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Airborne Particulate Emissions from a Chromic Acid
Anodizing Process Tank
Robert C. Pegnam
a
& Michael J. Pilat
a
a
Department of Civil Engineering University of Washington , Seattle , Washington , USA
Published online: 07 Mar 2012.
To cite this article: Robert C. Pegnam & Michael J. Pilat (1992) Airborne Particulate Emissions from a Chromic
Acid Anodizing Process Tank, Journal of the Air & Waste Management Association, 42:3, 303-308, DOI:
10.1080/10473289.1992.10466994
To link to this article: http://dx.doi.org/10.1080/10473289.1992.10466994
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ISSN 1047-3289 J. Air Waste Manage. Assoc. 42: 303-308
Airborne Particulate Emissions from a Chromic Acid
Anodizing Process Tank
Robert C. Pegnam and Michael J. Pilat
Department of Civil Engineering
University of Washington
Seattle, Washington
Particulate mass concentration, particle size distribution, and
particle chemical composition measurements have been con-
ducted on the gases exhausting from a chromic acid anodizing
process tank. Particle mass concentrations in the 200 to 20,000
ftg/m
3
range were measured using open-faced filters (47 mm
diameter) adjacent to the process tank liquid and with closed
filters (90 mm diameter) in the exhaust duct. Particle size
distributions, measured using University of Washington Mark 3
and Mark 20 Cascade Impactors, showed the particle aerody-
namic mass median diameter was about 3 microns. Chemical
analysis of the particle samples obtained by the Modified EPA
Method 5 sampling train, the Mark 20 UW Cascade Impactors,
and by the 47 mm and 90 mm diameter filters showed Cr
+6
concentrations in the 20 to 1,500 |xg/m
3
range with over 99
percent of the chromium in particles larger than 1.0 microns
diameter. An integrating nephelometer was used to measure the
light scattering coefficient of the exhaust gases upstream of the
wet scrubber. The light scattering coefficient increased by a
factor of about 2-3 over the background level during the 40
minute time period while a part was being anodized. The b
scat
values ranged from 3 x 1O~
5
to 3 x 10~
4
meters"
1
for the
aerosol particles less than about 6 microns aerodynamic diame-
ter.
The objectives of this research were to characterize (mass
concentration, size distribution, and chemical composition)
the airborne particulate emissions from the chromic acid
anodizing of aluminum and relate the emissions to process
variables (electrical current usage in units of amp-hours,
Implications
Airborne emissions of hexavalent chromium are facing
increasingly strict air pollution emission standards. Mea-
surements of the particulate mass concentration, parti-
cle size distribution, and particle chemical composition
provide information of significance to the design of
particulate control equipment used to reduce the Cr
+6
emissions. For the particulate emissions from chromic
acid anodizing of aluminum, over 99 percent of the
chromium was in particles larger than 1 micron diame-
ter and accordingly very high control efficiency for the
smaller submicron aerosol particles may not be neces-
sary.
square feet of aluminum part surface area, and time during
processing of the aluminum parts). This research has
significance to the control of emissions of aerosol particles
and hexavalent chromium from chromic acid anodizing
process tanks. Hexavalent chromium is regulated by the
Puget Sound Air Pollution Control Agency
1
with an emis-
sion standard of 99.0 percent control efficiency and 0.03 mg
Cr
+6
/amp-hour (if facility-wide Cr
+6
emissions are greater
than 1 kilogram/year after obtaining 95 percent control)
and 99.8 percent control efficiency and 0.006 mg Cr
+6
/amp-
hour (if facility-wide Cr
+6
emissions are greater than 1
kilogram/year after obtaining 99.0 percent control).
Literature Review
Chromic acid anodizing of aluminum was developed by
Bengough and Stuart in England in 1923, as reported by
Wernick and Pinner (1964).
2
The electrolytic process pro-
duces an almost insoluble and strongly adherent protective
film on the aluminum part. Anodizing can also be used for
decorative purposes as well as the formation of a porous and
adsorptive base for further coatings applications, such as
painting. The consideration of hexavalent chromium as
both a toxic and carcinogenic air pollutant has caused metal
finishers to conform to more strict air pollutant emissions
standards.
The methodology of measuring the air emissions of Cr
+6
testing has been reported by Bivens and DeWees (1987).
3
Similar emission test methods were prepared by Pacific
Environmental Services, Inc. for the Metal Finishing Asso-
ciation of Southern California.
4
In both cases a form of the
EPA Method 5 Sampling Train was used for field source
sampling followed by laboratory chemical analyses of the
samples for Cr
+6
. Chemical analysis methods for hexava-
lent chromium concentrations include the diphenylcarba-
zide colorimetric and ion chromatography procedures. Ana-
lytical methods for hexavalent and total chromium
concentrations in the airborne particle samples were re-
ported by Bhargava et al. (1983),
5
Abell and Carlberg
(1974),
6
and Thomsen and Stern (1976).
7
All concur that
the colorimetric method using diphenylcarbazide is an
accurate means of measuring hexavalent chromium concen-
trations in aqueous solutions down to about 0.5 u,g of Cr
+6
.
Total chromium concentrations are measured by atomic
absorption (AA), ion chromatography (IC), and inductively
coupled plasma (ICP).
Koropchak and Roychowdhury (1990)
8
reported Cr
+3
/
Cr
+6
ratios in the 2 to 6 range as a function of particle
diameter in the 2.5 to 25 micron diameter range for
airborne particles in the room air of a small chrome
electroplating shop. No reports have been found of the size
Copyright 1992Air & Waste Management Association
March 1992 Volume 42, No. 3 303
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1
Chromic
Anodizing
Tank
1
; < - Port A
>
!
Wet
Scrubber
P o r t B
Figure 1. Schematic of air flow from chromic acid anodizing
tank.
distribution or chemical composition as a function of
particle size for airborne emissions from chromic acid
anodizing process tanks.
14
"
16
Chromic Acid Anodizing Process Tank
The chromic acid anodizing tank studied is located at the
Auburn Facility of the Boeing Commercial Airplane Com-
pany. The tank is one of several other (cleaning, alodining,
rinse, etc.) tanks used in the final processing of aluminum
parts prior to painting. The tank dimensions are 115 feet
long, 5 feet wide, and 15 feet deep. The chromic acid liquid
level is usually maintained at about one foot below the
upper edge of the tank, which corresponds to a volume of
chromic acid of about 8,050 cubic feet (60,200 gallons). The
air from the anodizing tank is exhausted through horizon-
tal vents (mounted flush with the vertical sides of the tank
along both sides but not on the tank ends) located about 6-9
inches above the liquid surface and via ducting to a wet
scrubber, as shown in Figure 1, Connected to the upper
edge of the process tank are 38 air exhaust ducts (19
exhaust ducts on the south side connect to one south side
duct and 19 ducts on the north side connect to one north
side duct). The north side and the south side ducts join
together about 30 ft. upstream of the scrubber. The total air
flow into the exhaust ducts is about 45,000 acfm (68-80F
and static pressure of -1.2 "H
2
O) or about 1200 acfm per
duct. The exhaust air flows at a velocity of about 49 ft/sec.
through the 4 ft. by 4 ft. main duct and into the wet
scrubber.
Formation of Aerosol Particles During Anodizing Process
Aerosol particles are formed during the anodizing process
from the bursting of gas bubbles generated by the anodizing
Mounting Rack
Part
Hanger
^ Gas
C h r o m i c A c i d S o l u t i o n
Aluminum
Part
(Anode)
T _
Tank
Wall
(Cathode)
To
Scrubber
To
Scrubber
Figure 2. Formation of hydrogen and oxygen gas bubbles
during anodizing.
bubble f i l m drops jet drops
Figure 3. Aerosol formation from bursting of gas bubbles.
process and by the air sparging operation to mix the liquid.
The aluminum parts to be anodized are suspended from a
frame rack platform. This platform and rack are lowered
into the tank of chromic acid. The platform rests on the
process tank mounts which are located just above the air
exhaust ducts. Once in position, the platform is locked and
the electrical connections are set in place (by a hydraulic
mechanism). At the start of the anodizing process, the
voltage and current are increased slowly for the first five
minutes. For the remaining 35 minutes, the voltage is
constant at about 22.5 volts DC. The electrical current
(amperage) may peak as high as 7000 amps in the first 5
minutes but reduces to a lower magnitude for the remain-
ing 35 minutes. The current magnitude is dependent upon
the total surface area of the parts in the tank. The current
density is maintained between 5 and 10 amps per square
foot of part surface area. Air sparging is used for channelled
parts. The air sparging is operated prior to anodizing to mix
the acid solution and to ensure that air pockets are removed
from the channelled parts. Air sparging was sometimes
operated for the duration of the anodizing process (about 40
minutes) whereas other times it occurred for the first 5
minutes.
Anodizing is an electrochemical process. When electrical
direct current is applied through an aqueous chromic acid
solution, gases are formed at each of the electrodes. Oxygen
gas is formed on the positively charged (anode) aluminum
parts and hydrogen gas on the negatively charged (cathode)
tank walls, as is shown schematically in Figure 2. After the
oxygen and hydrogen gas bubbles rise to the liquid surface,
they burst and emit liquid aerosol droplets (particles) which
are swept away in the air flowing to the exhaust ducts.
Resch (1986)
9
reported that the bursting of a gas bubble at
the surface of a liquid generates two distinct types of
aerosol droplets, liquid film aerosol droplets and liquid jet
aerosol droplets, as shown in Figure 3. The liquid film
aerosol droplets are of small diameter (perhaps in the 0.1 to
10 microns diameter) whereas the liquid jet aerosol droplets
are somewhat larger (about 0.1 of the diameter of the gas
bubble).
Experimental Measurements
The aerosol particle emissions were characterized using
four measurement methods including filters (47 mm and 90
mm diameter), Greenburg-Smith impingers, cascade impac-
tors (Mark 3 and Mark 20 University of Washington
Cascade Impactors), and an integrating nephelometer. The
sampling was performed over the liquid surface of the
chromic acid anodizing tanks, at the inlet to the exhaust
ducts adjacent to the process tank (port A), and in the main
duct upstream of the wet scrubber (port B in Figure 1).
Modified EPA Method 5
An EPA Method 5 sampling train was modified for use as
a sampling system for airborne particulate chromium,
similar to that required by the Puget Sound Air Pollution
Control Agency.
10
The entire sampling section (sampling
nozzle, sample probe, connecting tubes, and impingers) of
the train was glass. The glass sampling nozzle was posi-
304 J . Air Waste Manage. Assoc.
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tioned about midway inside the 4 ft x 4 ft duct transporting
the 45,000 acfm air flow from the processing tank to the wet
scrubber (port B in Figure 1). The unheated glass sampling
probe was connected to the Greenburg-Smith impingers
with ground-glass fittings. The ice-cooled impinger box
contained four modified and one standard Greenburg-
Smith impinger. The first three impingers contained 150
mL of 0.1N NaOH, the fourth was dry with a glass wool
plug, and the last contained 200 g silica gel and a glass wool
plug. The standard Greenburg-Smith impinger was the
second of the four impingers in the train. The sampled
aerosol particles were collected on the glass nozzle, the glass
sampling probe, and the impingers. Trace amounts of Cr
+6
were found in the fourth impinger (dry) but these concentra-
tions were usually lower than the instrument detection
limit of 0.5 |xg Cr
+6
. Impinger samples, probe wash, and
connector washes were analyzed colorimetrically for Cr
+6
and by atomic adsorption for total Cr. The water vapor
concentration was obtained from the amount of water
collected in the impinger silica gel and the ice cooled
impingers (typically the water vapor concentration ranged
from 0.5 to 1.5 percent water vapor).
Mark 3 UW Cascade impactor
The Mark 3 University of Washington Cascade Impactors
were operated at an air sampling rate of about 1.0 to 1.5
acfm for about 3 to 5 hours in order to obtain a sufficiently
large volume of air (about 200 to 400 cubic ft. of air) to be
able to weigh the particle samples. The Mark 3 University
of Washington Cascade Impactors measure particles in the
range of 0.3 to 20 microns aerodynamic diameter as re-
ported by Pilat et al. (1978).
n
Samples were obtained
during air sparging with no aluminum parts being pro-
cessed (anodized). The two cascade impactors (operated
simultaneously) were located with the sampling nozzles
about 6 to 9 inches above the acid liquid level. This distance
was approximately the same as the distance from the acid
liquid level to the middle of the exhaust duct openings
(openings are about 2 to 4 inches high and about 10 inches
horizontal). The air sparge (air injection from the bottom of
the tank) was then activated and operated for the duration
of the tests (about 150 to 300 minutes). Six cascade
impactor emission source tests were conducted for time
periods of up to 330 minutes. During the sampling, it was
observed that the droplets impacted on both the inside and
outside of the sampling nozzle. These tests provided data on
the size distribution of aerosol particles formed by the air
sparging part of the process. Stainless steel foil substrates
were used to collect the particles sampled on the cascade
impactor collection plates. The stainless steel substrates
were prepared using ultrasonic cleaning in acetone and
followed by rinsing with deionized water. At the conclusion
of the tests and final weighings, the substrates and inside of
the nozzles were washed and stored in sample bottles with
0.IN NaOH.
Filters
Open faced filter tests were conducted in order to obtain
particle concentrations at the inlet to the air exhaust ducts
from the chromic acid anodizing tank. The 47 mm diameter
filter holders were mounted in two of the exhaust air ducts
(port A in Figure 1) such that the entrance to the filter
holder was flush with the face of the exhaust duct. The filter
holders were connected to a 0.5 inch diameter steel sam-
pling probe. Tygon tubing was used to connect the sampling
probe to a modified Greenburg-Smith impinger containing
silica gel. The impingers, filled with a known amount of
silica gel, were used for the measurement of the water vapor
concentration. Sampling times were 40 to 50 minutes
which simulated the anodizing process time of 40 minutes.
Final weighings of the filters and silica gel in the Boeing
Quality Control Lab immediately followed the tests. The
glass fiber filters were stored in a solution of 0.1N NaOH
and analyzed colorimetrically and by atomic adsorption at
the University of Washington Department of Civil Engineer-
ing labs.
Two types of 90 mm filter tests were conducted upstream
of the scrubber (port B in Figure 1). The first type required
sampling for a period of 40 to 60 minutes for the collection
of particulate from a single anodizing process run. The
second type involved sampling for approximately 24 hours
for the collection of the aerosol particles emitted over an
entire working day. During this time multiple anodizing
runs (typically 12 runs in a 24 hour time period) were
processed through the tank. The 90 mm diameter filter
holders used a 0.5 inch diameter sampling nozzle. The filter
outlet was connected via a 0.5 inch diameter sampling
probe and Tygon tubing (3/8" ID thick walled tubing) to the
vacuum pump and then to the dry gas meter. Preparation of
the Teflon 90 mm diameter filters consisted of desiccation
for at least 24 hours. Blanks were weighed with each test.
Mark 20 UW Cascade Impactor
Seven tests were conducted upstream of the scrubber
(port B in Figure 1) during July, August and November
1990 using a University of Washington Mark 20 Cascade
Impactor. The Mark 20 cascade impactor sampled at the 1.8
to 2.4 cfm (stack conditions) air flow range for about 24
hours, using a 2-stage Leybold-Heraeus vacuum pump. The
Mark 20 Impactor consists of 14 jet stages plus a backup 90
mm filter. The inlet to the Mark 20 cascade impactor
includes a sampling nozzle (that is the first jet stage) which
leads directly to the first particle collection plate. Stages 2
through 14 consist of multiple round jets. The Mark 20
impactor operates at low pressure at the jet stages 10
through 14 and hence the air pressure downstream of jet
stage 14 was monitored during the sampling with a Wallace
and Tiernam pressure gauge (the absolute pressure ranged
from 8-9"Hg). The mylar substrates were washed in dis-
tilled water, dried, and then stored in a desiccator. The
backup Teflon filters were desiccated for 24 hours prior to
weighing. Prior to sampling, each substrate, filter, and
blank were weighed and the impactor assembled in the
Boeing Quality Control lab. One substrate and one filter
blank were used for each test. Each blank was stored in a
desiccator. After sampling, all substrates and filters were
weighed and the samples were stored for later inductively
coupled plasma (ICP) analysis at the University of Washing-
ton Department of Chemistry.
Integrating Nephelometer
The integrating nephelometer was developed at the Uni-
versity of Washington Department of Civil Engineering in
about 1966 and was first used in optical studies of humidity
effects on hygroscopic aerosols, as reported by Pilat and
Charlson (1966).
12
The UW integrating nephelometer mea-
sures the light scattered by air molecules and aerosol
particles, integrated over the 5 to about 175 degree angle
(hence the name "integrating" nephelometer) as reported
by Ahlquist and Charlson (1967).
13
The instrument mea-
sures the light scattering coefficient or "b
sca
t," most com-
monly reported in units of 1/meters. The relationship of
bscat to the light transmittance is given by the equation:
In = -(b
scat
, meters~
1
)(L, meters)
Where L is the distance through the volume of air for which
the light transmittance is being described or measured. For
this research project the UW Integrating Nephelometer
March 1992 Volume 42, No. 3 305
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10
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is 10
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10*
1 I I I ! 1 1 m i
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7
Trmr
-I
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1
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/'
r"
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i n
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Y-
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Y
i n I I mil
o47mm Filters (Tank Exhaust]
-o-90mm Filters (Scrubber inlet)
Mark 3 (Over Tank)
Mark 20 (Scrubber Inlet)
mi I I I
:
Sampl
Time
0.67 hr
0.67 hr
3-5 hr
24 hr
1 1 1
!
s
s
S
s
1O
1
0.01 0.1 1 5 10 20 3040506070 80 90 95 99 99.9 99.99
Percent of Samples Less Than Stated Particle
Mass Concentration
Figure 4. Distribution of particle mass concentrations.
was modified in order to protect the instrument from the
corrosive acids in the aerosol emissions from the process
tanks. The air was sampled at a flow rate of about 1 to 2 cfm
from the duct (port B in Figure 1) and was treated to
remove the larger (above about 5 microns aerodynamic
diameter) particles which were more likely to impact on the
walls in the nephelometer. The air treatment apparatus
consisted of a UW Mark 3 Cascade Impactor inlet section
together with a BCURA cyclone and a 0.375 inch diameter
sampling nozzle. The UW Mark 3 impactor included the
second and third jet stages of the normally seven stage
Mark 3, whereas the jet stages 4 through 7 were omitted.
This configuration provided for the removal of the larger
particles and prevented the larger particles from contami-
nating the inside surfaces of the nephelometer. Substrates
were used on the particle collection plates downstream of
the second and third jet stages. No filter was used at the
outlet of the impactor to allow the fine aerosol particles to
flow on and into the integrating nephelometer. An addi-
tional air purge pump and new filters were installed within
the nephelometer. Each air purge pump provided an air
flow of about 200 cc/min. to the phototube section and to
the light trap section of the instrument. The purge air flow
prevented the aerosol particles from entering these sections
and contaminating the sensitive components. The average
air sampling flow rate through the nephelometer utilizing
the external vacuum pump was about 2 cfm. The air
sampling flow rate was adjusted with a valve located
upstream of the external vacuum pump. The zero and span
checks of the nephelometer were conducted about every
three days. A zero check was performed by allowing the
instrument to be filled with the purge air (requiring about 5
minutes). A span check was performed by injecting the
instrument with a standard gas with a known b
s cat
(Freon
12 which has a b
s cat
of about 3.6 x 10~
4
meters"
1
at
atmospheric pressure and 70F). Both the zero and span
magnitudes were recorded as shown on the recorder output
sheet along with the 24 hour b
s cat
data.
Particle Sample Analysis
The particle samples were weighed using a Mettler
electrobalance (Model AE 240) located at the on-site Boeing
Quality Control Lab. For the cascade impactor substrates,
the outlet filter was weighed first, followed by the last
collection plate substrate (number 7 collection plate on the
UW Mark 3) on up, assembling the impactor with each
stage. The 47 and 90 mm filters were also assembled after
weighing. After sampling, the reverse of the loading weigh-
ings were conducted. Visual inspection of the samples was
useful in providing a qualitative indication of the particle
samples. The yellowish color of the chromic acid was clearly
visible on the Mark 20 impactor substrates from the inlet
jet stage (cut diameter of about 25 microns) to about the
eleventh stage (cut diameter of about 0.8 microns), which
qualitatively indicated that there was probably little chro-
mic acid below 1 micron diameter. A colorimetric method
(spectrometer at a wavelength of 420 nanometers) was used
for hexavalent chromium concentrations of the Modified
Method 5 samples and the 47 mm samples. A color indicator
(1,5-diphenylcarbazide) was added to a diluted portion of
each sample. The magnitude of the light transmittance
through a 1.0 cm sample curvette cell was then compared to
a curve generated from known concentration standards to
obtain the Cr
+6
concentration.
Results and Discussion
Particle Concentrations
The distribution of the particle mass concentrations for
the four measurement methods used are presented in
Figure 4. The particle mass concentration immediately
adjacent to the process tank at the inlet to the exhaust
ducts, as measured by the 47 mm diameter open faced
filters, ranged from 86 to 4200 |xg/m
3
. During December
1989 to March 1990, 12 (five sets of paired simultaneous
samples and two single samples) open-faced filter samples
were obtained. The particle concentration differences were
possibly caused by the differences in the distance between
the part being anodized and the sampling filter (i.e., the
nearer the part, the higher the particle concentration). One
sampling port allowed for an open-faced filter holder to be
located near the aluminum part being anodized; however,
the 2nd sampling port positioned the 2nd filter holder some
distance from any aluminum part. From this data, it
appears that the aerosol particles are formed near the part
being anodized. The UW Mark 3 Cascade Impactor tests
were conducted during air sparging of the process tank but
no parts were being anodized. The cascade impactors were
located over the process tank liquid (nozzle about 6-9
inches over the liquid) and at the inlet to the air exhaust
ducts, thus sampling the aerosol particles near their place
of generation. The total particulate concentrations from
these tests ranged from 75 to 290 jxg/m
3
as is shown in
Figure 4. Note that the particle mass concentrations sam-
pled during air sparging were considerably lower than those
obtained during anodizing. Measurements of the particle
mass concentration in the main duct upstream of the wet
scrubber were conducted with 90 mm diameter filters and
with the Mark 20 cascade impactor. Figure 4 shows that the
particle mass concentrations measured by these two meth-
ods are in approximate agreement (the lower magnitude of
the Mark 20 concentrations being due to the longer sam-
pling times). The particle mass concentrations measured
isokinetically by the 90 mm diameter filters ranged from
about 200 to 20,000 }ig/m
3
with sampling times ranging
from 40 to 60 minutes. The Mark 20 Cascade Impactor
tests conducted over a 24 hour sampling time provided
particle mass concentrations in the 2,360 to 7,613 jig/m
3
meter range (4,986 |xg/m
3
average concentration).
Particle Size Distributions
The size distribution results are presented in Figures 5
and 6. The results of the Mark 3 Cascade Impactor measure-
306 J. Air Waste Manage. Assoc.
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100
Mark 0
0

n
i
l
Nov ember- December 1989
]
r
i
/
i

4
J
i
i
i
/
m
] /
I
p
n
Particle Cone.
(nn/m
3
\
- o-
0
- o-
V-
-
M3A 131
M3B 192
M3C 115
M3D 86
M3E 75
M3F 83
-
0.01 0.1 1 5 10 20 3040506070 80 90 95 99
Percent Mass Less Than Stated Diameter
99.9 99.99
Figure 5. Size distribution of aerosol particles near process tank during air
sparging.
10
4
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1
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10
4- i -
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11'
!.| j L.......UJ.1JJ ! ! JJ jJ J 1 1 ! 1 ! !!!|
47mm Filter Tests
N ovember 198 9 - February 1990
i f.. i L.L.U.iijJ 1 i U.J..J.M] '' 1 : " Hi !
I
jttti:::::::
44.

o Cr
+6
Concentration
Process Concentration
:
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t 10
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.
o
:i ::i 10
2
J= 10
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2
10
3
10*
Total Particulate Concentration
(M9/m
3
)
Figure 7. Comparison of Cr+
6
and process emission rate with particle mass
concentrations.
ments conducted during air sparging over the process tank
and at the inlet to the exhaust ducts at the process tank
show in Figure 5 that the particle mass median diameter
ranged from 0.5 to 2.5 microns aerodynamic diameter and
the mass concentration from 75 to 192 |ig/m
3
. The particle
size distributions measured with the Mark 20 in the main
duct upstream of the wet scrubber show in Figure 6 that
the particle mass median diameters ranged from 2 to 4
microns and the mass concentrations from 2,360 to 7,613
|xg/m
3
.
Chromium Concentrations in the Aerosol Particles
The distribution of total chromium as a function of
particle diameter is also shown in Figure 6 for the averaged
data from five Mark 20 tests. The particle median diameter
of the Cr distribution was 4.0 microns and over 99 percent
of the chromium was in particles of diameter greater than
a 1
0.01
1
Mark 20
July - August 199C
i
P
M
A
d
r #
l/l\i
m
1
f
{
r
i
s
i -i
J"Tk'jO A
- Concentration (/g/m
3
)
Particles
-c
-
- - a
- A
~ -
, t
< A 7,613
- B 6,411
K C 4,68 0
- D 5,48 2
- E 2,362
- F 2,360
- G 3,596
UU. mi
Chromi

42.C
59.-
44..
5O.f
32.1
DO
re
22
:
8
...I I-.I I L
0.01 0.1 1 5 10 20 3040506070 80 90 95 99 99.9 99.99
Percent Mass or Cr Less Than Stated Diameter
Figure 6. Distribution of mass and chromium in aerosol particles
upstream of scrubber.
1.0 microns. Note that the smaller aerosol particles less
than about 1 micron did not contain much chromium (0.5
percent of Cr in particles less than 0.8 microns diameter
compared to about 10 percent of the particle mass in
particles less than 0.8 microns diameter). Concentrations of
hexavalent chromium measured with 47 mm diameter
open-faced filters in the vent ducts adjacent to the chromic
acid anodizing process tank ranged from about 1 to 1300
|i,g/m
3
of air sampled as is shown in Figure 7. The Cr
+6
concentration was related to the particle mass concentra-
tion (shown on the abscissa in Figure 7) and the concentra-
tion ratio of Cr
+6
/mass ranged from 0.15 to 0.24. Figure 7
also shows the process concentration (mg Cr
+6
/amp-hour)
as a function of total particulate concentration (|xg/m
3
).
Process concentrations ranged from 0.018 to 65 mg Cr
+6
/
amp-hour and the total particle mass concentration was in
the 190 to 4,000 |xg/m
3
range. The distribution of Cr
+6
process concentrations (mg Cr
+6
/amp-hour) measured from
the Modified Method 5 train are shown in Figure 8. The
concentrations ranged from 2.5 to 58 mg Cr
+
/amp-hour
with a median value of about 18 mg Cr
+6
/amp-hour.
10
1
lodii ied Nlethn d 5
/>
f
/
/
4
Y
J uly - September 1989
[
0.01 0.1 1 5 10 20 3040506070 80 90 95 99 99.9 99.99
Percent of Samples Less Than Stated
Process Concentration
Figure 8 . Distribution of Cr
+6
process concentrations.
March 1992 Volume 42, No. 3 307
D
o
w
n
l
o
a
d
e
d

b
y

[
1
1
1
.
2
2
3
.
2
5
2
.
1
5
]

a
t

0
3
:
3
0

0
5

M
a
r
c
h

2
0
1
4

0.0003
0.0002
Figure 9. Light scattering coefficient of aerosols in main duct.
N ephelometer Test Results
The integrating nephelometer was installed to sample air
from the main duct upstream of the wet scrubber on July
26,1990. The instrument was able to show the variation in
the aerosol particle concentration on a continuous time
basis and reported b
s cat
values in the 3 x 10~
5
to 3 x 10~
4
meters"
1
range. Figure 9 presents an illustration of the
chart recorder trace of b
s cat
versus time from midnight
September 8 to midnight September 9, 1990 (Saturday
midnight to Sunday midnight) and shows that 13 loads of
parts were anodized during this time period. The light
scattering coefficient while no part was being anodized was
about 1 x 10~
4
meters"
1
and increased rapidly to about 2 x
10~
4
meters"
1
when the anodizing process was initiated.
The b
s cat
peak width is about 40 minutes, which corre-
sponds exactly with the part anodizing time. This data
shows that a continuous monitor such as the integrating
nephelometer can be used to indicate the aerosol emission
concentration for the chromic acid anodizing process ex-
haust gases.
Conclusions
The conclusions of this research project to characterize
the particle emissions from a chromic acid anodizing tank
are as follows:
1. The aerosol mass concentration ranged from about 40
to 20,000 u.g/m
3
with the higher concentrations occur-
ring during the anodizing process.
2. The aerosol particle size distributions were in the 0.05
to 24 micron aerodynamic diameter range. The mass
median diameters were in the 2 to 4 micron range in the
duct and in the 0.6 to 4 micron range near the process
tank.
3. The mass median diameter of the total chromium
concentration of the particles was 4 microns and over
99 percent of the chromium was in particles of greater
than 1.0 microns diameter.
4. The hexavalent chrome concentrations were in the 20
to 1,500 |Ag/m
3
range and approximately correlated
with the total particle mass concentration.
5. The integrating nephelometer was able to detect the
aerosol mass concentration increase when the anodiz-
ing process was initiated and demonstrated its capabil-
ity for operating as a continuous aerosol emission
monitor.
6. Measured process concentrations ranged from 2.5 to 58
mg Cr
+6
/amp-hour with the Modified Method 5 train
and 0.7 to 65 mg Cr
+6
/amp-hour with 47 mm filter
tests.
Acknowledgments
The authors would like to acknowledge the Boeing Com-
pany for making this research possible. We greatly appreci-
ate the assistance of Hal Alsid, Mary Jane McGarity, David
Mummey, Herb Gasgill, Rich Clasen, Andy Gay, Randy
Love, and Kirk Thompson of the Boeing Company. Special
thanks to the plumbers stationed in the 17-06 building (Jeff
Bement, Curt Kinlock, and Kelly Meeds) and also to the
process line operator, Jimmy Cook. The assistance of Jacek
Anuszewski, Gail Dorf, William Dunn, Stacia Dugan, and
Ron Sletten of the University of Washington Department of
Civil Engineering with the source testing and chromium
analysis was very helpful.
References
1. "Chromic Acid Plating and Anodizing," Reg. Ill of the Puget
Sound Air Pollution Control Agency, Section 3.01.
2. Wernick, S.; Pinner, R. Th e Surface Treatm ent and Finish ing
of Alum inum and Its Alloys, 3rd Ed, Robert Draper, Ltd.,
Teddington, England, pp. 349,1964.
3. Bivens, D.; DeWees, W. "Method Development and Testing for
Measurement of Source Levels of Hexavalent and Total
Chromium," Paper presented at 80th Annual Air Pollution
Control Association Meeting, New York City, NY (June 1987).
4. Pacific Environmental Services, Inc. "Efficiency of Harshaw
Chemical's MSP-ST for Controlling Chrome Emissions From
a Chromic Acid Anodizing Tank," Conducted for Metal Finish-
ing Assoc. of Southern California, March 1989.
5. Bhargava, O.; Bumsted, H.; Grunder, F.; Huni, B.; Manning,
G.; Riemann, R:j Samuels, J.; Tatone, V.; Waldschmidt, V.;
Jeff, S.; Hernandez, P. "Study of an analytical method for
hexavalent chromium," Am . Ind . Hyg. Assoc. J. 4:433 (1983).
6. Abell, M.; Carlberg, J. "A simple reliable method for the
determination of airborne hexavalent chromium," Am . Ind .
Hyg. Assoc. J. 35: 229 (1974).
7. Thomsen, E.; Stern, R. "A simple analytical technique for the
determination of hexavalent chromium in welding fumes and
other complex matrices," Scand . J. Work Environ. & Health
5: 386 (1979).
8. Koropchak, J.; Roychowdhury, S. "Evidence for aerosol ionic
redistribution within aerosols produced by chrome
electroplating," Environ. Sci. & Tech nol. 24; 1861 (1990).
9. Resch, F. J. "Liquid Aerosol Formation By Air Bubble
Bursting," in Aerosols: Form ation and Reactivity, Proceed-
ings of the 2nd International Aerosol Conference, Berlin,
Pergamon Press, pp. 79-82,1986.
10. "Determination of Hexavalent Chromium Emissions from
Decorative and Hard Chrome Electroplating and Chromic Acid
Anodizing," Puget Sound Air Pollution Control Agency Source
Test Method, August 9,1990.
11. Pilat, M.; Raemhild, G.; Powell, E.; Fioretti, G.; Meyer, D.
"Development of a Cascade Impactor for Sampling 0.02 to 20
Micron Diameter Particles," EPRI Report No. FP-844, Vol. 1.
(1978).
12. Pilat, M.; Charlson, R. "Theoretical and optical studies of
humidity effects on the size distribution of a hygroscopic
aerosol," J. Rech erch es Atm osph eriques 2:165 (1966).
13. Ahlquist, N.; Charlson, R. "A new instrument for evaluating
the visual quality of air," JAPC A 17: 467 (1967).
14. U.S. EPA "Locating and Estimating Air Emissions From
Sources of Chromium," EPA-450/4-84-007g, Research Trian-
gle Park, NC, 1984.
15. U.S. EPA "Locating and Estimating Air Emissions From
Sources of Chromium (Supplement)," Research Triangle Park,
NC, 1989.
16. California Air Resources Board "Chrome Plating Control
Demonstration Project Staff Report." Sacramento, CA, 1989.
Dr. Pilat is a professor in the Department of Civil
Engineering, University of Washington, Seattle, WA 98195.
R. Pegnam has a BSCE and is a graduate student working
towards the MSCE degree in the Department of Civil
Engineering, University of Washington. This paper was
submitted for peer review on January 18,1991. The revised
manuscript was received on November 12,1991.
308 J . Air Waste Manage. Assoc.
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.
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3
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3
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5

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r
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