 101ฐF, and the low
was 62ฐF at Riverside. As noted previously, three of the cases,
10/12/79, 10/24/79, and 5/22/81 occurred on days preceding frontal
passages through northern California. On 10/25/79 significant rain
reached as far south as central California. The usually stagnant con-
ditions and subsidence inversions seemed to inhibit the removal of PMj5
from the Los Angeles basin on these days.
On the highest day at Rubidoux, 2/22/82, the PMis fine/coarse ratio
was 3.08, while the PM^Q concentration was a factor of 10 smaller, 19.9
yg/m . The fine/coarse ratio is 3/52. The fine/coarse ratios in the
previously discussed five cases did not exceed 1.95. The PM]^ and the
data for 2/22/82 are probably erroneous.
El Paso, TX (3 Site-Days)
Neighborhood-scale influences (in 1979) included busy streets,
construction of a ten-story building, and parking lots and garages.
Urban-scale influences in El Paso include a refinery, a lime kiln,
copper and lead smelting, and iron and steel foundry operations. Watson
95
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et al. (1931) e'so point out that the city of Juarez, Me.r;o, just
acrass the Rio Grande River frv)ir> El Peso, contributes substantial and
un, arscLeri zee eirri ssions. -'.tm''i-'-p'"e*'c c-ojncJircs fror. El Pt.ic *e~e
p]. ' : -~cr n/2:/79 and 12'. '9,
anc' K wero sligrt'y elevated in Dotr- size fractions, a"rd Ca ^as
d-"sr,-. :t"y elevated, t;soecia"n.y on 11/29/79, wh-sn the c&srse con-
c.fcr; (:'on exceeded It ug/ra*. The K and C1- values ?rey ht.v "fcsulted
~iC7, .-e D'jrninc of va-ious mats^'a" s in .".irez, but very ' kely fซ
cce "S^ C' result-: frcir nearby oist Auction.
1 ; .el ":e. . ~2 w?*e mode.-st / elevated in :-oth cases .(in about
*>
ihc "-ctio 2..r ..E or the ' . Fe ctrcsr tr?t .rns vi yg/^'}. The
L.r/.:\ -arios a~? ' :at've of e-. ,-xhaust, ranginc frcm C.2 to 0.3.
, vtf and * ? >}vel" - ~'ery lc> : v:' th^re is *; /idence of
.-e-r ' sca^e ei
El Daso ฃ , tc-s at C f-n botn GO>S in 1579 sho^ inversions.
Cn I" f'^/79 the . ?ce teiip--'".. -'re was a ccol 50ฐF, end a very pro-
.ioc i.-d subsi".-' .^version ?j-ed at 700 Tib v/ith surff-ce high
c.rer fre systs .*r both Hex' : .rd the northern Rockies. Or 1./11/79
a we:i-. inve^sicr jr^ared at 69C nt with a stationary front sh;*-i on tne
rur-f\xe nap over the rorthern t>o~der o^ New Mexico. Surface tem-
per r r?:; wera nwch warmer in this case (70*'f).
On 11/2&/79, teTioeratures -were ceo! enough that residential heating
ac aiqrt may exr'v'n the elevatec, -' and Cl values nctej earlier. The
sjr^". ;e maos ""or -e.ist four dc-v; oj*ior to 12/11/79 .':ica"i'e cry ?,-
-------
stagnant conditions that would encourage the accumulation of PM^, even
in the absence of a strong inversion.
On 4/29/82, the PM^ total concentration was 399. 6 yg/m3, PM^ fine
and PM}5 coarse concentrations were 380.5 and 19.1 yg/m3, and the HIVOL
3
concentration was 104.2 yg/m . The dichotomous sampler data for this
day are therefore suspect not only because the total concentration was
nearly four times the HIVOL value, but also because the fine/coarse
ratio was out of bounds at 19.92.
Fresno, CA (1 Site-Day)
This date, 12/11/80, is bracketed by two high site-days at
Bakersfield, CA, on 11/17/80 and 12/23/80. Two different meteorologi-
cal regimes have been hypothesized for the Bakersfield cases.
The Fresno site survey indicates neighborhood-scale influences
including busy traffic in a suburban - light commercial neighborhood.
No urban-scale influences are noted, although some agricultural activi-
ties, such as burning of harvested fields, could be important in the
Fresno area.
i
There was a modest crustal contribution with Al/Si/Fe in the propor-
tions of about 4/12/2 yg/m . Small elevations appeared in the coarse K
and Ca concentrations. The Br/Pb ratios in both the coarse and fine
modes were typical of auto exhaust at 0.21 and 0.25, respectively.
A larger fine-mode contribution from local sources is seen in the
nitrate concentration of 29 pg/m . At least three days of high pressure
98
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and clear skies preceded 12/11/80, indicating that other photochemical
secondary aerosols ;say also have cont'ib'jtad to PMi 5>
Tne 12./II/SO CoMand, C*, sDurf'nc ^s the nearest to Fresno, be: it
'er about IfC1 ni'.es t:- the ':-. - rt of Fresno at -'.he ec > o* ^an
F,-ฃr ;co Bay. Wit" tnis caveat, th* .ounding i no-Kites a strong sub-
i? inversion between 859 mb g-'^1 ;l , -b, low enough to substantially
- -jarlie-, strong blockiio high
" r nee before 12/9/80, ano hfgh
t-red over Nevada. Cond"'~ions
id inver. - j.
i ?s 'ions near the surface. '-.
5 ^d been over the west .
"? the su^'ace rrsp is s^ '
ct Fre-jr-: ?rs undoubted"* v both st_
:.a"\ JOSS,
-In urb3.n-ฃ "?'e scurce i-f'v-
p of va*rcu-o.r t--affic, > :?
letting. There are prODdMy
^'.tivities in the greater Sar.
southern end of t*.e 5IS':M>;^"
rsco Bay. In the 'latter CT-
; for salt production are seen
nearby
A -.ypical and modest crustal co? '*
-------
ocean shore to the west of San Jose. The K values were more signifi-
cantly elevated at about 0.6 yg/m in both size ranges, and may have
resulted from agricultural burning. The coarse and fine mode Br/Pb
ratios were both characteristic of auto exhaust, at 0.25 and 0.29,
respectively.
Nitrate was moderately elevated at about 14 yg/m in the fine .mode,
and as in Fresno, it probably resulted from three days of clear skies,
high pressure and sluggish circulation.
The OOOOZ Oakland sounding shows the expected subsidence inversion
at 830 mb, with warm surface temperatures (72ฐF) and a surface wind of 3
knots out of 290ฐ. High pressure at the surface and strong ridging
aloft'were features on the weather maps for at least two days preceding
this case. As is often the case with high site-days in California, the
common subsidence inversion combined with sluggish winds and warm tem-
peratures to allow considerable photochemical activity and the accumula-
tion of secondary aerosols.
Portland. OR (1 Site-Day)
Portland, OR, emerged from the first examination of the quarterly
statistical summaries with six high site-days. Another four days were
selected in the second examination, but only the highest day and one
other of the ten candidate days proved to have chemical information.
Further examination of the data revealed an apparently chronic problem
100
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in Portland. Many instances of PM^= exceeding HI ฅ01 were noted.
Portlands hi-qne?.t PNSij concentration occi-r-ec DT 10/32/79.
"he site de^. "let ion indicates heav- -r?'fic on pe-v^ri roads nssr &?
Sฃ;',f ars. The ii' "e-'S a~e locat?- ~, a c'J;y -.-f-'i'.er-consai-rcr ;
envi-onment, and urtcn-sca'e influences ;-c)uce QtiiDcr ^i'.'s, a-u.Tit^u'
sme'ting, iron and steel foundries 2Td arc ''"'irrvaces., glass furnaces.,
cement works, anc "~;~; and grain nandiHg. i*;iosonos observations fr-ar
Salersi, OR, 4C 7,1 les f-.vjth o' Port" and, are rs-i-ivant.
j-e, V ar,u ''- were not *?le/ate<*. Mn end IT were sli^fritly elevated VT,-
the -me mocL at 0.12 cnj C. 13 yg/m"'ป res.'fec: vely. Cu was '3'i5rt",,y
s
ป" e1-'.' ,: fcl in bctr, modes a: '. '-: t C. C9 ug/n?". *.' -ire K wsre slightly e' s-
/atec , with both showing C.2 to 0.3 ug/rn" in the course and 0.5 to
U 0 vq'v in ttvป fine ^si-?r 'h? rost "tซm3rtc3olfi r,^-rf.cent Cation o" the
Pr lU; .--' ";st \L-- A. rt 42 vC;V .1 tn-ป coarse anjd >g/m" iti -the fine
mode. 3otn of these values were rnore than an order c i^aonltud-e higher
then the Si concentrations, which in turn were greater than the Fa can-
centrations, and a c-t -v*"" crioin se-irrts ruled out. With Al snsltin-c
opere -ons a major incjstr-' in Port "ป anc, it, is tempting to s't.t ri buts
tKes-; concentrations to a v?i1id industrial source. A caver.t must te
raised. ho.ve^2r, in th=*. th-: Al industries a>'ป geGgrsphics'.ly distant
from the samp "ing site.
To furthe explore the .'"'questions, the v-eleTปent non-r^porteMe
data listing for Al was consu'tec1. ;.s explained earlier, tn:s report
gr-)',-s all Al concentrations f,>r ell sites and dares. Qui.. ' >' sc\j/ ring
101
-------
this listing, it was noticed that 10/12/79 was not the only example of
high coarse Al concentrations from three Oregon sites, Portland,
Deschutes County, and Eugene. For example, coarse Al values at
Deschutes County on 2/9/80 and 3/28/80 were 61 and 16 yg/m3. At Eugene,
16 yg/m3 of Al were reported on 9/18/80. At Portland, the Al analysis
days bracketing 10/12/79, 9/30/79 and 10/24/79 reported 28 and 21 yg/m3
of Al. Other Al values in Portland on 2/9/80 and 3/28/80 were 27 and 24
yg/m , respectively.
It is not clear that these elevated Al values, more prominent in
Oregon than in any other state in the IP Network, can be attributed to
the aluminum industry, especially given the elevated_readings in other
parts, of the state. It is suspicious that most of the high readings
occured in Portland, closest to the industrial activity, but judgement
on the question must be reserved in light of two caveats.
First, these Al concentrations were taken from the non-reportable
XRF analyses, and as mentioned earlier, large inter-laboratory differen-
ces have been noted in these data. At this time the question of whether
or not all the Oregon data came from one laboratory's Al analyses, and
i
the validation of those analyses, should be raised. It is unlikely,
however, that samples covering more than one year from Oregon were ana-
lyzed differently from samples taken over the same time period at other
IP Network sites. None of these other sites show such high Al values,
lending credence to the validity of the measurement process.
102
-------
Second, Watson et a".. (1981) (Taite 9,1.5 on pac* 9-16 of that
report) r>eoo!"t a coerss Al anomaly t.t theSig Sister, NY, (near Buffalo)
site. Coarse A" cor r &. *~et ions of 4^ z?,d 2* : ง/u' w=:-rs attributed to
:*, ";ect1cn on the . ; :comc>us semplsr ~ilte~s cf Al chips from the
sampler inlet coraporH:.* , Very smell cfc:ps, ปป th^ order of tenths of
m'THneters in di^s.is"5 : , can :eus tte repartee "1 concentrations.
A,part frcn the Aj questicn the-^ is f)u convrtring 2ป'ideซ5ce in the ele-
Terta' cata to *mp'-'catf; industrial SOUTHS.
:* end Pb were pr* -:'. >sir ret*:' i-aarse ar-d f^'na modes both
*". .:.te typical., lev ":.ฃ" :uto e^rvc.. t ..^xes, Crastal Si and Fe
we'.- o^esent on!/ i "> lev. ""(trse ane-s".. Jt>as 1 the proportion of
3
about 4/2 yo/ns", r.- fgctive";
:i.;"fate cunc"'. a^ior- -Kceedec i ,*;te, Wth 12.2 yg/m and
4. , yCj/^' , respec" .l^'. ' ฃ high so'"\.:e value occurred at a time of
./ear when sulf -- Draining fuels used fir heeting seisms unlikely. In
'act, rscor \ ^"' . lerperatu^es were reported is Oregon on 10/9/79. The
12%'e amci; : jj's,* menuf x-c.'.u^ing. botti ^ *:v:e Pcrtland Metropolitan
a~eo and t-- * ; orth and so.vi of th:s fersi, coulc 'be a major contribu-
4
to" of S':' . expounds, 'r^-^ levels are rrsbably more indicative of
nearby irซ.' al sources t . -hey are of regional -scale events.
lO'/ii. :-s a hioh :?:-. 'v toth Portland and Rubidoux, causing one
co suspect -igicnal -'..'. i" e veatner eveni^ Tte 3BDr;Z and 1200Z Salem
touidings . s'low c." ! "dene-: 'n--/ers .ofs in the 823 TO 850 mb layer.
Sigh prei' - .*. tne sir "ace over the -r'!?rth//esr''-i r states and ridging
103
-------
aloft had been a map feature for three days preceding 10/12/79. On
10/12/79, a weak cold front caused precipitation to start in western
Washington. Record high temperatures were recorded at several western
stations, with a record high of 81ฐF at Portland on 10/9/79. Evidence
of stagnation is given by the winds below 850 mb in this case. On the
3DC3Z Salem sounding, the wind was a maximum of 2 knots out of about
34C3 us to 900 mb, and was 6 knots, 266ฐ at 850 mb. As was the case
w-t-1 rrost. of the California site-days, it appears that warm and dry
weather with high pressure, stagnation, and a subsidence inversion
contributed to the accumulation of PMj5 in Portland.
104
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-450/4-84-016
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE , , . .,
Potential Causes Of Elevated PM _ And PJL _
Concentrations In The Inhalable Particulate Network
5. REPORT DATE
June 1984
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
C. Fred Rogers And John G. Watson
8. PERFORMING ORGANIZATION REPORT NO.
PERFORMING ORGANIZATION NAME AND ADDRESS
Desert Research Institute
Reno, NV 89506
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
US EPA
Office Of Air Quality Planning And Standards
Monitoring And Data Analysis (MD 14)
Research Triangle, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
EPA Project Officer: Thompson G. Pace
16. ABSTRACT
This report discusses and characterizes 50 high PM, 5 site-days selected from
the Inhalable Particulate (IP) Network over the years 1979 to 1982. The study is
intended to characterize the potential causes of high PM-_ concentrations in the
U. S., and therefore the correlation between PM Q and PM_ levels is shown and
discussed. The available PMin data are too sparse to support the study by them-
selves. The PM.,. data from the IP Network were analyzed with respect to five
hypothetical causes of elevated concentrations: 1) local industrial emissions:
2) local nonindustrial emissions; 3) regional secondary particle events;
4) meteorological factors, such as stagnation and inversion; and 5) measurement
anomalies.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
8. DISTRIBUTION STATEMENT
19. SECURITY CLASS (ThisReport)
21. NO. OF PAGES
112
20. SECURITY CLASS (This page)
22. PRICE
EPA Form 22201 (Rev. 477) PREVIOUS EDITION is OBSOLETE
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