Pergamon

Atmospheric EnvironmentVol. 30, No. 12, pp. 2079-2112, 1996

Copyright 1996 Elsevier Science Ltd
Printed in Great Britain. All rights regrved
1352-2310/96 $15.00:4-0.00

1352-2310(95)00402-5

DESCRIPTIVE ANALYSIS OF PM2.5 AND PMlo AT

REGIONALLY REPRESENTATIVE LOCATIONS DURING
SJVAQS/AUSPEX
JUDITH C. CHOW,* JOHN G. WATSON,* ZHIQIANG LU,*
DOUGLAS H. LOWENTHAL,* CLIFTON A. FRAZIER,*
PAUL A. SOLOMON,~" RICHARD H. THUILLIER/f
and KAREN MAGLIANO:~
*Desert Research Institute, University and Community College System of Nevada, 5625 Fox Avenue,
Reno, NV 89506, U.S.A.; tPacific Gas and Electric Co., 4301 Crow Canyon Road, San Ramon, CA 94583,
U.S.A.; and ~California Air Resources Board, P.O. Box 2815, Sacramento, CA 95814, U.S.A.
(First received 9 March 1994 and in final form 21 July 1995)
Almtraet--SJVAQS/AUSPEX acquired PM2.5 and PM to samples at ten sites in Central California for five
ozone episodes over 14 intensive sampling days. Four sample sets per day were acquired for 5 and 7 h
durations and measured for particle mass; elements; water-soluble chloride, nitrate, sulfate, ammonium,
sodium, and potassium ions; and organic and elemental carbon. Gaseous ammonia, nitric acid, and sulfur
dioxide concentrations were acquired with absorbent filter material. To guard against contamination of
these gases after sampling, the filter packs were sealed and refrigerated prior to analysis. Crustal species
such as aluminum, silicon, calcium, titanium, iron, and calcium, were found in coarse particles at most sites.
Substantial amounts of sodium and chloride were detected in the coarse particle fraction at the coastal
Point Reyes site. Organic carbon and sulfate were the most abundant species in the PM2.5 fraction.
Elemental carbon concentrations were low at all sites. Only one 24 h average PMo concentration exceeded
the U.S. PMto standard of 150/tgm -3 during the study period, and this occurred at the agriculturaloriented Buttonwillow site. The highest concentrations of most chemical species were found at sites in the
Southern San Joaquin Valley. Cop)right 1996 Elsevier Science Ltd
Key word index: SJVAQS/AUSPEX, San Joaquin valley, PM2.s, PMlo, aerosol.
INTRODUCTION

During the summer of 1990, a major field study

was conducted in central California as part of the
San Joaquin Valley Air Quality Study/Atmospheric
Utilities Signatures, Predictions, and Experiments
(SJVAQS/AUSPEX) program (Solomon, 1994). The
primary objective of SJVAQS/AUSPEX was to enhance the modeling and understanding of excessive
ozone levels in central California. Several of the chemical end products of ozone-producing photochemistry
result in nitrogenous and organic particulate matter
(e.g. Grosjean, 1992; Seigneur and Wu, 1992; Wexler
et al., 1992; Watson et al., 1994), and further understanding of the relationship between ozone precursors
and PM~o (particles with aerodynamic diameters less
than 10/~m) is essential for both ozone and PM~o
standards attainment. A ten-station particulate monitoring network was operated as part of SJVAQS/
AUSPEX to determine the nature and causes of excessive PM2.5 (particles with aerodynamic diameters
less than 2.5/an), PMIo, and visibility impairment
during ozone episodes in central California (Chow
and Richards, 1990a, b).

Chow etal. (1994a) describe the rationale for, and

the implementation of, field monitoring for PMlo and
visibility, and summarize the information from previous SJVAQS/AUSPEX planning (e.g. Chow et al.,
1990,1992a, 1993a). Particulate monitoring was intended to estabfish a database with specified accuracy,
precision, and validity which can (1) determine the
temporal and spatial distribution of particulate matter and light extinction; (2) estimate the contributions
from primary and secondary sources to particulate
matter and light extinction; and (3) explain the mechanisms for secondary aerosol formation and the relationship between ozone chemistry and secondary
aerosols in central California.
The objectives of this paper are (1) to describe the
particulate measurements taken during SJVAQS/
AUSPEX; (2) to evaluate the quality of these measurements; (3) to examine the chemical characteristics of
PM2.s and PMIo; and (4) to describe the temporal and
spatial distributions of suspended particles during
ozone episodes. Related papers describe the visibility
measurements (Watson e t a l . , 1996) and gaseous
measurements (Chow etaL, 1996) which correspond to
the PM2.s and PM~o measurements reported here.

2079

2080

J.C. CHOW et al.

Joaquin Valley (SJV); air masses were expected to
contain a mixture of particles from both natural and
man-made sources. The Crows Landing site was near
a resource recovery incinerator and in the midst of
agricultural fields. The Academy site characterized
concentrations in the middle of the SJV and downwind of Fresno. The Buttonwillow site was in the
midst of agricultural activities and close to oilfield
operations in Kern County. The Edison and Caliente
sites were downwind of Bakersfield and measured
both fresh and aged emissions; previous measurements in this area have shown large components of
secondary particles (Rogers and Watson, 1984;
Trijonis et al., 1988; Chow et al., 1992a; White and
Macias, 1991). The Sequoia and Yosemite National

AMBIENT MEASUREMENTS

The SJVAQS/AUSPEX ground-based aerosol

monitoring network, shown in Fig. 1, was designed to
represent boundary, source, and receptor areas which
characterize regional-scale phenomena (Blumenthal
and Lurmann, 1994; Blumenthal and Watson, 1994).
Sampling sites in urban areas with many local sources
were avoided. Chow et al. (1994a) specify the site
locations, identification codes, street addresses, coordinates, and elevations of these sites. The Point Reyes
site characterized aerosols transported into the study
region from the Pacific Ocean. The Altamont Pass
and Pacheco Pass sites sampled gases and particles
transported from the coastal areas into the San

i
~18.

1
u~es

~o

20

3o

4o

5O

N
%.
o

ii::!~!~
!:

tockton

. ;(i"

~_~c.r.----J
" '~.
:,
\~<::%

"

' ,
CRO
'./
"': ~-<

LBp.,t~

:rb~
~P~C .
~ ~~%-

:3

Aerosol
Sampling
Summer
1990 Field

Sites
Program

"~

.i?

!\

.....

2_;~_c.~~-

. . . . . . . . . . . . .

"~.
O

Meteorological
PM2.5
Both

end
~ite$

Pal0

Sites

Only

Sites

Only

'~ . . . . :~":

"

~"

= ~--:"

--C r,~

Sar~Lui~Ob[sl~o
~

~ Bakersfield.
-'~_,

BUT

,.~.(-. i.~i_< , :.

"-~g~UAIL
r

. .

:'

&EDI

- "

,i-

,-....

Fig. 1. Monitoring network for the SJVAQS/AUSPEX aerosol and visibility study. Site codes are: Point
Reyes (PTR), Altamont Pass (ALT), Pacheco Pass (PAC), Crows Landing (CRO), Academy (ACA),
B u t t o n w i l l o w (BUT), Edison (EDI), Caliente (CAL), Sequoia L o w e r K a w e a h (SLK), and Yosemite (YOS).
M e t e r o l o g i c a l sites are: Los Banos (LBP) and Kesterson (KES).

: - ~ ,

Descriptive analysis of PMz.s and PMIo

Parks sites were in forested areas to which air from
the SJV is often transported by upslope flows (Ashbaugh et al., 1989).
Sampling days were determined by forecasting
periods of elevated ozone concentrations and included forest fire and harvesting emissions. The
9 July-31 August 1990 sampling period contained five
episodes on 14 days: (1) 13 and 14 July 1990; (2) 21
and 22 July 1990; (3) 27-29 July 1990; (4) 3-6 August
1990; and (5) 22-24 August 1990. Four sample sets
per day were acquired for 5 and 7 h durations:
0000-0700, 0700-1200, 1200-1700, and 1700-2400
Pacific Daylight Time (PDT).
Sampling system

Two modified sequential filter samplers (SFSs)

(Federal Register, 1989), one equipped with a Bendix/Sonsidyne Model 240 cyclone (Clearwater, FL)
and the other equipped with a Sierra-Andersen
SA254I medium-volume PMIo inlet (Atlanta, GA),
and one sequential gas sampler (SGS), equipped with
a PFA Teflon-coated Bendix/Sensidyne Model 240
cyclone and sampling plenum, were collocated at each
of the ten sampling sites to collect PM2.s, PMIo, and
precursor gases, respectively. Aluminum oxide-coated
nitric acid denuders were installed between the inlets
and the filters in the PM2.s and PMlo systems. These
denuders removed the nitric acid gases with high
efficiency, while allowing particles to pass through to
the filter substrate (Chow et al., 1993b). The use of
denuders in conjunction with the quartz/nylon filter
pack allowed for the collection and subsequent determination of acid aerosols (e.g. chloride, nitrate,
sulfate) nearly free of either negative or positive interferences (Hering et al., 1988; Solomon et al., 1988,
1992). The PM2.s and PMIo inlets provide the specified 50% cutpoints at flow rates of 113 groin-1. Solenoid valves controlled by a timer switched between
five sets of two filter packs at preset time intervals.
A vacuum pump drew air through each filter pack at
a flow rate of 20 ~'min- 1 per channel when the valves
were open. The remaining flow needed to attain a total flow of 113 gmin-1 required by the inlets was
drawn through an open port with no filter. Flow rates
were controlled by maintaining a constant pressure
across a ball valve with a differential pressure regulator and were calibrated with a rotameter transfer
standard. Samplers were placed on top of 1.5 m
woodvn platforms located at ground level, resulting in
an effective inlet height above the ground of about
3 m. Collocated samplers were placed at a minimum
of 1.5 m apart on the platforms. Detailed sampling
methods are documented by Chow et al. (1994a).
As diagrammed in Fig. 2, simultaneous measurements were made on four sampling channels which
employed singlo-and double-stage filter packs to accommodate various chemical analyses (Chow et ai.,
1994a). Data from the collocated sampler which
acquired ammonia and sulfur dioxide on citric acid
and potassium carbonate-impregnated filter media,

2081

respectively, and nitric acid on nylon filters, are

described by Chow et al. (1996).
Filter media

Lippmann (1995), Lee and Ramamurthi (1993),

Watson and Chow (1993,1994), and Chow (1995)
have evaluated substrates for sampling and analyses
of the chemical components in atmospheric aerosols.
Based on these evaluations, the 47 mm filters used for
PM2.s and PMto sampling were (1) Geiman (Ann
Arbor, MI) polymethylpentane ringed, 2.0/zm pore
size, PTFE Teflon-membrane filters (# R2PJ047) for
particle mass and elements; (2) Schleicher and
Schuell (Keene, NH) 1.2/an pore size, graded 66,
nylon-membrane filters (# 00440) for nitric acid and
volatilized particulate nitrate; and (3) Pallflox (Putham, CT) quartz-fiber filters (#2500 QAT-UP) for
carbon and ions.
Chemical analysis

The Teflon-membrane filters were analyzed for

mass by gravimetry and for elements (aluminum, silicon, phosphorus, sulfur, chlorine, potassium, calcium,
titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, arsenic, selenium,
bromine, rubidium, strontium, yttrium, zirconium,
molybdenum, palladium, silver, cadmium, indium, tin,
antimony, barium, lanthanum, gold, mercury, thallium, lead, and uranium) by X-ray fluorescence (XRF)
(Dzubay, 1977). The front quartz filter was analyzed
for water-soluble chloride, nitrate, and sulfate by ion
chromatography (Mulik et al., 1976), for water-soluble ammonium by automated colorimetry (Bolleter
et al., 1961), for water-soluble sodium and potassium
by atomic absorption spectrophotometry (Rhodes et
al., 1989), and for organic and elemental carbon (OC
and EC) by the thermal/optical reflectance (TOR)
method (Chow et al., 1993c). The backup quartz filter
was also analyzed for organic and elemental carbon.
Quality control

Precisions were estimated from flow rate performance tests and replicate analyses (Watson et al.,
1995). Precisions were typically within + 10% for
measured values which exceeded ten times lower
quantifiable limits (LQLs) of the analysis method and
are reported as an integral part of the SJVAQS/
AUSPEX databases (Chow et al., 1992b). The submission and evaluation of reference standards
through independent quality audits by the SJVAQS/
AUSPEX quality assurance manager was used to
estimate the accuracy of each measurement, which
was typically within + 5% of the standard value
(Gertler et al., 1990).
The measured chemicals, their analytical techniques, the root mean squared (RMS) precisions of
measurements, LQLs, and number of samples above
the LQLs are given in Table 1. The LQLs are defined
as concentrations corresponding to two times the
standard deviation of each species measured on the

2082

J.C. CHOW et al.

PMIo or

PM2.6 Inlet
113 lpm

Ion

Chromatography

Cl-, ~o~, so~

Automated
Colorimetry

Gravimetry

Atomic
Absorption
Na+, K +

Mass

20 lpm

73 Ipm
Make-up Flow

Thermal/Optical
Reflectance
"
OC, EC

X-ray
Fluorescence

Ion
f
Chromatography

3B Elements
from AI to Pb

Drain

Volatilized

NOn-r

Thermal/Optical
Reflectance

~ Nuclepore
liter Holder
(TQ)
/
Solenoid
Valve

OC, EC
Nuclepore
Filter Holder_

(aT)

Solenoid
Valve

~'~Flow
Controller

ontroller
\

Ball

Ball

Ball

Valve

Valve

Valve

To Pump

Fig. 2. Flow diagram for PM2.s and PMlo sequential filter samplers.
dynamic field blanks. Although actual volumes during sampling varied from sample to sample, a nominal
volume of 8.4 m 3 for a typical 7 h sample was assumed
in the LQL calculation. Table 1 shows that the RMS
precisions are comparable in magnitude to the LQLs.
PM2.s and PMIo mass, ions (i.e. sulfate, nitrate, ammonium), organic carbon, and elemental carbon were
detected in most cases. Several elements acquired by
X-ray fluorescence analysis, specifically those which
increase in atomic number from palladium to mercury, were not frequently detected. This is typical for
regionally representative sites without influences from
nearby heavy industry. Aluminum, silicon, potassium,
calcium, manganese, iron, and zinc were detected over
80% of the time; most of these elements are abundant
in resuspended dust.
Data were submitted to four data validation levels:
(1) Level 0 designates data as they come offthe instrument and ascertains that the field or laboratory instrument is functioning properly; (2) Level I flags
samples when significant deviations from measure-

ment assumptions have occurred, verifies computer

file entries against data sheets, invalidates measurements affected by instrument malfunctions, and adjusts values for quantifiable calibration or interference
biases; (3)Level II integrates data from various
measurement methods in a master database and
applies consistency tests based on known physical
relationships between variables; and (4)Level III
identifies deviations from expectation when data from
different samplers and sampling sites are compared
and when comparisons are made with models.
The first assumption upon finding a measurement
which is inconsistent with physical expectations is
that the unusual value is due to a measurement error.
If, upon tracing the path of the measurement, nothing
unusual is found, the value can be assumed to be
a valid result of an environmental cause. In Level III
data validation, suspect samples are identified when
(1) extreme values are found; (2) values do not track
the values of other variables in a time series; and
(3) values differ by large amounts from those at nearby

Descriptive analysis of PMa.s and PM10

2083

Table 1. Precisions and lower quantifiable limits for SJVQS/AUSPEX PM2.5 and PMl0 aerosol species

PM2.s

Species

Analytical"
method

RMS
precision ~
(~g m-3)

PMt0

LQL ~
(pg m-S)

No.
> LQL

No. of
samples

Precision
0~g m-3)

LQL
(pg m-S)

No.
>LQL

No. of
samples

Mass

Gravimetric

1.9953

1.8924

493

516

2.9417

2.1328

488

507

CINOi
SO~"
NH~
Na +
K+

IC
IC
IC
AC
AAS
AAS

0.0466
0.0811
0.1633
0.1343
0.0465
0.0309

0.0388
0.0993
0.1207
0.1815
0.0522
0.0332

202
457
518
478
429
373

524
524
524
524
524
524

0.2602
0.0944
0.1679
0.0647
0.0666
0.0284

0.0665
0.0501
0.0672
0.0226
0.0406
0.0198

216
514
528
525
473
492

528
528
528
528
528
528

OC
EC
Backup OC
Backup EC

TOR
TOR
TOR
TOR

1.4767
0.6905
1.4415
0.9119

1.7178
0.6041
1.6432
0.6795

481
450
442
231

524
524
496
496

1.5812
0.6928
NA d
NA

1.2885
0.7126
NA
NA

498
449
NA
NA

528
528
NA
NA

A1
Si
P
S
C1

XRF
XRF
XRF
XRF
XRF

0.0691
0.1513
0.0514
0.0598
0.0500

0.0440
0.0692
0.0272
0.0220
0.0478

404
441
13
516
72

519
519
519
519
519

1.1720
3.1112
0.0738
0.1599
0.6196

0.1419
0.2586
0.0388
0.0198
0.0600

467
475
54
522
159

524
524
524
524
524

K
Ca
Ti
V
Cr

XRF
XRF
XRF
XRF
XRF

0.0419
0.0347
0.0870
0.0403
0.0112

0.0409
0.0324
0.0984
0.0440
0.0120

460
399
50
0
2

519
519
519
519
519

0.1843
0.1951
0.0809
0.0412
0.0117

0.0449
0.0383
0.0985
0.0433
0.0115

497
491
158
1
9

524
524
524
524
524

Mn
Fe
Co
Ni
Cu

XRF
XRF
XRF
XRF
XRF

0.0070
0.0602
0.0154
0.0038
0.0064

0.0082
0.0488
0.0047
0.0042
0.0089

122
422
3
37
49

519
519
519
519
519

0.0064
0.1098
0.0309
0.0036
0.0041

0.0080
0.0462
0.0051
0.0042
0.0051

409
480
4
68
206

524
524
524
524
524

Zn
Ga
As
Se
Br

XRF
XRF
XRF
XRF
XRF

0.0048
0.0085
0.0112
0.0055
0.0041

0.0068
0.0092
0.0118
0.0059
0.0052

334
1
0
1
177

519
519
519
519
519

0.0041
0.0084
0.0113
0.0054
0.0038

0.0057
0.0094
0.0121
0.0060
0.0050

455
0
0
1
280

524
524
524
524
524

Rb
Sr
Y
Zr
Me

XRF
XRF
XRF
XRF
XRF

0.0043
0.0047
0.0059
0.0074
0.0120

0.0047
0.0053
0.0063
0.0081
0.0130

23
67
0
2
1

519
519
519
519
519

0.0043
0.0043
0.0059
0.0075
0.0122

0.0049
0.0055
0.0066
0.0084
0.0135

56
208
1
15
0

524
524
524
524
524

Pd
Ag
Cd
In
Sn

XRF
XRF
XRF
XRF
XRF

0.0468
0.0526
0.0533
0.0590
0.0757

0.0509
0.0573
0.0580
0.0641
0.0824

0
0
0
0
1

519
519
519
519
519

0.0466
0.0519
0.0529
0.0587
0.0764

0.0514
0.0574
0.0584
0.0649
0.0847

0
0
0
0
0

524
524
524
524
524

Sb
Ba
La
Au
Hg

XRF
XRF
XRF
XRF
XRF

0.0787
0.2209
0.2719
0.0138
0.0115

0.0857
0.2381
0.2962
0.0150
0.0125

0
0
0
0
0

519
519
519
519
519

0.0786
0.2256
0.2714
0.0138
0.0117

0.0871
0.2538
0.3016
0.0152
0.0130

0
2
0
0
0

524
524
524
524
524

TI
Pb
U

XRF
XRF
XRF

0.0111
0.0131
0.0106

0.0121
0.0147
0.0114

0
22
0

519
519
519

0.0110
0.0131
0.0108

0.0122
0.0153
0.0119

0
38
0

524
524
524

Analysis methods are ion chromatography (IC), automated colorimetry (AC), atomic absorption spectropbotometry
(AAS), thermal/optical reflectance (TOR), and energy dispersive X-ray fluoresGence (XRF).
b RMS or root mean squared error is the square root of the average of the squared uncertainties of the individual
uncertainties of the observations divided by the number of observations.
* LQL or lower quantifiable limit is equal to two times the uncertainty of the field blank~ The LQL is expressed here in
terms of mass per c~blc meter, after dividing by 8.4 m 3, the nominal volume for a 7 h sample.
d Data not available.

2084

J.C. CHOW et al.

locations. Level I validation flags and comments are

included with each data record in the master database
and are defined by Chow et al. (1992b). Level II
validation tests and results are described in this paper.
Level III validation will continue as this data set is
used in source and receptor modeling. Procedures for
substrate handling, chemical analyses, minimum detection limits, instrument interference, data processing/data validation, and quality control/quality assurance are documented by Chow and Richards (1990b).
The validated database is available via Internet in
XBase (*.DBF) format from the S A R M A P database
(Hackney et al., 1994).

CHEMICAL AND PHYSICAL CONSISTENCIESOF

AEROSOL MEASUREMENT

To evaluate the chemical data for internal consistency, the following tests were performed: (1) comparison with PM2.5 and PMlo, (2) adsorption of gaseous
organic carbon on quartz-fiber filters, (3) sum of chemical species vs mass, and (4) cation and anion balance.
Comparison with PM2.s and P M t o

PM2.5 mass and chemical concentrations should

not exceed the corresponding P M t o concentrations.
Table 2 presents the average and propagated uncer-

tainty ( R M S E - root mean squared error) of the ratios

of PM2.5 to P M l o mass, silicon, sulfate, nitrate, organic carbon, and elemental carbon, the most prominent components of PM2.5 and/or PMto. Only concentrations above the lower quantifiable limit (LQL,
Table 1) were used in these calculations. Individual
scatter plots were generated for these chemical species
at each site and suspect values are listed by Chow et
al. (1992b). These suspect values are flagged in the
database and excluded from statistical summaries.
The PM2.5/PM~o mass ratios were lowest ( < 0.5)
at the Buttonwillow, Crows Landing, Altamont Pass
sites, indicating that coarse particles (PMto minus
PM2.s) were a large portion of P M l o at these sites.
Note that at Point Reyes, 24 out of 45 valid PM2.5
mass concentrations and 31 out of 47 valid P M t o
mass concentrations were above the detection limit
and that the uncertainty of the average PM2.5/PMlo
mass ratio in the remaining samples were large. Average PM2.5/PMto mass ratios were highest ( > 0.68) at
the Edison and Yosemite sites.
Silicon is a major component of coarse particle
geological material (Chow et al., 1994b, c). While most
average ratios of PM2.5/PMIo silicon were less than
0.3, the average ratio at the Edison site was 0.81. Field
notes and audit results (Gertler et al., 1993) were
reviewed, and there is no indication that the sampler
at the Edison site was operating differently from any

Table 2. Ratios of PM2.5 to PMlo mass and chemical concentrations during the 1990 SJVAQS/AUSPEX Study at ten site:
Mass
Site
Point Reyes
Altamont Pass
Pacheco Pass
Crows Landing
Academy
Buttonwillow
Edison
Caliente
Sequoia
Yosemite

Silicon

Sulfate

Ratio a

RMSE b

n~~

n2 d

Ratio

RMSE

nt

n2

Ratio

RMSE

nl

n2

0.54
0.49
0.60
0.48
0.50
0.41
0.81
0.60
0.57
0.69

0.39
0.09
0.14
0.05
0.09
0.06
0.08
0.08
0.12
0.16

22
54
36
49
51
54
37
52
52
55

43
54
38
49
51
54
37
52
52
55

0.09
0.26
0.29
0.24
0.15
0.81
0.36
0.08
0.15

0.04
0.14
0.07
0.09
0.04
0.10
0.09
0.04
0.05

0
55
19
50
51
54
52
53
52
54

45
55
38
50
51
54
52
53
52
55

0.93
0.81
0.79
1.08
0.91
0.82
1.01
1.04
1.10
0.98

0.60
0.07
0.07
0.09
0.08
0.07
0.08
0.09
0.13
0.09

40
53
43
50
52
54
52
53
55
55

46
53
43
50
52
54
52
53
55
55

Nitrate

Organic carbon

Elemental carbon

Site

Ratio

RMSE

nl

n2

Ratio

RMSE

nl

n2

Ratio

RMSE

n~

n2

Point Reyes
Altamont Pass
Pacheco Pass
Crows Landing
Academy
Buttonwillow
Edison
Caliente
Sequoia
Yosemite

0.29
0.24
0.35
0.52
0.39
0.35
0.93
0.48
0.48
0.94

0.17
0.09
0.09
0.08
0.10
0.09
0.12
0.12
0.24
0.46

20
43
43
50
50
54
52
53
55
45

46
53
43
50
52
54
52
53
55
55

1.33
0.75
0.54
0.89
0.70
0.81
1.00
0.95
1.06
1.19

0.90
0.26
0.22
0.25
0.21
0.24
0.24
0.28
0.47
0.30

10
53
34
50
52
54
52
53
55
55

46
53
43
50
52
54
52
53
55
55

0.69
1.40
0.64
0.97
0.98
0.87
1.06
1.03
0.87
1.18

0.63
0.73
0.38
0.67
0.62
0.43
0.45
0.55
0.46
0.71

5
51
35
47
45
52
52
53
52
49

46
53
43
50
52
54
52
53
55
55

"Ratio of PM2. 5 to PMto concentration.

b Root mean squared error (propagated uncertainty of average ratio).
c Number of PM2.5 and PMto pairs with concentrations above the LQL.
d Number of PM2.s and PMt0 pairs with valid concentrations.

Descriptive analysis of PM2.s and PMlo

of the other sites. Given its alluvial nature and long
history of agricultural tillage, it is possible that soil at
the Edison site has a higher fine particle content than
soils near the other sites.
In contrast, average PM2.s/PMlo sulfate ratios
were greater than or equal to 0.79 at all ten sites, and
greater than 0.9 at seven sites. The average PM2.s/
PMlo sulfate ratio at Point Reyes was 0.93 but this
value is misleading because of its large uncertainty.
For example, in 33 out of 46 PM2.s and PM~o samples where sulfate concentrations were greater than
three times the LQL, the average PMz.s/PMxo sulfate
ratio was 0.53 :t: 0.06. However, increasing the precision for data inclusion in this comparison caused no
change in the average PM2.s/PMlo sulfate ratios at
the other sites. On average, 25% of coarse-particle
sulfate at Point Reyes can be accounted for by the
natural abundance of sulfate in sea water (Pytkowicz
and Kester, 1971). However, sulfate has also been
found to be further enriched in sea-salt particles by
the neutralization reaction with H2SO4 (McInnes et
al., 1994).
With the exceptions of the Edison and Yosemite
sites, with average PM2.s/PMlo nitrate ratios of
0.93 + 0.12 and 0.94 + 0.46, respectively, the average
PM2.s/PM~o nitrate ratios ranged from 0.24 at Altamont Pass to 0.52 at Crows Landing. In general, the
majority of PM~o nitrate was in the coarse particle
fraction. Having high PM~o nitrate relative to PM2.s
nitrate during the summer when temperatures are
high and relative humidities are low is not unexpected, since under these conditions, the ammonium
nitrate equilibrium with nitric acid (HNO3) and ammonia (NH3) favors the gas phase. Neutralization of
nitric acid by alkaline components of mineral and
marine aerosols adds nitrate to those particles
(Mamane and Mvhier, 1987; Mamane and Gottlieb,
1992; Putaud et al., 1993).
PM2.s organic and elemental carbon constituted
more than 50% of PM~o carbon at most of the sites.
The fractions of organic and elemental carbon in
coarse particles were highest at the Pacheco Pass sites,
with average ratios of PM2.s/PM~o organic and
elemental carbon equal to 0.54 and 0.64, respectively.
Adsorption of gaseous organic carbon on quartz-fiber
filters

Certain organic compounds in suspended particles

maintain a gas/particle equilibrium with their environments, similar to the situation for ammonium nitrate (Watson et al., 1994). Previous studies have
found that either some volatile organic compounds
evaporate from a filter (negative artifact) during
sampling, or that some gaseous organic species are
adsorbed (positive artifact) on quartz-fiber filters
(Eatough et al., 1990; McDow and Huntzicker, 1990;
Tang et al., 1994; Turpin et al., 1994). Several denuding and backup filter sampling systems have been
applied to evaluate these artifacts, but they were too
costly and inconclusive to justify using them during

2085

this study. Eatough et al. (1990) and Tang et al. (1994)

concluded that desorption of organic gases from particles on the front quartz filter was the dominant
sampling artifact (negative artifact), while Turpin et al.
(1994) concluded that adsorption Df organic gases by
the front quartz filter was the dominant sampling
artifact (positive artifact) for organic carbon. Turpin
et al. (1994) recommended that a backup quartz-fiber
filter behind the front Teflon-membrane filter (as
shown in Fig. 2) be used to estimate the amount of
organic gases which might adsorb onto quartz-fiber
filters in the absence of particles. These backup
quartz-fiber filters were acquired on both the PM2.~
and PMlo samplers, but only the PM2.s samples were
analyzed as part of this study. It was believed that
secondary organic aerosol material condenses almost
exclusively on the submicron aerosol (Pandis et al.,
1993) and that gaseous artifacts on these samples are
not particle-size-dependent.
Figure 3 compares the organic carbon measured
on the backup quartz-fiber filter behind the front
Teflon-membrane filter with the PM2.s particulate
organic carbon measured on the front quartz-fiber
filter which sampled alongside this filter pack. These
plots show that at all sites, the organic carbon concentrations on the backup filters were frequently 50% or
more of the front quartz-fiber filter concentrations.
The relationship between backup and front-filter organic carbon concentrations varied directly at
Caliente and Academy, for example, but appeared
invariant with respect to front filter concentrations at
Sequoia and Yosemite.
If the backup filter only quantifies organic gases
that are adsorbed on the quartz-fiber filter, then the
backup filter concentrations should be subtracted
from the front filter concentrations, as suggested by
Turpin et al. (1994). However, when this subtraction
was performed, the resulting organic carbon concentrations were negative in 163 out of 493 cases (33%).
The average OC concentrations in the samples with
negative and positive OC concentrations after subtraction of the backup OC concentrations were
-1.64 and 2.95 #gin -3, respectively. However, the
average EC concentrations in these two groups were
1.88 and 1.97 #g m-3, respectively. It is unlikely that
similar levels of (combustion-derived) EC would not
be accompanied by similar levels of OC in the atmosphere.
During the AUSPEX intensive, 103 cascade impactor (micro orifice uniform deposit impactor
- - M O U D I ) samples were collected concurrently with
filter samples at the Altamont and Edison sites.
Because the MOUDI samples were collected on aluminium substrates, we assume that there was no OC
adsorption artifact in the MOUDI. However, because
there are significant pressure drops in the two lower
stages, some organic material may have volatilized
from particles in the lower part of the MOUDI. During OC analysis of quartz filter samples by TOR, the
reflectance of a laser by the filter is monitored to

Point Reyes

=~.o.~1

N;.

............... !r=~4-~ .......... ~

16

Buttomeillow
I .t=~i,=zo=
. [ = O.,,ql
N*-~14 .
.....

;
i:.
i S

i
i

...... i

.....

" PM2.5 Front Orgl~ic Carbon (ug/m3)

~
~"

I-

"l~ 121--I

=~ O0
4
8
12
16
O.
PM2.5 Front Orginic Carbon (ug/m3)

~16

O.

._o
r.
~8
o
oo

Altamont

~p.= o.~

Pass

:.

........... i.....,~.;.,~e~ .........~

= z s=7,i

~.o.~
,m=.~

Edison

....

O0
4
8
12
16
n PM2.5 Front Organic Cartoon (ughn3)

20

O0
5
10
15
20
PM2.5 Front Organic Carbon (ug/m3)

== 5
It)
LI.

16

Pacheco
SI~ - 0.~

I , . ~ m ~ . ~.-,i

Pass
i

i
r= '7o
1 2 p .......... i--iq6-; ~ ..........

0~r~.

Caliente
,, o.a7

............

l ! ::;:T~

SlOpe = O.1D
:~
r : 0.77
i

............ ' ~ = ~. V
!
I i

....

"~:16

o
0

~4

16

Crows Landing
Sle~ = 0.'~4
Intemel~t = 0.13 ~
r =0.73

Sequoia

=~..0.i0
i No=311

Inlmrl:ept : 3.(~
r =0.14

'Ii

........... }.......... ::i-I

12 ....

u.~

,i ....

~16

t-

~8

01
4
8
12
16
PM2.5 Front Organic Carbon (ug/m3)

4 ....... .:~

.....

LD

Academy

Intercept- 1.11!

i,o

;.

.......... !...._.r.~.a,~s ........ i::::....j

Yosemite

,~allm" 0,~ 1

Inl,.mqat = S.llt

; m.--m i

10
20
30
40
PM2.5 Front Orgar~c ~
(ug/rn3)

o,

"~12o

40

i
tO.
J
n
~U3 0
01
4
8
12
16
4
8
12
16
~E 0 0
4
8
12
16
o. PM2.5 Front Organic Carbon (ug/rn3) O_ PM2.5 Fr~'tt Organic Carbon (ug/m3) - PM2.5 Front OrginJc Cll'tlon (ug/m3}

~16
12
8
4

0
,
i
;
i
4
8
12
16
PM2.5 Front Organic Carbon ( , g / ~ )

Fig. 3. Comparison between PM2. 5 particulate organic carbon and gaseous organic carbon artifacts at the ten SJVAQS AUSPEX sites.

Descriptive analysis of PM2.5 and PM~o

quantify the amount of OC which is pyrolyzed. The
pyrolyzed OC is then subtracted from the EC and
added back to the OC. This correction has not been
done with MOUDI aluminum substrates because
they are too reflective. However, in the Altamont and
Edison quartz filter samples, 29% (on average) of the
EC signal represented pyrolized OC. We summed the
EC and OC over the seven impactor stages of each
MOUDI sample. The average ratio of summed
OC/EC, uncorrected for pyrolysis, was 1.04, compared with 2.99 in the (unsubtracted) front quartz
filter samples. The 1.04 value reflects the lower limit of
OC in the MOUDI samples, and in a relative sense,
the lower limit of OC in the filter samples. The
MOUDI data, uncorrected for pyrolysis, do not support a zero-OC concentration occurrence of 33%,
which results from subtracting backup OC from the
front quartz filters. Assuming that 29% of the
MOUDI EC was pyrolyzed OC, the corrected average MOUDI OC/EC ratio is 1.87. Because the
MOUDI is not subject to the OC adsorption artifact,
the ratio 1.87/2.99 --0.63 can be used to adjust the
front quartz filter OC concentration to account for
organic vapor adsorption. However, if OC is desorbed
from particles by the drop in pressure across the lower
MOUDI stages, then the value of 0.63 would overestimate volatile organic adsorption by the front quartz
filter, although clearly not as much as subtracting the
backup quartz OC concentration.
Figure 4 compares organic carbon concentrations
adjusted for organic vapor adsorption by the two
approaches: (1) subtracting the backup from the front
OC concentration; and (2)multiplying the front
quartz filter OC concentrations by the MOUDIderived correction factor of 0.63, as described above.
Figure 4 indicates approximate agreement between
the two approaches in about a third of the cases.
Because the subtraction method results in a large
number of negative OC concentrations, we suggest

2087

that the MOUDI-derived correction provides a more

reasonable description of the adsorption artifact.
Figure 5 shows the relationship between the ratio of
backup to front filter OC and PMz.s mass. A similar
relationship exists between the backup/front filter OC

~4

"

J~2~-...'"j.

~'~"::"
0 L.0

i "~'~'""

~o':'-"

30

"".

"

60

90

""
120

PM2.s Ma~ (ug/mS)

Fig. 5. Relationship between the ratio of backup to front
filter organic carbon and PM2.5 mass:

160

OC not con'ected

x OCcorrected

120

QO
i

X.
X

SO

30

60
PM2.6

90

120

160

Mass (ug/m4)

160

36

i'so

120

!.o
i"

~l

:q;t

i'
0

10

PM~.SOC~

16

20
26
30
by MOUDI (ug/mS)

36

Fig. 4. Comparison of sampling-artifact adjusted organic

carbon by the backup filter concentration and the MOUDIderived factor of 0.63.

30

60

90

120

PMIO Idees

160

(uglm:l)

Fig. 6. Scatterplot of PM2.5 and PMIo sum of species vs

mass in samples from all ten sites during the 1990
SJVAQS/AUSPEX study.

J. C. CHOW etal.

2088
3

OC omitted from sum of species

2:I

2.6 !
m

E 2~,
~r

1.5~

is

"I

"

,.,f~r~,'.

o.s~.;.i.. ~?~b ,... ,'..

L~" ,.: "

0L

30

60

90

i
120

150

O/
0

I
30

J
60

PM2.S M a s s (ug/m$)

..
i
120

i
90

150

PM2.5 Mass (ug/m3)

31

OC omitted from sum of species

2.5tn

2.5

2l.

ql

1.5

~" .

. . ~ |.

**

:;':" i..::..01-

0
0

30

60

90

120

150

PMIO Mass (ug/m3)

30

60

90

120

150

PMIO Mass (ug/m3)

Fig. 7. Relationship between the ratio of sum of species of PM2.5 and PMlo mass as a function of PM2.5
and PMIo mass concentration, including and excluding organic carbon from the sum.
and front filter OC. The ratio is fairly constant at
PM2. 5 concentrations greater than 30/~gm-3 but is
variable and frequently higher at lower PM2.5 concentrations. Relatively larger organic vapor artifacts
at lower PM2.5 concentrations suggests that particles
provide additional adsorption sites on the front filters.
While this explanation is consistent with the AUSPEX observations, further experimental studies are
needed to improve our understanding of the organic
carbon sampling artifact.
Sum of chemical species vs mass

The sum of the individual chemical concentrations

for PME.s and PM~o should be less than or equal to
the corresponding gravimetrically measured mass
concentrations. This sum includes chemicals quantified on the front Teflon-membrane and front quartzfiber filters. Total sulfur, soluble chloride, and soluble
potassium are excluded from this sum to avoid double
counting, since sulfate, chlorine, and total potassium
are included in the calculation. Measured concentrations do not account for 'unmeasured' metal oxides
in crustal material, unmeasured cations, or hydrogen and oxygen associated with the organic carbon.

Figure 6 shows scatter plots of PM2. ~ and PMlo sum

of species vs mass in samples from all sites. Each plot
contains a solid line indicating the one-to-one relationship. The PM2.5 plot presents the sum of species
calculated using unsubtracted, front filter OC, and
front filter OC minus backup filter OC for comparison. Suspect data were examined and removed from
future statistical analysis if sampling or analytical
anomalies were identified.
Similar relationships between mass and sum of species are found in the PM2.s and PM10 size fractions.
Figure 7 plots the ratios of sum of species (including
and excluding front filter OC) to mass for the PM2.5
and PMlo size ranges. The ratios are relatively constant above 30/~g m - a but increase below this level
for both PM2. ~ and PM~0. Some of this increase is
probably due to the OC sampling artifact, as suggested by Fig. 5. Higher ratios of sum of species to mass
below 30/~gm- a also occur when OC is omitted from
the sum although omitting OC from the sum has
a smaller effect in the PMIo fraction. Crustal abundances were estimated by converting Al, Si, Ca, and Fe
concentrations to their oxides using factors described
below. Average crustal abundances relative to mass

Descriptive analysis of PM2.s and PMIo

below and above 30 i z g m - 3 were 15 and 35%, respectively, for PM2.5, and 39 and 55%, respectively for
PMto. Because the sums of Species do not include
oxygen associated with crustal material, lower ratios
of sum of species to mass are also attributable to
higher relative crustal abundances at the higher mass
concentrations.
Cation and anion balance

Ammonium nitrate (NH4NO3), sodium nitrate

(NAN03), ammonium sulfate ([NH412SO), ammonium bisulfate (NHeHS04), and sodium sulfate
(Na2SO4) are the most likely nitrate and sulfate compounds to be found in central California. Ammonium

2089

(NH2) can be calculated based o n the stoichiometric

ratios of the different compounds and compared with
that which was measured. In the left panels of Fig. 8,
ammonium is calculated from nitrate and sulfate, assuming that all nitrate is in the form of ammonium
nitrate and all sulfate is in the form of either ammonium sulfate (i.e. calculated ammonium--0.38
x sulfate+ 0.29 x nitrate) or ammonium bisulfate (i.e.
calculated ammonium = 0.192 x sulfate + 0.29 x nitrate). These calculated values are compared with
the measured values for ammonium. Figure 8 shows
reasonable agreement for PM2.5 ammonium when
ammonium sulfate is assumed. Since calculated
ammonium concentrations are above the one-to-one

with Na2S04and NAN03Correction

~,3

....."1

=E

"o
~ 2

"D
0

]'
O
It}

3E
{L 0

1
2
3
PM2.5 Measured Ammonium (ug/m3)
AmmoniumSulfate
41-

nO
0

AmmoniumBisulfate

1
2
3
PM2.5 Measured Ammonium (ug/rn3)
A m m o n i u m Sulfate
t

,B

A m m o n i u m Bisulfate
.a-

with N a 2 S 0 4 and NAN03 Correction

O')

03

=,9.

=E

Eo

"0

"U
0

0
o
Q.
0

I
2
3
4
PMI0 Measured Ammonium (ug/m3)
Ammonium S u h t e
i

Ammonium Bisulfate
g

o0

I
2
3
PM10 Measured Ammonium (ug/m3)
A m m o n i u m Sulfate
41.

A m m o n i u m Bisulfate
41-

Fig. 8. Comparison between calculated and measured ammonium at the ten SJVAQS/AUSPEX sites for
PM2.s and PMIo size fractions.

2090

J.C. CHOW et al.

It is suspected that these ions originate from marine
air transported over the coastal mountains into the
SJV. During this transport, nitric acid formed as
a photochemical end-product reacts with sodium
chloride particles to create particulate sodium nitrate
and gaseous hydrochloric acid (Eldering et al., 1991).
Some of the sulfate in the marine air may also

line for PM,o, this suggests that coarse aerosol is

either more acidic, or that coarse particle nitrate is
associated with cations other than ammonium, such
as sodium.
The water-soluble ion measurements show significant quantities of soluble sodium and chloride, espedally at the coastal and northern SJV sampling sites.

Reyes

Point

~8o

=" "I:

(2.

......................

01,

. . . .

m .

. . . . . .

i - - ,

_ i n

~n

_ _ ~

[] PM2,5 [] Coarse

Pass

Altamont
1 i

~:tl

~ii_ii .... i i ............ i ...........

iiiiiiiiiiiiiiiiiiiiii

i_i i i

~: ['ILIIII:::
...........
~ : : I b , = . : iII lllhll~- : ~ i
0

[] PM2.5 Coarse
Sampling Dates and Starting Hours (PDT)

P a c h e c o Pass
~lOOr
E
!

~so!

6O !

~i '
4o

20 i

O.

iii ii ii iiiii ~oli ii

.

'

[] PM2.5 m Coarse

C r o w s Landing
~~r

o.

20

"

.~

16,

I,~1

--

~.~

2~0 10,
,~.,~

,22

. . . . . .

~. . . . . . . .

[] PM2.5 Coarse
Sampling Dates and Starting Hours (PDT)

Fig. 9. Day-to-day variation of laMz.s and PMIo mass for each SJVAQS/AUSPEX episode between
7/13/90 and 8/24/90 at the ten SJVAQS/AUSPEX sites.

Descriptive analysis of PM2.s and PM~o

2091

Academy
~

80

so

g'f

...........

N,-

PM2.5 [ ] Coarse

Buttonwillow
~'E 1 t

"~ 8o .
60

~.

20

[]

154

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

- - -

PM2.5 [] Coarse
Sampling Dates and Starting Hours (PDT)

Edison
~'100

8o !
cn
~;

. . . . . . . . . . . . . . . . . . .

.........

60 . . . . . . . . . . . . . . . . . . . . . . . . .

40

---

. . . . . . . . . . . .

,%
__

,~:'

.~

____

=~. . . .

......
,_~

__.~

__

r -

- ....

200

PM2.5 [] Coarse

Caliente

8o

40

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

' . . . . . .

~.

PM225 Coarse
Sampling Dates and Starting Hours (PDT)

Fig. 9 (Continued).
be present as sodium sulfate. If this is the case, the
sulfate associated with sodium sulfate (0.25 x Na +)
(Pytkowicz and Kester, 1971) can be subtracted as
equivalent ammonium from the total calculated ammonium. Sodium nitrate is only significant when
C1;(E1.8 x Na +] - CI-) exceeds zero. An equivalent
concentration to account for sodium nitrate is estimated (2.7 x Cld-) and subtracted as its ammonium
equivalent from the total calculated ammonium. In

this way, a more complete ion balance is made on the

sodium,: ~i01"ide,~nit~ate, and sulfate. The results are
shown in the right panels of Fig. 8. There is an apparent downward shift of the calculated ammonium with
the correction for sodium sulfate and sodium nitrate,
and correlation coefficients are higher with the correction. These plots imply that (1) the sulfate, nitrate,
ammonimn, sodium,~ and chloride measurements
must be fairly accurate and precise to allow a close

2092

J. C. C H O W et al.

Sequoia Lower Keweah

loo

aI
~

40

20

P--

F PM2.5 ~:;!Coarse

Yosemite
~" 100
E
~o
,~ so

40

~o; .h_o=_
0 I ~lllllll
&

'
4
PM2.5 iiill Coarse
Sampling Dates and Starting Hours (PDT)
Fig. 9. (Continued).

relationship to be found between calculated and

measured ammonium; (2) sulfate is primarily present
as neutralized ammonium sulfate, while ammonium
bisulfate and sulfuric acid are not present in great
abundances as evidenced by slopes that approach
unity when ammonium sulfate is assumed; and
(3) marine aerosol (or other sources of sodium chloride which mimic this aerosol) reacts with sulfuric acid
and nitric acid, especially in the PMao size fraction, to
form sodium sulfate and sodium nitrate.

RESULTS AND DISCUSSIONS

Twenty-four hour PMlo standard exceedances

According to the California Air Resources Board

(ARB) compliance monitoring network (California
Air Resources Board, 1991), the 24 h federal PMlo
standard of 150 #g m - 3 was exceeded 3 times in the
San Francisco Bay Area, 2 times in the Sacramento
Valley, 41 times in the SJV, and 3 times in the Mountain Counties during 1990. Nearly all of the 24 h
exceedances occurred during the fall and winter seasons and only a few occurred during the summer field
program, between 7/13/90 and 8/24/90. The 24 h California State PMlo standard of 5 0 # g m -3 was exceeded at all of the ARB sites in the study domain.
Exceedances of the annual PMIo federal standard of
50 #g m - a were also recorded at 21 out of the 66 sites
in central California during 1990.
Crows Landing is the only SJVAQS/AUSPEX
aerosol sampling site which was collocated with an

ARB compliance sampler, and ARB reported one 24 h

PM lO standard exceedance of 180 #g m - 3 at that site
on 9/20/90, a day when the SJVAQS/AUSPEX was
not monitoring. SJVAQS/AUSPEX recorded only
one 24 h PMIo exceedanee at the Buttonwillow site
(182 ggm -3) on 8/24/90, which was not a sampling
date for the ARB compliance monitoring network.
PM2.5 and PMlo mass concentrations
Figure 9 shows that PM2.5 and PMto mass
changed from sample-to-sample and site-to-site during each ozone episode. Multi-day PM~o buildups
were not observed during the ozone episodes except
possibly at the Crows Landing site between 8/3/90
and 8/6/90. The final three episodes had higher PM2.5
and PMlo mass concentrations than the first two
episodes at each of the sites. The coarse particle fractions at the Edison and Yosemite sites were lower
than those at the other sites, especially during the
episode of 8/22/90 to 8/24/90 when forest fires occurred near the Yosemite site. PM2.5 and coarse particle
concentrations were below 2 0 # g m -3 at the Point
Reyes site. PM~o concentrations were often highest
during the morning (0700-1200 PST) at the Sequoia
Lower Kaweah and Yosemite sites, and during the
nighttime (1700-2400 PST) at the Edison site. The
diurnal variability at the Altamont Pass, Academy,
and Caliente sites was less pronounced than that seen
at the other sites.
Large coarse particle concentrations were found at
the Crows Landing site during the last three episodes
and at the Buttonwillow site during the last two

Descriptive analysis of PM2.5 and PMlo

episodes. PMIo concentrations at the Buttonwillow
site reached 550 #g m- 3 on the morning of 8/24/90,
and lasted through the afternoon period with a PM lo
mass of 204 #g m - 3. SJVAQS/AUSPEX meteorological data at the Buttonwillow 10 m tower (Thuillier et
al., 1993) show that wind speeds during the five ozone
episodes were typically 1-2 m s- 1. Wind speeds were
low (1.3-1.8 m s- 1) on 8/24/90 during the early morning (0300--0600 PDT), increased to 2.5-4.5 m s- 1 during mid-morning (0700-1200PDT), and exceeded
8.0 m s- 1 during the late afternoon (1600-1700 PDT).
Field station logs also indicated earth moving activity
of storage piles in the maintenance yard adjacent to
the samplers. It is suspected that local events, coupled
with moderate wind speeds, resulted in the 24 h PM lo
standard exceedance (182 #gm-3) at the Buttonwillow site on 8/24/90. The 24 h average PMlo silicon
concentration during this period was 48.0 #g m-3,
indicating that the high PMIo mass concentration
was caused by geological material. An elevated
PMIo concentration of 154/~gm -3 was also recorded at this site during the nighttime period on
8/60/90, while wind speeds were in the range of
3-5 m s-1. Figure 9 also shows that PMIo concentrations during these ( > 150 #g m- 3) periods were three
to nine times higher than the corresponding PM2.5
concentrations.
P Mlo concentrations exceeding 150 #g m-3 were
found during daytime at the Crows Landing site on
7/27/90, 8/6/90, and 8/22/90. With the exception of the
morning of 8/6/90, the PM lo concentrations were two
to ten times higher than the corresponding PMz.5
concentrations. The nearby Kesterson 2 m tower reported wind speeds of 1.5-3 m s- 1, while wind speeds
exceeding 6 m s- 1 were often recorded at the nearby
Los Banes 10 m tower site. Truck traffic near the
sampling site during melon and tomato harvesting
might have resulted in larger coarse particle concentrations.
Tables 3 and 4 summarize maximum and average
24 h concentrations of PM2.5 and PMIo mass and its
chemical constituents at each site. The samplevolume-weighted average of four diurnal samples was
calculated to derive the 24 h concentrations for comparison with results from other studies.
Average 24 h PMlo mass concentrations ranged
from 7 #g m - 3 at the Point Reyes site to 70 #g m- 3 at
the Crows Landing site. Average PMlo concentrations at the Crows Landing, Buttonwillow, and
Edison sites were approximately 20 #gm-3 higher
than those observed at the Altamont Pass, Academy,
and Caliente sites, 30 #g m-3 higher than those observed at the Pacheco Pass, Sequoia Lower Kaweah,
and Yosemite sites, and 40-50/zgm-3 higher than
those observed at the Point Reyes site.

Variations of PM2.5 and PMIo chemical compositions

With the exception of the coastal and forested sites
(i.e. Point Reyes, Sequoia Lower Kaweah, and
Yosemite), the most abundant ( > 1 #g m - 3) chemical

2093

components found in the PMz.5 and PMIo samples

were organic carbon, elemental carbon, sulfate, nitrate, ammonium, aluminum, silicon, potassium, calcium, and iron. Table 4 shows that maximum 24-h
concentrations for PM xo mass and crustal species (e.g.
silicon, potassium, calcium, titanium, iron, strontium,
zirconium) were found at the Buttonwillow site on
8/24/90, and the highest average PMIo mass and
crustal species concentrations were found at the
Crows Landing site. This suggests that the impact of
local geological material on elevated PM lo mass concentrations occurred more frequently at the Crows
Landing site than at the other sites. Maximum PMto
aluminum concentrations at the Crows Landing
(17.3 #g m - 3) and Buttonwillow (15.0/~gm- 3) sites
were 10 #gin -3 higher than at the other sites.
Average and maximum PMlo soluble sodium and
chloride at the Point Reyes site rank highest among
all sites and constituted over 50% of the PMlo mass,
two to five times higher than concentrations at the
downwind Altamont Pass and Pacheco Pass sites.
These concentrations decreased along with the prevailing wind direction of northwest to southeast. This
is evidence of marine aerosol transport from the
coastal to inland areas. Figure 10 compares the diurnal patterns of PMlo soluble sodium and chloride
among the ten sites. Elevated soluble sodium concentrations were more pronounced at the northern SJV
sites during the last two episodes.
PMlo soluble sodium concentrations at the Point
Reyes site increased during the daylight hours on
8/3/90, with high concentrations observed between
the nighttime hours on 8/3/90 and daytime hours on
8/4/90. Corresponding peaks were also found at the
Altamont Pass, Pacheco Pass, and Crows Landing
sites with approximately a 5-7 h time delay in peak
concentrations. A similar peak was observed on
8/6/90 during the afternoon and nighttime periods at
these northern SJV sites. Synoptic descriptions of the
episode (Holets, 1992) confirm that an on-shore flow
originated in the coastal areas, which routed marine
air into the SJV during this episode.
The largest PMlo soluble sodium and chloride
concentrations were recorded at all sites during the
final day of the 8/22/90 through 8/24/90 episode.
Peak concentrations were found during nighttime
hours on 8/23/90 at the Point Reyes sites during
the early morning hours on 8/24/90 at the Altamont
Pass, Pacheco Pass, and Crows Landing sites, during
the afternoon hours on 8/24/90 at the Buttonwillow
site, and lasted through the nighttime hours on
8/24/90 at the remaining sites. Holets (1992) identifies
a strong sea breeze near San Francisco on the morning of 8/23/90, that reached the inland valleys by
afternoon. This strong flow continued through
8/24/90 in the San Francisco bay area, the Sacramento delta region, and in the Sacramento and San
Joaquin Valleys. Winds aloft (500-1000 m) were generally strong and predominantly from the west in the
San Francisco bay area and into the Sacramento

1.539
0.266
2.151
0.484
1.056
0.081

2.693
5.117
0.553

0.070
0.048
0.004
1.039
1.303

0.064
0.033
0.007
0.002
0.002

0.007
0.089
0.001
0.001
0.005

0.038
0.003
0.002
0.001
0.006

0.001
0.001
0.001
0.001
0.003

0.456
0.113
1.110
0.231
0.387
0.025

1.533
1.389
0.362

0.016
0.010
0.000
0.520
0.334

0.027
0.015
0.002
0.001
0.000

0.001
0.018
0.000
0.000
0.002

0.006
0.001
0.001
0.000
0.001

0.000
0.001
0.000
0.000
0.001

O(27
Backup OC"
EC

A1
Si
P
S
C!

K
Ca
Ti
V
Cr

Mn
Fe
Co
Ni
Cu

Zn
Ga
As
Se
Br

Rb
Sr
g
Zr
Mo

so~

5.901

2.687

Mass

NH2
Na +

Altamont Pass

Pacheco Pass

Crows Landing

Academy

Buttonwillow

Edison

Caliente

Sequoia

Yosemite

0.001
0.001
0.000
0.000
0.001

0.013
0.001
0.001
0.002
0.003

0.003
0.111
0.000
0.001
0.003

0.116
0.067
0.011
0.001
0.001

0.076
0.279
0.001
1.181
0.086

4.848
6.637
2.609

0.050
0.238
2.331
0.839
0.275
0.053

11.014

9.544

0.001
0.002
0.001
0.001
0.003

0.021
0.003
0.002
0.004
0.007

0.007
0.244
0.001
0.003
0.008

0.338
0.137
0.066
0.003
0.004

0.236
0.675
0.007
1.511
0.835

7.173
15.871
3.927

0.001
0.001
0.000
0.001
0.002

0.009
0.001
0.001
0.000
0.003

0.002
0.106
0.000
0.001
0.002

0.080
0.050
0.005
0.001
0.001

0.237
0.252
0.000
0.968
0.051

3.193
3.338
1.018

0.330
0.076
0.648
0.465
3.287
2.145
1 . 1 7 9 0.652
0.618
0.244
0.184
0.037

15.166

0.001
0.003
0.001
0.003
0.003

0.027
0.003
0.002
0.001
0.007

0.007
0.364
0.001
0.008
0.004

0.165
0.156
0.029
0.008
0.002

0.653
0.927
0.000
1.459
0.645

6.104
7.998
1.293

0.366
1.383
3.071
1.056
0.544
0.089

0.733
2.028
4.329
1.218
0.850
0.277

70.418

0.002
0.005
0.001
0.002
0.001

0.017
0.001
0.001
0.002
0.006

0.021
1.184
0.001
0.003
0.004

0.533
0.331
0.087
0.003
0.003

0.008
0.016
0.001
0.006
0.003

0.037
0.002
0.002
0.004
0.011

0.069
3.884
0.003
0.008
0.012

1.485
0.960
0.306
0.008
0.010

1 . 3 9 0 4.823
3.392
11.447
0.001
0.006
1.148 1.769
0.092
1.141

7.397 1 2 . 7 4 9
5.728 1 4 . 7 2 3
1 . 7 6 3 2.538

0.086
0.797
3.083
0.815
0.296
0.108

1 5 . 3 2 3 29.933

0.001
0.002
0.000
0.001
0.001

0.015
0.000
0.001
0.000
0.006

0.009
0.391
0.001
0.001
0.009

0.267
0.180
0.023
0.001
0.000

0.631
1.065
0.002
1.084
0.030

5.945
6.108
1.429

0.038
0.350
2.448
0.938
0.179
0.125

0.002
0.004
0.001
0.001
0.003

0.021
0.001
0.002
0.001
0.011

0.016
0.695
0.001
0.002
0.020

0.467
0.323
0.053
0.004
0.002

1.024
1.939
0.007
1.829
0.314

8.732
14.467
2.402

0.176
0.891
4.123
1.447
0.608
0.229

16.953 27.910
0.185
0.983
4.059
1.076
0.438
1.014

39.354

0.001
0.003
0.000
0.001
0.001

0.018
0.001
0.001
0.001
0.007

0.007
0.427
0.001
0.004
0.005

0.381
0.371
0.024
0.003
0.000

0.469
1.454
0.002
1.099
0.025

0.003
0.010
0.001
0.005
0.003

0.030
0.002
0.003
0.001
0.014

0.024
1.590
0.002
0.011
0.011

1.846
1.447
0.126
0.008
0.001

1.956
6.810
0.007
1.802
0.289

6.363
10.580
5.873 22.932
1 . 8 6 3 2.729

0.067
0.498
2.455
0.758
0.228
0.171

18.735
0.721
2.273
4.687
1.687
0.880
0.657

72.225

0.004
0.011
0.001
0.003
0.002

0.025
0.001
0.002
0.001
0.010

0.033
1.953
0.001
0.003
0.010

1.186
1.043
0.151
0.003
0.000

1.824
5.020
0.027
1.301
0.145

0.008
0.019
0.002
0.006
0.005

0.037
0.004
0.005
0.002
0.013

0.049
3.066
0.002
0.005
0.037

1.928
1.647
0.246
0.006
0.002

2.969
9.222
0.073
1.907
1.020

10.018 12.796
6.123
11.955
2.949
4.110

0.136
1.488
3.330
1.152
0.474
0.388

49.647

0.001
0.003
0.000
0.001
0.001

0.015
0.001
0.001
0.000
0.007

0.009
0.541
0.001
0.001
0.004

0.285
0.255
0.032
0.002
0.000

0.416
1.180
0.001
1.137
0.013

7,386
6.278
3.328

0.020
0.396
2.971
0.983
0.137
0.089

0.004
0.007
0.001
0.002
0.003

0.027
0.002
0.003
0.001
0.009

0.028
1.622
0.002
0.004
0.013

0.692
0.769
0.103
0.004
0.001

1.250
3.471
0.007
1.586
0.116

10.709
15.606
4.400

0.082
1.085
4.169
1.520
0.282
0.169

1 9 .9 8 3 33,484

0.001
0.001
0.000
0.001
0.001

0.010
0.001
0.001
0.000
0.004

0.001
0.074
0.001
0.000
0.003

0.139
0.035
0.004
0.001
0.000

0.121
0.201
0.000
0.857
0.004

5.324
3.445
1.641

0.010
0.243
2.007
0.712
0.083
0.076

10.738

0.001
0.002
0.001
0.002
0.003

0.026
0.002
0.002
0.002
0.006

0.003
0.119
0.002
0.001
0.007

0.230
0.047
0.007
0.002
0.001

0.396
0.419
0.000
1.456
0.026

7.004
6.369
2.964

0.030
0.384
3.085
1.133
0.135
0.144

15.186

0.001
0.001
0.000
0.001
0.001

0.009
0.001
0.001
0.000
0.003

0.003
0.160
0.000
0.000
0.001

0.148
0.082
0.009
0.001
0.000

0.159
0.391
0.000
0.766
0.011

12.073
8.049
1.870

0.059
0.230
1.831
0.494
0.096
0.064

15.973

0.001
0.004
0.001
0.001
0.003

0.016
0.002
0.002
0.001
0.004

0.005
0.242
0.001
0.001
0.004

0.226
0.172
0.020
0.003
0.001

0.242
0.609
0.003
1.034
0~071

25.819
15.618
3.515

0.165
0.457
2.528
0.820
0.235
0.136

38.016

Avg
Max
Avg
Max
Avg
Max
Avg
Max
Avg
Max
Avg
Max
Avg
Max
Avg
Max
Avg
Max
Avg
Max
(/.tgm -3) ~ g m -3) ~ g m -3) (~gm 3) (~gm 3) ~ g m - 3 ) (/agm-3) (/.tgm- 3) ~ g m - 3 ) ~ g m - 3 ) ~ g m - 3 ) ~ g m - 3 ) 0tgm-3) (ugm 3) ~ g m - 3 ) (ugm-3) ~ g m - 3 ) Oagm-3) ~ g m - 3 ) ~ g m 3)

CINO~

Chemical
species

Point Reyes

Table 3. Statistical summary of 24 h PM2. 5 measurements between 7/13/90 and 8/24/90 at ten SJVAQS/AUSPEX sites

t~

.~

0.006
0.043
0.029
0.002
0.001

0.000
0.001
0.001

13

Sb
Ba
La
Au
Hg

Tl
Pb
U

No, in average

0.001
0.003
0.003

0.013
0.068
0.065
0.005
0.003

0.011
0.009
0.009
0.006
0.019

14

0.000
0.011
0.001

0.006
0.052
0.018
0.002
0.001

0.005
0.004
0.004
0.004
0.011

0.001
0.018
0.001

0.017
0.100
0.046
0.005
0.003

0.011
0.007
0.010
0.008
0.025

"Backup OC ffi Backup quartz filter organic carbon.

0.004
0.003
0.002
0.002
0.007

Pd
Ag
Cd
In
Sn

13

0.000
0.003
0.001

0.006
0.056
0.015
0.001
0.001

0.004
0.005
0.004
0.004
0.010

0.001
0.006
0.003

0.016
0.106
0.053
0.003
0.002

0.010
0.011
0.015
0.013
0.023

14

0.000
0.010
0.001

0.005
0.062
0.015
0.001
0.001

0.005
0.005
0.005
0.004
0.009

0.001
0.016
0.002

0.017
0.088
0.058
0.003
0.002

0.010
0.013
0.022
0.011
0.020

14

0.000
0.005
0.001

-0.006
0.047
0.018
0.001
0.001

0.004
0.006
0.003
0.003
0.005

0.001
O.O08
O.003

0.018
0.154
0.054
0.002
0.003

0.012
0.015
0.010
0.016
0.023

14

O.000
0.007
0.001

0.003
0.066
0.017
0.001
0.001

0.004
0.006
0.004
0.003
0.008

0.001
0.010
0.002

O.009
0.158
O.095
0.004
0.001

O.O09
0.012
0.011
0.010
0.039

14

0.001
0.009
0.000

0.006
0.070
0.021
0.001
0.000

0.006
0.006
0.004
0.004
0.010

0.003
0.013
0.001

0.023
0.122
0.043
0.004
0.003

0.013
0.019
0.015
0.012
0.022

14

O.000
0.007
0.001

0.006
0.057
0.016
0.001
0.001

0.006
0.009
0.005
0.003
0.007

0.002
0.016
0.002

0.018
0.110
0.039
0.003
0.002

0.013
0.015
0.018
0.011
0.019

14

0.000
0.004
0.001

0.006
0.048
0.015
0.001
0.001

0.006
0.006
0.004
0.003
0.009

0.000
0.007
0.002

0.016
0.086
0.033
0.003
0.002

0.015
0.012
0.013
0.006
0.022

14

0.000
0.003
0.001

0.007
0.052
0.018
0.001
0.001

0.O04
0.005
0.005
0.005
0.012

0.001
0.005
0.002

0.015
0.081
0.043
0.003
0.002

0.013
0.013
0.013
0.014
0.029

t~

t~

"u

Altamont Pass

Pacheco Pass

Crows Landing

Academy

Buttonwillow

Edison

Caliente

Sequoia

Yosemite

7,269

2.277
0,473
1.977
0.253
1.604
0.073

1.241
0.481

0.003
0.018
0.006
0.980
4.128

0.095
0,065
0.002
0.002
0.001

0.001
0.014
0.000
0.001
0.004

0,007
0.001
0.001
0,001
0,005

0,000
0.001
0.000
0.001
0.001

Mass

OC
EC

A1
Si
P
S
CI

K
Ca
Ti
V
Cr

Mn
Fe
Co
Ni
Cu

Zn
Ga
As
Se
Br

Rb
Sr
Y
Zr
Mo

0.001
0,004
0.001
0.002
0,001

0.033
0.002
0.002
0.002
0.018

0.002
0.087
0.001
0,001
0,024

0.274
0.202
0.007
0.004
0.003

0.040
0,155
0.037
1,704
15,028

3.231
0.913

9,316
1,368
3.669
0.674
5,355
0.203

0.001
0.005
0.000
0.002
0.1301

0.019
0.001
0,001
0,002
0,006

0.015
0.617
0.000
0.002
0.004

0.410
0.406
0.055
0,004
0.003

1,147
3,534
0.012
1.339
0.638

6,831
2.044

0.426
1.295
2.970
0.815
0,757
0.146

20 , 8 79 23,289

0,002
0,008
0.001
0.003
0.003

0.034
0.002
0.002
0.004
0.009

0.025
1,188
0,001
0.004
0.007

0.720
0.761
0,116
0.008
0,008

2,495
7,160
0,040
1,794
6.360

8.626
3.204

3.364
2.577
3,908
1.177
2,629
0.296

35,344
4,050
3.540
3.859
1.253
2.812
0.152

0.001
0.002
0.000
0,001
0.000

0.011
0.000
0.001
0.000
0,003

0.009
0.364
0,001
0.003
0.003

0.247
0.203
0.027
0.002
0,001

0.552
2.066
0.000
1.250
0.459

8.892
2.197

0,201
1,790
2.919
0.914
0,613
0.208

69,872

0.002
0.005
0.001
0.005
0.002

0.026
0.002
0.004
0,001
0,006

0.031
0.796
0.002
0.012
0.012

0.535
0.514
0.062
0.012
0.003

0.007
0.014
0.002
0.006
0.002

0,027
0,001
0.002
0.002
0.007

0.058
3,161
0.001
0,006
0.008

1.624
0.965
0.262
0.006
0.005

1 . 2 7 8 6.972
5.402 15.720
0.005
0,010
2.248
1.316
5 . 0 7 3 0.303

6.454 10.220
1 . 8 4 7 2.580

0.351
1.471
2.856
0,781
0.636
0.061

16.168 25.874

0.014
0,025
0,004
0,011
0,004

0.053
0.003
0.005
0.004
0.014

0.124
6,603
0,006
0.012
0.020

3.301
1.695
0.536
0.012
0.017

17.316
33,168
0.037
1,948
1,555

12,260
3,726

0.693
3.329
4,485
1,342
1.374
0.428

119.983
0,937
2,036
4.420
1.579
1.263
0.261

46.036

0,003
0.007
0.001
0,002
0,001

0.019
0.001
0,001
0.001
0.008

0,026
1,187
0,000
0.003
0.019

0,775
0.617
0,095
0.003
0.001

2.218
6.143
0.030
1.198
0.135

8,036
2,316

0.198
1.530
2.981
0.803
0.525
0.278

53.696

0.004
0.009
0.001
0.003
0.002

0.041
0.002
0.003
0.002
0.012

0,033
1.563
0.001
0.004
0.051

1,083
0,899
0,130
0.006
0,003

0.005
0.015
0.001
0.004
0.002

0.025
0.001
0.002
0.001
0.009

0.034
1.929
0.000
0.006
0.005

1.316
1.9t8
0,162
0.007
0.002

3 . 0 8 3 3.697
8,104
11.285
0.059
0,017
2.064
1.282
1.780
0,221

8.578
10.291
1 . 6 0 4 2,920

0,134
0.991
2.653
0.926
0,332
0.177

35,923
0,089
1.595
3.291
1,067
0.475
0.407

52.464
0.555
2,606
4.701
1.614
1.169
0,672

70.283

0.018
0.050
0.004
0,016
0.003

0.043
0,003
0,003
0,002
0.017

0.123
7.892
0.003
0.013
0.016

4.695
7.588
0.689
0.019
0.011

14.971
48.023
0.096
1.926
1,956

0.005
0.013
0.001
0.003
0.001

0.028
0.001
0.002
0.001
0.010

0.036
2.140
0.001
0.004
0.011

1,378
1.204
0.173
0.003
0.001

2.684
6.708
0.050
1,445
0,166

0.007
0.017
0.002
0.005
0.003

0.046
0.004
0.004
0.001
0.016

0.049
3.022
0.002
0.005
0.038

1.970
1.602
0.248
0.006
0.002

5,395
9.573
0.134
2,147
0.951

10.902 10,337 1 3 . 7 2 9
3.353
2.968
3.891

1.197
2.237
4.519
1.109
1.331
1,326

181.675

0.002
0.006
0.000
0.001
0.002

0.024
0,001
0.002
0.001
0,010

0.020
1.132
0.001
0.002
0.010

0.611
0.612
0.080
0,002
0.001

1.507
4,036
0,009
1.204
0,067

8.174
3,720

0,043
0.955
2.909
1,005
0.235
0.160

33.486

0.005
0.010
0.001
0.004
0.005

0.044
0.003
0.003
0.001
0.040

0.034
1.898
0.002
0,004
0.022

0.910
0,915
0.144
0,007
0.002

2.172
5.565
0.030
1.826
0.530

10.434
5.493

0.347
1.821
4.131
1.524
0.513
0.274

46.424

0.001
0,003
0.001
0.001
0.001

0.014
0.001
0.001
0.001
0.006

0.014
0.527
0.000
0.001
0.013

0.452
0.299
0.043
0.001
0.001

1.135
2.923
0,002
1,102
0,009

5.212
1.961

0.001
0.687
1.889
0.781
0.108
0.112

21.135

0.081
0.318
1.898
0.650
0.129
0.087

23.658

0,332
0,816
2.600
0.862
0,416
0.201

49.728

0.002
0,005
0.001
0.002
0.002

0,025
0.002
0.002
0.001
0.009

0,018
0.787
0.001
0.003
0,023

0.582
0.440
0,071
0.002
0.002

1.767
4.631
0.012
1.609
0.046

0.001
0.003
0.000
0.001
0,001

0.012
0.001
0.001
0.000
0.004

0,013
0.567
0.000
0.001
0.002

0.387
0,279
0.048
0.002
0.000

1,145
2,702
0.002
0,873
0.043

0.002
0.007
0.001
0.002
0.002

0.017
0.003
0.003
0.001
0.006

0.021
0.835
0.001
0.001
0.006

0.583
0.553
0.079
0.004
0.002

1.821
4.038
0.014
1.162
0.558

7 , 3 1 1 1 0 ,4 3 7 22.280
3.261
1.746 4.213

0.010
1.191
3.137
1.235
0,224
0,170

25,910

Avg
Max
Avg
Max
Avg
Max
Avg
Max
Avg
Max
Avg
Max
Avg
Max
Avg
Max
Avg
Max
Avg
Max
(/~gm -3) (//gin -3) (/~gm 3) (#gm-3) (#gm-3) (~gm 3) (/tgm 3) (/tgm 3) (/~gm-3) (#gm-3) (#gm-3) ~ g m 3) (#gm-3) (pgm 3) (ugm-3) (#gm-3) (#gm-3) (jugm-3) (,ugm-3) ~ g m - 3 )

C1NO~
SO~
NH2
Na +
K+

Chemical
species

Point Reyes

Table 4. Statistical summary of 24 h PMl0 measurements between 7/13/90 and 8/24/90 at ten SJVAQS/AUSPEX sites

""

"~
"~
rV
O

O~

bo

Pd

0.001
0.002
0.001

13

TI
Pb
U

No. in average

La

Ba

Au
Hg

0.006
0L009
0.007
0.01Y'/
0.009

0.007
0.029
0.029
0.002
0.1301

Sb

Sn

CA
In

AS

0.002
0.003
0.002

0.017
0.049
0.089
0.005
0.003

0.020
0.016
0.016
0.014
0.025

14

0.002
0.012
0.001

0.008
0.033
0.016
0.002
0.031

0.006
0.010
0.007
0.009
0.009

0.003
0.017
0.002

0.023
0.066
0.043
0.004
0.002

0.014
0.016
0.014
0.020
0.029

14

0.001
0.003
0.000

0.004
0.035
0.021
0.001
0.000

0.004
0.008
0.006
0.005
0.008

0.003
0.007
0.001

0.010
0.082
0.047
0.004
0.002

0.010
0.018
0.016
0.011
0.014

14

0.001
0.012
0.001

0.006
0.090
0.028
0.001
0.001

0.006
0.012
0.008
0.006
0.010

0.004
0.007
0.006
0.005
0.004

0.002
0.021
0.003
14

0.001
0.008
0.030

0.019
0.005
0.148
0.051
0.05t
0.030
0 . 0 0 3 0.002
0 . 0 0 3 0.003

0.012
0.018
0.015
0.015
0.019

0.002
0.014
0.001

0.012
0.131
0.105
0.005
0.001

0.009
0.012
0.017
0.010
0.009

14

0.001
0.008
0.021

0.008
0.055
0.022
0.001
0.001

0.007
0.010
0.006
0.007
0.013

0.005
0.008
0.003
0.006
0.009

14

0.003 0.001
0.019
0.010
0.002
0.001

0.026
0.009
0.162
0.068
0.073 0.023
0.004
0.001
0.002
0.000

0.016
0.022
0.016
0.016
0.040

0.003
0.022
0.001

0.021
0.115
0.069
0.005
0.002

0.013
0.019
0.012
0.017
0.018

14

0.001
0.009
0.001

0.007
0.063
0.022
0.002
0.001

0.007
0.010
0.007
0.007
0.009

0.003
0.018
0.001

0.017
0.122
0.061
0.005
0.002

0.017
0.017
0.013
0.022
0.028

14

0.001
0.004
0.000

0.006
0.033
0.022
0.002
0.020

0.005
0.008
0.006
0.006
0.005

0.002
0.007
0.031

0.015
0.076
0.073
0.004
0.001

0.009
0.016
0.011
0.015
0.015

14

0.021
0.002
0.001

0.006
0.054
0.029
0.001
0.000

0.006
0.009
0.007
0.006
0.008

0.003
0.005
0.001

0.014
0.i05
0.077
0.005
0.002

0.013
0.020
0.020
0.024
0.025

o..

2098

J.C. CHOW

delta, and from the northwest in the SJV. The valleywide elevated sodium and chloride concentrations on
8/24/90 are consistent with the observed transport
phenomenon during this episode.

et al.

Figure 10 also shows that PM~o chloride concentrations exceeded the corresponding PMt0 soluble
sodium concentrations during the last episode at the
Point Reyes, Altamont Pass, and Pacheco Pass sites.

Point Reyes

"

"

iilj!i!i!!!~!i(

Altamont Pass

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

~"'~"" F F - ~ ' " F F

~'F:FF

FF:F:

Pacheco Pass

...................................................

' , ,r.r'~

....

- . ~

.. ~

I:::F'rF

r:F=F:

Crows Landing

Academy

.............................................................................

21

............................................................................................................................................................................

;.:: ...........

1 .........................................................................................................................................

0.5

PM10N~ PI~!_Q.CI"

PM~]K+

Fig. 10. Variations of PMto soluble sodium, chloride, and soluble potassium concentrations between
7/13/90 and 8/24/90 at the ten SJVAQS/AUSPEX sites,

.......

Descriptive analysis of PM2.s and PMlo

2099

tklltonwillow

!;l ............................................................
i .......................................................

P" ~l''-l'",.l'"'~ I"T'T"I""

+,

I"T+i "''

Edison
!:l ............................. .................................................................................................................................................................................................................
,

, flh,,,M~

~'1

: ' " P,. ' "

I'"I"T"T"

f" " " 't~ " ' t>

I " T " I ''+

CalimM

Sequoia Lower Keweah

0.6

......

+t ....................................................................................................................................................................................................................
:2--1711...................................ii?.........iiii???i ~ . . _ 7

'""'+'"',~ :

~.

_ . ............................i........ ?il........i??~?~?;?i??721?i;................. 7 - 7 - .

, .l~'~l
'"',,.I'"

|'"I'"I"T

""

I"T'I '''

Yosmmb

i0.

...........................................................................................................................................................................................................................

PMION; P.M.40.CI"

PM~IK

Fig. 10. (Continued).

When fresh marine aerosol is transported into the

SJV, sea salt reacts with nitric acid to form sodium
nitrate and gaseous hydrochloric acid, thereby reducing PMlo chloride concentrations. These changes in

ratios with respect to marine aerosol show that this

reaction is significant.
Forest fires at Yosemite National Park occurred
during the last episode, and valley-wide haze was

2100

J.C. CHOW et al.

from the northwest are consistent with channeling of
air flow from Bakersfield into the Tehachapi Pass.
Maximum PMlo concentrations for chromium
(0.017 #g m - 3), manganese (0.124 #g m - 3), zinc
(0.053 #g m - 3), and arsenic (0.005 #g m - 3) were found
at the Crows Landing site; these concentrations are
comparable to the maxima reported by Chow et al.
(1990, 1993a) for the data collected at the same location between 6/14/88 and 6/9/89. Similar observations
were found for the PMz.5 size fraction. The nearby
refuse incinerator might have some impact on these
metal concentrations, depending on the materials being burned. Figure l l b shows the distribution of
PMto Zn concentrations at Crows Landing with respect to wind directions measured at the Kesterson
tower. High concentrations in the northwest sector
are consistent with emissions from the refuse incinerator located one kilometer to the north-northwest of
the Crows Landing site.
Maximum PM~o (uncorrected) organic carbon
concentrations of 22.3 #gin -3 were recorded on
8/22/90 at the Yosemite site, which resulted from the

recorded. Since elevated potassium concentrations

can result from vegetative burning, PM~o soluble potassium concentrations are also plotted in Fig. 10.
Elevated soluble potassium is evident only at the
Yosemite site, where PM~o soluble potassium increased twofold during the last episode relative to the
entire study period. Soluble potassium concentrations
also increased at the Sequoia Lower Kaweah and
Caliente sites, but not by large amounts.
Average and maximum elemental carbon and bromine concentrations rank highest at the Caliente site.
Average ( + standard deviation) 24-h PMlo lead
(0.009 +0.007#gin -3) and barium (0.63 + 0.12
#g m-3) concentrations at the Caliente site were two
to four times higher than those found at the Sequoia
Lower Kaweah and Yosemite sites. These higher concentrations at the Caliente site reflect the influence of
motor vehicle exhaust from California Route 58
which runs west to east to the south of the sampling
site. This is demonstrated by Fig. lla, which shows
the distribution of lead concentrations with respect to
wind direction at Caliente. High lead concentrations

Coliente

Pb

Wind

Rose

/J

~'\

~ ~ -- --

\ \

20

'

I ~

"

'~
\

\\\\

'

\\

'5.

XX

%1

'

l/

\'..

.~
--

//

ii
i

I E

x
\ x~~J
L
~ ~

25 I

i5

II

20

10

\ x\
\\

'

\\
\

\\

NX

~"

/
J

\x,\\

ii

//

""

s
AUSPEX
Summer

1990

Intensive

1-3 4-8 7-10 11-16 17-21 22-SS

(8 S) (15 Z)(24 m)(2e s)(14 i ) ( 9 a)

PB CONCENTRATION (NC/M3)
NOTF - WIND DIRECTION iS THE
DIRECTION WIND IS BLOWING FROM

Fig. 11. (a) Lead wind rose at Caliente; (b) zinc wind rose at Crows Landing.

Descriptive analysis of PM2.s and PM~o

2101

Crows Lending Zn Wind Rose

N

,'

,,

W L

..\r~

,'

/ \
I

~"

2e,

X
\

\~

~
\

~
\

~1~'
~

~"

~ "

..

~-I=1-

"~'~

I
,

,
3o~s

,K"

I---I

>/.

Ya

~2

'
,

\
\

',

// /

'

3o l

IE

I
I

l
I
I

I
I
/

//

/~"

'

/
..

iI

/
/

~,

AUSPEX 1990
Summer Intensive
,

'""' u

1-3
4-6
7--10 11-16 1"/-21 Z,~"gl
(0 m) (0 S) (1 ~) (g " ) 0 9 ! ) ( 7 1 ~)

ZN CONCENTRATION (NG/M3)
NOTE - WIND DIRECTION IS THE
D)REGTION WIND IS BLOWING FROM

Fig. 11. (Continued).

forest fire in Yosemite National Park during that

period. The average ( standard deviation) (uncorrected) PMIo organic carbon concentrations were
10.4 5.3#gm -3 at the Yosemite site, and
10.3 1.6 #g m - 3 at the Edison site. The larger standard deviation at the Yosemite site reflects the effects
of forest fires on organic carbon concentrations.
Total carbon (also termed carbonaceous aerosol, is
the sum of the organic (uncorrected) and elemental
carbon) constituted 40--60% of PM2.5 mass and
25-35% of the PM xo mass, and was the single largest
component of PM2.5 and PMlo mass at the ten sites.
A similar abundance of carbonaceous aerosol
(30-40%) was reported for PMxo in southern California (e.g. Pratsinis et al., 1984, 1988; Gray et al., 1986;
Solomon et al., 1989; Chow et al., 1994d). Elemental
carbon, which has a chemical structure similar to
impure graphite, originates primarily from direct
emissions of particles, predominately during combustion, while organic carbon originates either from
direct emissions of particles or from atmospheric

transformation of organic gases. Secondary organic

carbon is formed by condensation of low vapor pressure products during photo-oxidation of hydrocarbons (Larson et al., 1989; Pandis et al., 1992, 1993;
Grosjean, 1992). Atmospheric formation of secondary
organic carbon is expected during ozone episodes.
Organic to elemental carbon (OC/EC) ratios exceeding 2.0 (i.e. TC/EC > 3.0) have been used to identify
the presence of secondary organic aerosols (Gray et
al., 1986; Turpin et al., 1990; Hildemann et al., 1991)
during summertime afternoon samples at downwind
receptors. Diurnal patterns of the total to elemental
carbon (uncorrected for OC sampling artifacts) ratios
at the ten sites are illustrated in Fig. 12. The summertime TC/EC ratios were variable, with peaks occurring mostly between 1200 and 1700 PSI'. The TC/EC
ratios exceeded 10 at the Point Reyes, Crows Landing, Academy, Buttonwillow, Caliente, and Yosemite
sites on different sampling days. It is possible that
there were some contributions to the afternoon samples from particulate organic carbon which formed

X ~

C2.

>=

Oo

,<=
>~-.

I:Z,~
oo ~

0
o

12

12

I"C/EC

8/24/00

~/24~0

12

12

8/23/00

~/23/00

12

8/6/00

12

:
:
:

TC/EC

if'
,__.
.-,-,,,

12

~/24/00

12

~/23/00

12

o ,o .= o, = ~ ~,

ir

rC/EC

12

8/24/00

12

8/23/00

12

8/22/00

12

8/6/O0

12

12

8/4/'00

8/3/00

815/00

12

I I

3/22/00

815/00

ml

7/29100

7/28100

8/4/00
12

8/3/00

7/29/00

12

7/28/00

12

ii8

7/27/00

7/27/00
12

12

12

12

12
7/22/00

7/21/00

7/21/00

7/22/00

12

12

12

12

7/13/00

7/14/00

3oncenb'ation [IJg/m3]

12

8/22/00

.3once~-,b=atkxl[iJg/m3]

7/14/00

7113/OO

~/22/00

~nc:=ee~'~ion [pg/m3]

F=

lip

TC/EC

Jq

Ol

3oncenb'ation [iJg/m3]

==

~'

12 ~

8/3/00

7/27/00

12~'~

O~ CO O

TC/EEC

7/14:

JL

7/13~o~
I

Concentration [pglm 3]

(m

<

"3

~'J
.~

7/28/00
12

12

7Q~O0

12

7Q1~

-I

m=

==

o~

7113K

7/28/00
12
7/29/00

D
r

71291(

7128K

7/27K
1

os

12

7/27/00

12

7/13/0012i

7Q7~

o~ ~

7/21K
12
7/22/00
12

~ncerd~k)n [pg/m 3]

7/21/00 "
12
7/22/OO
12

7114/00
12

"O

,?,oncentratmn[po/m 3]

7114K
1

Conce~,b=a;on [pg/m 3]

7/14/00
12

H13/00

_l]

Concentration [iJg/m3]

rl?

2104

J.C. CHOW

24-Hour Average ~ . 5
Concentrations

et

al.

Sulfate and Nitrate

4
3.2

3.4

, ~

.................................................................

;:.,-..,.::

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

++"

%.%

1 ........................................................................0,7"

........................................................... ;." ............................

0.II
........
0 41
o.i . . . . . . . . . . . . . . . . . . . . .
~ o ? . . . . . . . . . . . . .'+

t~+

Oi

....

- - r "+"

rR

ALT

"3

PAC

CRO

AC.I.

+" ". .%. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

",o 3

BUT

o3

EDI

CAl.

.......

8LK

YOS

4.4

4.3

~ .....................................................................................

27,

2
1 .................................................................. :.,~.0J).+.+.........................................................,:.:~........................;:~'.:. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

_.o~3_......... ~

.................

..~

....

.o.o.y'"

"'u.

o.:

.... .o.:..+.. . . . . . .

II

0 IIq'R

.lilT

PAO

AC,A i I ~

BUT

EDI

CAl.

8LK

Y06

...................................................................- - - .....................................................................'4;'/'.................................................................................

...........

+_...

;?+ . . . . . . . . . . . . . . . .

Z ::;: : :
'1

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i
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.---.--':~"" . . . . . . . . .
~
,
PAC
~

~.:7.
,
~

. .
,
BUT

. .
,
EDI

4.1 +

....

"@.2

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o;

1".............. r. . . . . . . . . . . . ,
CAL.
SLK
YOS

4.4
4.1

~a

4 ............................................................................ .-.. . . . . . . . . . . . .

"

1.3
;:~.~.

............................................

L2
,,I -

01~m

0.2.

,+i.T

.....

..........

"

._

I .o ..................

;+'~': .......... ~ + ; : - 0 . 6 ~. .. . . . . . ... .

0 , : " . 4 . .. . . . . . .. . . . . . . . . .

' : ".~ ' ~ .

." . . . ... . . . . . ... . . . . . . . . . . . . . . . . . . .

~.15+.........................................

.,

;;++. .". . . . . . . . . 3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

I ~ ........

RI~

ClIO

ACA

BUT

EDI

CAL.

804s

0.2

....

'I--" .........

8LK

"-'"
0.,
m"l

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NO3-

F i g . 13. S p a t i a l v a r i a t i o n s o f P M 2 . s s u l f a t e a n d n i t r a t e d u r i n g t h e e p i s o d e o f 8 / 3 / 9 0 t o 8 f 6 / 9 0 a t t h e t e n
SJVAQS/AUSPEX
sites ( t h e site c o d e s a r e e x p l a i n e d in F i g . 1).

Descriptive analysis of PMz.s and PMto

~'~'F'-- 7

-~. . . . . . .

~ ,-~

/---U"

, -

. . . . . ~-

/' ',>

/-

I"-~ . . . .
~ . . . . .

L)

__

/ .......

20 4o eo

80

.:(
.,

~['~

,>~'-..Jx]; " ~

<'~

ye~

,."%'~.

..-

h"'-',,
~\

"~

,,~llllllllllll~

~
xx

'
.

~l

. . . . . . . . .

____..~./

,.

o. .to . 20. 30
. . 40 so

Kilorneters

j"

....
""

Miles

|
~

-C ~. . . . ~

"
~

%4

~ ' J _r~J

I
~-{

2105

~
//

3- . . . .

8LK

11

Orgunic
Elemental CIrbon
Ammonium Ion
Nltrlte Ion

ul1~tteIon
Crustal

/-" q

"--L . . . . . . . . . .

-~

I Trace Species
Madne
i

Unidentified
I

\\\
t

Fig. 14. Average 24 h PM2.s mass and chemical concentrations (~gm -3) between 7/13/90 and 8/24/90 at
the ten SJVAQS/AUSPEX sites (the site codes arc explained in Fig. 1).
from organic gases, but these contributions need to be
further investigated.
Average PM2.5 sulfate concentrations ranged from
1.1 to 3.3#gm -3. Average PM2.s nitrate and ammonium concentrations ranged from 0.1 to
1.5 # g m -3 at the ten sites, which is < 5 0 % of average
PM2.s sulfate concentrations. Nitrate, sulfate, and
ammonium constituted 25-35% of the PMz.s mass
and 15-25% of the PMto mass at all but the Point
Reyes site. The PM2.s ions to mass ratio reached 0.5
at the Point Reyes site. Maximum and average PM2.5
mass, nitrate, sulfate, and ammonium were highest at
the Edison site.
Twenty-four hour PM2.s sulfate and nitrate concentrations were highest during the 8/3/90 to 8/6/90
episode. Figure 13 shows that sulfate and nitrate concentrations were stable over this 4-day episode, with

a possible build-up at the Pacheco Pass, Academy,

and Buttonwillow sites. A region-wide phenomenon
was seen on 8/6/90, when PM2.s sulfate gradually
increased from the northern SJV sites (Point Reyes,
Altamont Pass, Pacheco Pass), remained constant
through the central SJV sites (Crows Landing, Academy, Buttonwillow, Edison), and decreased at the
southeastern exit site (Caliente). PM2.5 nitrate concentrations were low ( < 2 # g m - 3), less than half of
the corresponding PM2.s sulfate concentrations.
These nitrate concentrations followed a similar pattern among the four days and peaked at the Crows
Landing and Edison sites.
Figures 14 and 15 show variations of material balances for average organic carbon (uncornx~ted), elemental carbon, ammonium, nitrate, sulfate, crustal
material, trace SlX)cies, sea salt, and unexplained mass

2106

J.C. CHOW et al.

~--~

...........

--

l: ;
~t[

---

)~/
~ ~'~-

Idil . . . . . . . . . . . . .

= . . . . . . . . .

Kilometers

2o

40

6o

~o

/
.

,\

_,,~

fie

\,
x

"

,,

",

ACA

"'18"

:
I.
'.

,
I

'..... ~ ~
'

Organm

Elemental Carbon

"-\~ . . . . . . . . . . . . . .

SLK

~
r~
I

' "
%.

/
~
i

~ ....

21

....................

- A ~ t ~ - -

I=DI

)--

5l

e?

Ammonium lon
I

NItrite Ion
Sulfate Ion

"5

Crustal
[---~

..~-_

~ii~IIllllllllII~
sa

~w~

Trace Species
/

Marine

tI

Unidentified

\
I

Fig. 15. Average 24 h PMto mass and chemical concentrations (#gm-3) between 7/13/90 and 8/24/90 at
the ten SJVAQS/AUSPEX sites (the site codes are explained in Fig. 1).

abundances in PM2.s and PMlo. The material balance (Solomon et al., 1989; Chow et al., 1994d) applies
the following steps: (1) multiply average organic carbon concentrations by 1.4 to account for unmeasured
hydrogen and oxygen in organic material; (2) sum the
aluminum, silicon, calcium, and iron oxides (i.e.
[1.89 x aluminum] + [2.14 x silicon] + [1.4 x calcium] + [1.43 x iron]) to estimate the crustal material; (3) sum the soluble sodium and chloride to
account for sea salt; and (4) add the concentrations
of other species listed in Tables 3 and 4, without
double-counting chloride, soluble potassium, and total sulfur.
The unexplained portion is usually less than 10% of
average PM2.5 or PMIo mass concentrations. When
crustal materials are a larger fraction of the total mass

in the PM to fraction, the portion of unexplained mass

is insignificant.
The crustal material abundances in the PM2.5 fraction were 40% at the Crows Landing site, 37% at the
Edison site, and less than 30% at the remaining sites.
Total carbon aerosol constituted over 50% of the
PM2.s mass except at the Crows Landing and Edison
sites. In the PM2.5 fraction, the abundances of trace
species and sea salt at the Point Reyes site were
~ 10% and over 30%, respectively; these abundances
accounted for less than 3% of the PM2.5 fraction at
the remaining sites. PM2.5 nitrate concentrations
were more uniform across the SJV, with slightly (2%)
higher abundances at the Point Reyes and Pacheco
Pass sites. PM2.s sulfate was more abundant ( > 2%)
at the northern SJV sites such as Point Reyes,

Descriptive analysis of PM2.s and PMto

Altamont Pass, and Pacheco Pass, even though the

difference in absolute concentrations was within
1-2#gin -3 at all sites. Similar observations were
found for PM2.s ammonium, with a lower percent
mass.

2107

Contributions from crustal material and trace species in the PMIo fraction were lowest (41%) at the
Yosemite site and highest (79%) at the Crows Landing site, whereas PMlo contributions from organic
carbon were highest (62%) at the Yosemite site and

Point Reyes
~ 40
E

uo -~u
i

-~-u~uu~u~
~

-uHuuHu~-~
l

ou
l

O~O ~

i,

L...........................................................................................................................................................................................................................
~
.

inOrganic mEle. Carbon ~Ammonlum INlrato

~uuuuu

Pass

Altamont

6o

~8ulfate

~Cmstal Marine I~TracaSpecles I-IUneXl~ed

Pacheco Pass
60

I:

o 0
~,

.........................................................................................................................................................................................................................

~ii i i:i ii: :iiii',ihi:: ::iidi ~ii: :,~iit~

, , , ,uUuU

....

I,I,

, , I,IT,

, , VUt,ITW

,~,UWUl,ll,l~,

, U,

, WVU,

, , I,II,II,IuUI,I

....

NOrgaric liNe, Carbon Iln.a~nmonlum IiNitate NSulfate QCtustd ilMwine NTrsceSpedes

Crows

........................................................................................
.............................................................

0 srl~l

DUnex~

Landing

....................................................................
.........................................................................

Ele. Carbon
Marine

WI,IWUL~I,I, ~ , VV~J

~ Ammonium
[ ] Trace Species

::i:::iiiiiiiii.... IE: i i i:i ...... IIIIILIIII:

....o...

Sibllte
[ ] Sulfate
[ ] Unexplained

Fig. 16. Diurnal variations of PMIo chemical compositions by material balance between 7/13/90 and
8/24/90 at the ten SJVAQS/AUSPEX sites (the site codes are explained in Fig. 1).

2108

J.C. CHOW et al.

Academy
~100

i"

4O

20

(3
o

'-/, I j t J L ~ U ,

[ ] Organic

hl'd,

, ; Ul,rl,I,

Ele. C a r b o n

, h i ,LJ ,

, L J [ , I _ , ' T ' L d _ , LJ'f, -- , , , I,li,IM . . . . . .

[] Ammonium

[ ] Nitrate

[ ] Sulfate

~ Crustal

LI . . . . . . . . . . . .

Manne

[ ] T r a c e Species

I,I,

, 7.,

[ ] Unexplained

Buttonwillow
2O4

100

.........................

- ..
80

J!ll~

~liil[iil

~o
40
o
o
o

20

L,JI,ILIULII II rLJ

LJUI.,J~I ILl

I r t-,JII

Ull

LIL,J

LJ

L,J

tO

[J

'--'

II

[ ] Organic

Ele. C a r b o n

[] Ammonium

Nitrate

Sulfate

[ ] Crustal

Madne

[ ] Crustal

[ ] Marine

[ ] T r a c e Species

[ ] Unexplained

Edison
1oo

g~o
E
o

60

[ ] Organic

[ ] Ele. Carbon

El A m m o n i u m

[ ] Ni~ate

~ Sulfate

[ ] Trace Species

[ ] Unexplained

Caliente
~80

E I

9,10

k i

lL
p-.

LJ, ,JLLL~ . . . .

'79 I US' . . . .- - -L ; ~

~ ~,
'

4JVgLI

, , ,

Vr,I

i J ~"~
~ i i , , i J ; uu'-'lru
~ J i~r't i I

UJ

p-.
[ ] Organic

B e . Carbon

[] Ammonium

[ ] Nitrate

F~ Sulfate

[ ] Crustal

[ ] Marine

[ ] Trace Species

D Unexplained

Fig. 16. (Continued).

lowest (18%) at the Crows Landing site. Sea-salt

abundances in PMlo ranged from 53% at Point
Reyes, 5 to 6% at Altamont Pass and Pacheco Pass,
and less than 1.5% at the remaining sites. PMlo
nitrate and ammonium abundances were similar to
those found in the PM2.5 fraction, with higher fractions found at the Pacheco Pass site. PM~o sulfate

ranged from 13 to 27% at the Point Reyes, Altamont

Pass, and Pacheco Pass sites, and 4 to 9% at the
remaining sites, with the absolute concentrations similar to those found for PM2.5.
Figure 16 presents diurnal variations of chemical
compositions calculated from the material balance for
each of the sampling sites. Crustal material was the

Descriptive analysis of PM2. s and PMIo

2109

8oquola Lower Kewoah

i

~0

...........................................................................................................................................................................................................................

20

...................................................................................................................................

4O

"~ (10)
iOrgimlc IEle. Cirbon ITgAmmorlum nnNitrlte ~ l l t e

r~Cruotnl I Madne IlraceSpodel

NUnexlpl~od

Yosemite

- : : i ; ; /77 Z Zillliii.li21111...iZ/illl................................................................................................................................................................................

::
j+i+,
.............

k+

.....i l l ........................
...........................................................................................................................
+
.

[] Or(lade Be. Carbon [] Ammonium Ill Nitrate [] Sulfate [] CnJtol l l n e

[] TraceSpecie= [] Ul~xplitod

Fig. 16. (Continued).

major source and constituted over 50% of PM~o.

Trace species were most pronounced ( > 5/~g m - 3) at
the Point Reyes site during the last two episodes, and
at the Crows Landing (on 7/27/90, 8/6/90, and
8/22/90) and Buttonwillow sites (on 8/6/90 and
8/24/90) when elevated coarse particle concentrations
~ r found. Sea-salt contributions were only significant ( > 5 #gm -3) at the Point Reyes site during the
last two episodes and at the Pacheco Pass site during
the last episode.
Elemental carbon concentrations were typically in
the range 1-3/~g m -3. These concentrations were
higher at the southern SJV sites, especially at the
C.aliente site during nighttime (1700-2400 PDT) and
early morning (0000--0700 PDT) periods when elemental carbon concentrations often exceed~ 5/~g m - 3.
Contributions from organic carbon tended to increase
from northwest to southeast within the SJV, with the
exception that the highest contributions were observed at the Yosemite site during forest fires between
8/22/90 and 8/24/90. Reconstructed organic carbon
(1.4 x OC) was found to be over 20/~g m -3 at the
inland SJV sites (Pacheco Pass, Crows Landing,
Academy, Buttonwillow, Edison, and Caliente), with
peaks
occurring
mostly
during
afternoon
(1200-1700 PDT) samples.
PMlo ammonium and nitrate concentrations were
typically 0.5-2/~gm -3. Two high PMto nitrate concentrations (6.5/~gm -3 at the Crows Landing Site on
7/27/90 and 7.5/tgm -3 at the Pacheco Pass site on
8/5/90) were recorded during the early morning
(0000-0700 PST). PM~o sulfate concentrations usu-

ally excceded PM 1o nitrate concentrations by a factor

of two, and were 1-1.5 #gm -3 higher at the Edison
site than at the remaining sites.

SUMMARY AND CONCLUSIONS

The SJVAQS/AUSPEX aerosol data set has been

documented and evaluated. Temporal and spatial
variations of PM2.s and PMto mass and chemical
compositions have been examined. The results of
these efforts are as follows:
PM2.s and PMIo mass, ions (i.e. nitrate, sulfate,
ammonium), organic carbon, elemental carbon, and
crustal species (e.g. aluminum, silicon, potassium, calcium, iron) were found above the lower quantifiable
limRs in over 80% of the cases. The sum of the
chemical species explains more than 90% of the measured PM2.s or PMlo mass.
Comparisons of PM2.s to PMlo mass chemical
concentrations showed the majority of values to be
valid. A few outliers were identified and flagged.
The collection of particulate organic carbon on
quartz-fibre filters is subject to error from both adsorption of organic gases (positive artifact) and by
volatilization of paniculate organic carbon (negative
artifact) during sampling. Organic carbon measurements on the front quartz-fiber filters may possess
a positive bias owing to this artifact, but the cascade impactor data obtained during AUSPEX suggest that the organic carbon measured on the backup

2110

J.C. CHOW et al.

quartz-fiber filter may overestimate this artifact in

many cases. Additional work is needed to understand
better the uncertainties associated with the collection
of organic carbon.
Anion/cation balances support the accuracy and
precision of ion chromatographic measurements for
nitrate and sulfate and of automated colorimetric
measurements for ammonium. Sodium sulfate and
sodium nitrate were found to be significant in the
coarse particle fraction, while ammonium sulfate and
ammonium nitrate were found to be significant in the
PM2.5 fraction.
Elevated PMI0 soluble sodium and chloride concentrations were found at the northern San Joaquin
Valley sites during the episode of 8/3/90 to 8/6/90,
and at all California sites during the episode of 8/22/90
to 8/24/90. This is an indication of the influence
and extent of transport from the coastal to the inland
sites.
The 24-h federal PMlo standard was exceeded
only at the Buttonwillow site on 8/24/90, with PM~o
mass being 182#gm -3, during the ozone episode
studies.
PM2.s constituted 30--70% of PMlo mass. Organic carbon was the most abundant species and
constituted 25-35% of the average PM~0 mass.
Sodium, aluminum, silicon, calcium, and iron
were abundant mostly in the coarse particle fraction,
consistent with their presence in marine aerosol
(sodium) and suspended dust (aluminum, silicon, potassium, calcium, iron). Other trace element concentrations were generally lower in coarse particles than
in PM2.5. Sulfate, ammonium, organic carbon, and
elemental carbon were abundant in the PM2.5 fraction; nitrate was abundant in the PM2.5 and coarse
particle fractions.
Elevated PMI0 concentrations occurred sporadically and at individual sites such as Crows Landing and Buttonwillow. Higher wind speed coupled
with the local activities adjacent to the sampling
sites may have resulted in these elevated PM~o concentrations.
It is evident from this study that local and regional
emissions and meteorology influenced the PM2.5 and
PM lo concentrations. The effect of precursor gases on
secondary aerosol concentrations needs to be examined in order to derive quantitative relationships of
the primary and secondary aerosol contributions to
PM2.s and PMlo.
Acknowledgements--Field monitoring and chemicalanalysis
of the SJVAQS/AUSPEXwas sponsored by PacificGas and
Electric Company (PG&E). The analyses presented in this
paper were sponsored by the San Joaquin Valley Joint
Power Agencyand the California Air Resources Board. The
authors are grateful for the assistance of Stephen Andersen
of SEACOR (formerlywith ENSR, Fort Collins, CO) for his
efforts in conducting the field sampling program. The
authors would also like to thank Ms Barbara Hinsvark and
Mr William Dippel of the Desert Research Institute (DRI)
for coordinating the sampling program, and Ms Kim Snow

and Ms Dana Dondero, also of DRI, for assembling and

editing the manuscript.
Statements and conclusions in this paper are those of the
authors and not necessarilythose of the sponsors. The mention of commercialproducts, their sources, or uses in connection with material reported herein is not to be construed as
actual or implied endorsement of such products.
REFERENCES

Ashbaugh L. L., Watson J. G. and Chow J. C. (1989) Estimating fluxes from California's dry deposition monitoring
data. Document # 89-65.3, Presented at the 82nd Annual
Meeting, Anaheim, California. Air & Waste Management
Association, Pittsburgh, Pennsylvania.
Blumenthal D. L. and Lurmann F. W. (1994) Design rationale for the SJVAQS/AUSPEX meteorological and air
quality measurement network to support regional air
quality modeling and analyses.In Planning and Managing
Air Quality Modeling and Measurements Studies: A Perspective Through SJ V AQS/A U SPEX (edited by Solomon
P. A.), pp. 131-170. Lewis Publishers, Chelsea, in conjunction with Pacific Gas and Electric Company, San
Ramon.
Blumenthal D. L. and Watson J. G. (1994) SJVAQS/
AUSPEX collaborative field study plan. In Planning and
Managing Air Quality Modeling and Measurements Studies: A Perspective Through SJVAQS/AUSPEX (edited by
Solomon P. A.),pp. 107-130. Lewis Publishers,Chelsea, in
conjunction with Pacific Gas and Electric Company, San
Ramon.
Bolleter W. T., Bushman C. T. and Tidell P. W. (1961)
Spectrophotometric determination of ammonium as indophenol. Anal. Chem. 33, 592-594.
California Air Resources Board (1991) California air quality
data: summary of 1990 air quality data: gaseous and
particulate pollutants. Volume XXII, Annual Summary.
Technical Support Division, California Air Resources
Board, Sacramento.
Chow J. C. (1995)Critical review--measurement methods to
determine compliance with ambient air quality standards
for suspended particles. J. Air Waste Man. Ass. 45,
320-382.
Chow J. C. and Richards L. W. (1990a) San Joaquin Valley
Air Quality Study (SJVAQS)/Atmospheric Utility Signatures-Predictions and EXperiment(AUSPEX).Monitoring and analysis for aerosols and visibility,Vol. I: program
plan. DRI Document 8743.1F, Prepared for Pacific Gas
and ElectricCompany by Desert Research Institute, Reno.
Chow J. C. and Richards L. W. (1990b) San Joaquin Valley
Air Quality Study/Atmospheric Utility Signatures--Predictions and EXperiment (AUSPEX), Part E: monitoring
and analysis for aerosols and visibility,Vol. II: standard
operating procedures. DRI Document 8743.1F, Prepared
for PacificGas and Electric Company by Desert Research
Institute, Reno.
Chow J. C., Watson J. G., Lowenthal D. H., Pritchett L. C.
and Richards L. W. (1990) San Joaquin ValleyAir Quality
Study, Phase 2:PM10 modeling and analysis, Vol. I:
receptor modeling source apportionment--final report.
DRI Document 8929.1F, Prepared for The San Joaquin
Valley Air Pollution Study Agency by Desert Research
Institute, Reno.
Chow J. C., Watson J. G., Lowenthal D. H., Solomon P. A.,
Magliano K., Ziman S. D. and Richards L. W. (1992a)
PMIo source apportionment in California's San Joaquin
Valley. Atmospheric Environment 26, 3335-3354.
Chow J. C., Watson J. G., Lowenthal D. H., Lu Z., Frazier
C. A., Pritchett L. C. and Hinsvark B. A. (1992b) San
Joaquin ValleyAir Quality Study (SJVAQS)/Atmospheric
Utility Signatures--Predictions and EXperiment (AUSPEX), monitoring and analysis for aerosols and visibility,

Descriptive analysis of PM2.s and PM l0

Vol. HI: aerosol measurements and data bases--final report. DRI Document 8743.3F, Pacific Gas and Electric
Company by Desert Research Institute, Reno.
Chow J. C., Watson J. G., Lowenthal D. H., Solomon P. A.,
Magliano K., Ziman S. D. and Richards L. W. (1993a)
PMIo and PM2.s compositions in California's San
Joaquin Valley. Aerosol. Sci. Technoi. lg, 105-128.
Chow J. C., Watson J. G., Bowen J. L., Gertler A~W., Frazier
C. A., Fung K. IC and Ashbaugh L. (1993b) A sampling
system for reactive species in the western U.S. In Sampling
and Analysis of Airborne Pollutants (edited by Winegar E.
and Keith L. H.), pp. 209-228. American Chemical Society, Washington, District of Columbi~L
Chow J. C., Watson J. G., Pritchett L. C., Pierson W. R.,
Frazier C. A. and Purcell R. G. (1993c) The DRI thermal/optical reflectance carbon analysis system: description, evaluation, and applications in U.S. air quality studies. Atmospheric Environment 27A, 1185-1202.
Chow J. C., Watson: J. G., Solomon P. A., Thuillier R. H.,
Magliano K. L., Ziman S. D., Blnmenthal D. L. and
Richards L. W. (1994a) Planning for SJVAQS/AUSPEX
particulate matter and visibility sampling and ~nalysis. In
Planning and Managing Air Quality modeling and Measurements Studies: A Perspective Through SJVAQS/AUSPEX (edited by Solomon P. A.), pp. 171-216. Lewis Publishers, Chelsea, in conjunction with Pacific Gas and Electric Company, San Ramon.
Chow J. C., Watson J. G., Houck J. E., Pritchett L. C.,
Rogers C. F., Frazier C. A., Egami R. T. and Ball B. M.
(1994b) A laboratory resnspension chamber to measure
fugitive dust size distributions and chemical compositions.
Atmospheric Environment 2,8, 3463-3481.
Chow J. C., Fujita E. M., Watson J. G., Lu Z., Lawson D. R.
and Ashbaugh L. L. (1994c) Evaluation of filter-based
aerosol measurements during the 1987 southern California air quality study. Envir. Mon. Assess. 30, 49-80.
Chow J. C., Watson J. G., Fujita E. M., Lu Z. and Lawson
D. R. (1994d) Temporal and spatial variations of PMz.5
and PMI0 aerosol in the southern California air quality
study. Atmospheric Environment 28, 2061-2080.
Chow J. C., Watson J. G., Lu Z., Divita, F. Jr, Lowenthal
D. H., Solomon P. A., Thuillier R. H. and Magliano K.
(1996) Diurnal variations of regional PMI0 precursor
gases and photochemical reaction products during
SJVAQS/AUSPEX ozone episodes. J. Inhalation Toxicol.
(to be submitted).
Dzubay T. G. (1977) X-ray FluorescenceAnalysis of Environmental Samples, 2nd edn, pp. 289-306. Ann Arbor Science
Publishers, Ann Arbor.
Eatough D. J., Aghdaie N., Cottam M., Gammon T., Hansen
L. D., Lewis E. A. and Farber R. J. (1990) Loss of semivolatile organic compounds from particles during sampling on filters. In Transactions, Visibility and Fine Particles
(edited by Mathai C. V.), pp. 146-156. Air & Waste Management Association, Pittsburgh.
Eldering A., Solomon P. A., Salmon L. G., Fall T. and Cass
G. R. (1991). Hydrochloric acid: a regional perspective on
concentrations and formation in the atmosphere of southern California. Atmospheric Environment 25A, 2091-2102.
Federal Register (1989) Air monitoring reference and equivalent methods: reference method designation. Federal Register 54, 12273.
Gertler A. W., Coulombe W. G. and DeWitt D. (1990) San
Joaquin Valley Air Quality Study and Atmospheric Utility
Signatures, Predictions and Experiments standard operating procedures evaluation report. Prepared for Pacific
Gas and Electric Company by Desert Research Institute,
Reno.
Gertler A. W., Coulombe W. G. and DeWitt D. (1993)
Quality assurance report for SJVAQS/AUSPEX. DRI
Document 8403.4F1, Prepared for Pacific Gas & Electric
Company and the San Joaquin Valley Joint Study Agency
by Desert Research Institute, Reno.

2111

Gray H. A., Cass G. R, Huntzicker J. J., Heyerdahl E. K. and

Ran J. A. (1986) Characteristics of atmospheric organic
and elemental carbon particle concentrations in Los
Angeles. Envir. $ci. Technoi. 28, 580-589.
Grosjean D. (1992) ln-situ organic aerosol formation during
a smog episode. Atmospheric Environment 26A, 953-963.
Hackney R. J., Hughes V., Magliano K. L., Niccum E. M.,
Phelps W., Watson J. G. and Anderson J. (1994)
SJVAQS/AUSPEX and SARMAP data management. In
Planning and Managing Air Quality Modeling and Measurements Studies: A Perspective Through SJVAQS/
AUSPEX (ecfited by Solomon P. A.), pp. 301-334. Lewis
Publishers, Chelsea, in conjunction with Pacific Gas and
Electric Company, San Ramon.
Hering S. V., Lawson D. R., et al. (1988). The nitric acid
shootout: field comparison of measurement methods. Atmospheric Environment 22, 1519-1539.
Hildemann L. M., Markowski G. R. and Cass G. R. (1991)
Chemical composition of emissions from urban sources of
fine organic aerosol. Envir. Sci. Technol. 25, 744-759.
Holets S. H. (1992) Description of atmospheric conditions
during ozone episodes in SJVAQS/AUSPEX. Interim Report, Pacific Gas & Electric Company, San Ramon.
Larson S. M., Cass G. R. and Gray H. A. (1989) Atmospheric
carbon particles and the Los Angeles visibility program.
Aerosol Sci. Technol. 10, 118-130.
Lee K. W. and Ramamurthi M. (1993) Filter collection. In
Aerosol Measurement: Principles, Techniques and Applications (edited by Willeke K. and Baron P. A.), pp. 179-205.
Van Nostrand, Reinhold, New York.
Lippmann M. (1995) Sampling aerosols by filtration. In Air
Sampling Instrumentsfor Evaluation of Atmospheric Contaminants, (edited by Cohen B. and Hering S. V.), 8th Edn,
American Conference of Governmental Industrial Hygienists, Cincinnati.
McDow S. R. and Huntzicker J. J. (1990) Vapor adsorption
artifact in the sampling of organic aerosol: face velocity
effects. Atmospheric Environment 24A, 2563-2572.
McInnes L. M., Covert D. S., Quinn P. K. and Germani
M. S. (1994) Measurements of chloride depletion and
sulfur enrichment in individual sea-salt particles collected
from the remote marine boundary layer. J. geophys. Res.
99, 8257-8268.
Mamane Y. and Mehler M. (1987) On the nature of nitrate
particles in a coastal urban area. Atmospheric Environment
21, 1989-1994.
Mamane Y. and Gottlieb J. (1992) Nitrate formation on
sea-salt and mineral particles---a single particle approach.
Atmospheric Environment 26A, 1763-1769.
Mulik J., Puckett R., Williams D. and Sawicki E. (1976) Ion
chromatographic analysis of sulfate and nitrate in ambient
aerosols. Envir. Sci. Technol. 9, 653-663.
Pandis S. N., Harley R. A., Cass G. R. and Seinfeld J. H.
(1992) Secondary organic aerosol formation and transport. Atmospheric Environment 26A, 2269-2282.
Pandis S. N., Wexler A. S. and Seinfeld J. H. (1993) Secondary organic aerosol formation and transport-II. Predicting the ambient secondary organic aerosol size distribution. Atmospheric Environment 27A, 2403-2416.
Pratsinis S. E., Ellis E. C., Novakov T. and Friedlander S. K.
(1984) The carbon containing component of the Los
Angeles aerosol: source apportionment and contributions
to the visibility budget. JAPCA 34, 643~550.
Pratsinis S. E., Zeldin M. D. and Ellis E. C. (1988) Source
resolution of the fine carbonaceous aerosol by principal
component---stepwise regression analysis. Envir. Sci.
Technol. 22, 212-216.
Putaud J.-P., Belviso S., Nguyen B. C. and Mihalopoulos N.
(1993) Dimethylsulfide, aerosols, and condensation nuclei
over the tropical northeastern Atlantic ocean. J. geophys.
Res. 98, 14,863-14,871.
Pytkowicz R. M. and Kester D. R. (1971) The physical
chemistry of sea water. Oceanogr. Mar. Biol. Ann. 9, 11.

2112

J.C. CHOW et al.

Rhodes J. R., Guinn V. P. and Thompson R. J. (1989) General

atomic absorption procedure for trace metals in airborne
material collected on firm. In Methods of Air Sampling and
Analysis (edited by Lodge J. P.), pp. 608-618. Lewis Pubfishers, Chelsea.
Rogers C. F. and Watson J. G. (1984) Potential causes of
elevated PMIo and PMls concentrations in the inhalable
particulate network. EPA-450/4-84-016, U.S. Environmental Protection Agency, Research Triangle Park, North
Carolina.
Seigneur C. and Wu A. (1992) Quantitative assessment of the
effect of various emission control technologies on aerosol
formation. In Transactions, PMlo Standards and Nontraditional Particulate Source Controls (edited by Chow
J. C, and One D. M.), pp. 794-806. Air and Waste Management Association, Pittsburgh.
Solomon P. A. (ed.) (1994) Planning and Manaoing Air Quality Modeling and Measurements Studies: A Perspective
Throuoh SJVAQS/AUSPEX. Lewis Publishers, Chelsea,
in conjunction with Pacific Gas and Electric Company,
San Ramon.
Solomon P. A., Larson S. M., Fall T. and Cass G. R. (1988)
Basinwide nitric acid and related species concentrations
observed during the Claremont nitrogen species comparison study. Atmospheric Environment 22, 1587-1594.
Solomon P. A., Fall T., Salmon L., Cass G. R, Gray H. A.
and Davison A. (1989) Chemical characteristics of PM10
aerosol collected in the Los Angeles area. JAPCA 39,
154-163.
Solomon P. A., Salmon L., Fall T. and Cass G. R. (1992). The
spatial and temporal distribution of atmospheric nitric
acid and particulate nitrate concentrations in Los Angeles.
Envir. Sci. Technol. 26, 1594-1601.
Tang H., Lewis E. A., Eatough D. J., Burton R. M. and
Farber R. J. (1994) Determination of the particle size
distribution and chemical composition of semi-volatile
organic compounds in atmospheric fine particles with
a diffusion denuder sampling system. Atmospheric Environment 28, 939-947.
Thnillier R. H., Blumenthal D., Roberts P., Gertler A. and
Watson J. (1993) Meteorological field measurement program for SJVAQS/AUSPEX. Environmental Health and
Safety Report #009.2-93.4.
Trijonis J., McGown M., Pitchford M., Blumenthal D.,
Roberts P., White W., Macias E., Weiss R., Waggoner A.,
Watson J., Chow J. and Flocchini R. (1988) The

RESOLVE project: visibility conditions and causes of

visibility degradation in the Mojave Desert of California.
Prepared for Naval Weapons Center/China Lake by
Santa Fe Research Corporation, Santa Fe.
Turpin B. J., Cary R. A. and Huntzicker J. J. (1990) An
in-situ, time-resolved analyzed for aerosol organic and
elemental carbon. Aerosol Sci. Technol. 12, 161-171.
Turpin B. J., Huntzicker J. J. and Hering S. V. (1994) Investigation of organic sampling artifacts in the Los Angeles
Basin. Atmospheric Environment 28, 3061-3071.
Watson J. G. and Chow J. C. (1993) Ambient air sampling. In
Aerosol Measurement: Principles, Techniques, and Applications (edited by Willeke K. and Baron, P. A.), Chap. 28, pp.
622-639. Van Nostrand Reinhold, New York.
Watson J. G. and Chow J. C (1994) Particle and gas
measurements on filters. In Sampling of Environmental
Materials for Trace Analaysis (edited by Markert B.),
pp. 125-161. VCH-Publisher, Weinbeim, New York, Tokyo.
Watson J. G., Lioy P. J. and Mueller P. K. (1995) The
measurement process: precision, accuracy, and validity. In
Air Sampling Instruments for Evaluation of Atmospheric
Contaminants (edited by Cohen B. and Hering S. V.), 8th
Edn. American Conference of Governmental Industrial
Hygienists, Cincinnati, Ohio.
Watson J. G., Chow J. C., Lurmann F. and Musarra, S.
(1994) Ammonium nitrate, nitric acid, and ammonia equilibrium in wintertime phoenix, Arizona. J. Air Waste
Man. Ass. 44, 405-412.
Watson J. G., Chow J. C., Lu Z., Bowen J. A., Egami R. T.,
Solomon P. A. and Richards L. W. (1996) Components of
light extinction in the San Joaquin Valley and in the
Mohave Desert. Atmospheric Environment (to be submitted).
Wexler A., Lurmann F. and Seinfeld J. (1992) An episodic
aerosol/visibility dispersion model. In Transactions, PM1 o
Standards and Nontraditional Particulate Source Controls
(edited by Chow J. C. and One D. M.), pp. 209-228. Air
and Waste Management Association, Pittsburgh.
White W. H. and Macias E. S. (1991) Chemical mass balancing with ill defined sources: regional apportionment in
the California desert. Atmospheric Envirnoment 25A,
1547-1557.
Zhang X. Q., Turpin B. J., McMurray P. H., Hering S. V. and
Stolzenburg M. R. (1994) Mie theory evaluation of species
contributions to wintertime visibility reduction in the
Grand Canyon. J. Air Waste Man. Ass. 44, 153-162.