-------
6.0 Materials
Methyl Chloride - Matheson, Chicago, IL.
Methyl Bromide - Matheson, Chicago, IL.
Durapak, n-octane/Poracil C (100/120 mesh) - Applied Science Lab., State
College, PA.
Six-port, 2 position Valve - Valco Inst., Houston, TX.
7.0 Procedure
7.1 Collection of Field Samples
Aluminum sampling containers with a capacity of 280 ml are used to
collect ambient air samples of methyl chloride and methyl bromide. The
containers are equipped with a vacuum-tight valve which allows the evacuation
of the container in the laboratory and filling at the sampling site. This
collection procedure is for obtaining "instant grab" samples.
During collection of the samples, observations are carefully recorded
with regard to the meteorological conditions surrounding the sampling area.
The aluminum cannister containing the collected sample are identified with a
code and recorded according to the approximate information such as date, time
of sample collection, location of sample collection which corresponds to the
meteorological conditions at that sampling location.
7.2 Transport and Storage
The aluminum sampling containers are impermeable to hydrocarbons and
freons and thus free of external contamination. Storage experiments on
samples of ambient air containing freons which are related to methyl chloride
and methyl bromide have shown the samples to be relatively stable upto four
weeks after collection (6). However, analysis will be performed as soon as
possible after collection.
7.3 Range of Methyl Chloride and Methyl Bromide Concentrations
Anticipated
The ambient air concentrations have been shown to be in some cases,
about 0.5 to 5 ppm at ground level (2). The methyl bromide concentration has
been observed to be considerably less. Thus, the analytical technique employed
for the analysis of methyl chloride and methyl bromide surrounding the bromine
industry should have sufficient sensitivity for the measurement of these
compounds above background levels.
17
-------
8.0 Calibration and Standards
Calibration standards for methyl chloride and methyl bromide are prepared
in hydrocarbon free air or Ar. The retention time is used for identifying
methyl chloride and methyl bromide and the peak areas are measured for quanti-
fication of these compounds. Standard calibration mixtures are based on a
commercial source of methyl chloride and methyl bromide. Dilutions from the
primary standard of methyl chloride and methyl bromide are made in the aluminum
sampling containers. This is accomplished by introducing a predetermined
amount of methyl chloride and methyl bromide from a permeation tube into
hydrocarbon free air and the synthetic air-vapor mixture is metered into the
sampling container. Based upon flow-rate of gas to the sampling container
(280 ml) and the permeation rate of methyl chloride and methyl bromide tubes,
the final dilution is calculated. A series of dilutions is prepared by
adjusting the flow rates across the permeation tubes.
Approximately 10-15 ml of the standard gas mixture is flushed through
the 5 ml stainless steel sampling loop of the six-port valve. A 5 ml sample
of the standard gas mixture is then injected into the gas chromatogram.
9.0 Calculation
The concentrations of methyl chloride and methyl bromide in ambient air
samples collected in the field and returned to the laboratory are calculated
according to the following procedure. The response of the electron capture
detector to known concentrations of methyl chloride and methyl bromide is
recorded on the strip chart recorder as they are eluted fron the chromatograp-
hic column. The time of elution is recorded for each compound. Peak area is
used for quantitating methyl chloride and methyl bromide and the concentration
is determined in the unknown sample by using the calibration response factor:
ppb, halogenated hydrocarbon = f x peak response x attenuation where f is the
calibration response factor for methyl chloride or methyl bromide in units of
2 2
ppb/mm peak area, peak response is the peak area in mm for methyl bromide
and attenuation is the electrometer attenuation setting.
The response factors for methyl chloride and methyl bromide at three
different concentrations are averaged. The concentration of the standard
(ppb) divided by
response factor.
2
(ppb) divided by the detector response (mm ) times the attenuation yields the
18
-------
10.0 References
1. Farwell, S. 0. and R. A. Rasmussen, J. Chromat. Sci., 14, 224 (1976).
2. Grimsrud, E. P. and R. A. Rasmussen, Atm. Environ., 9, 1014 (1975).
3. Robinson, E. and R. A. Rasmussen, "Halocarbon Measurements in the
Troposphere and Lower Stratosphere", Final Report for Manufacturing
Chemists Assoc., Washington, D. C., 1976.
4. Pellizzari, E. D. , Chromatog. Rev., 9_8, 323 (1974).
5. Pellizzari, E. D., J. Chromatogram., 92, 299 (1974).
6. Denyszyn, R. B., L. T. Hackworth, F. M. Groshe, and D. E. Wagoner, Inst.
Conf. Photochem. Oxid. Poll, and its Control, Raleigh, NC, 1976.
Analytical Protocol revised 1/24/77.
19
-------
E. SAMPLING AND ANALYSIS FOR METHYL CHLORIDE, METHYL BROMIDE, VINYL
CHLORIDE AND VINYL BROMIDE IN AMBIENT AIR
1.0 Principle of Method
Methyl chloride, methyl bromide, vinyl chloride and vinyl bromide are
concentrated from ambient air on SKC carbon in a short, glass tube (1).
Recovery of these volatile halogenated hydrocarbons is accomplished by thermal
desorption and purging with helium to transfer the trapped vapors from the
carbon cartridge to a Tenax GC cartridge through a calcium sulfate drying
tube to remove excessive amounts of water. Then the vapors are recovered
from Tenax by thermal desorption and purging with helium into a liquid nitrogen
cooled nickel capillary trap (2) and the vapors are introduced onto a high
resolution glass, gas chromatographic column where the constituents are
separated from each other (2). Identification and quantification of methyl
chloride, methyl bromide, vinyl chloride and vinyl bromide in the sample are
accomplished by mass spectrometry either by measuring the intensity of the
total ion current signal or mass fragmentography (3). The collection and
analysis systems are shown in Figure El.
2.0 Range and Sensitivity
The linear range of the mass spectrometric signals for the halogenated
compounds depend upon two principle features. The first is a function of the
breakthrough volume of each specific compound trapped on the SKC carbon
sampling cartridge and the second is related to the inherent sensitivity of
the mass spectrometry for methyl chloride, methyl bromide, vinyl chloride and
vinyl bromide (3,4). Thus, the range and sensitivity is direct function of
each compound. The linear range for quantification on the gas chromatograph/
mass spectrometry/computer (gc/ms/comp) is generally over three orders of
magnitude. Tables El and E2 lists the breakthrough volumes for methyl chloride,
methyl bromide, vinyl chloride and vinyl bromide on SKC charcoal (104).
Table E3 lists the approximate limits of detection for methyl chloride,
methyl bromide, vinyl chloride and vinyl bromide based upon these break-
through volumes. As it might be expected, the highest sensitivity is observed
for vinyl bromide, and the lowest for methyl chloride. Nevertheless, the
limits of detection are in the parts per trillion range.
20
-------
GAS
METER
FLOW
/METER
-0-
t
PUMP
carbon
......
4i_ .. .. ,
Tenax
CARTRIDGE
NEEDLE
VALVE
GLASS
FIBER
FILTER
VAPOR COLLECTION SYSTEM
GLASS
JET
SEPARATOR
T
CARRIER
GAS
TWO
POSITION
VALVE
CAPILLARY
GAS
CHROMATOGRAFH
PURGE
GAS
i
CAPILLARY
TRAP
Figure El.
ANALYTICAL SYSTEM
Vapor collection and analytical systems for analysis of
organic vapors in ambient air.
21
THERMAL
DESORPTICN
CHAMBER
HEATED
8i_OCK5
EXHAUST
-------
Table El. ESTIMATION OF BREAKTHROUGH VOLUMES FOR VINYL CHLORIDE AND
VINYL BROMIDE ON SKC CHARCOAL (104)
Temperature
°C (°F)
10 (50)
15.5 (60)
21.1 (70)
26.7 (80)
32.2 (90)
37.8 (100)
A/g
104
81
63
49
38
30
Vinyl Chloride
H2.52 ga
262
204
159
123
96
76
Vinyl
A/g
388
306
241
190
150
118
Bromide
A/2.52 ga
978
771
608
479
378
298
o
A 1.5 cm i.d. x 4.0 cm bed of charcoal weighs 2.52. g.
Table E2. ESTIMATION OF BREAKTHROUGH VOLUMES FOR METHYL CHLORIDE AND
METHYL BROMIDE ON SKC CHARCOAL (104)
Temperature
°C (°F)
10 (50)
15.5 (60)
21.1 (70)
26.7 (80)
32.2 (90)
37.8 (100)
Methyl
A/g
14.3
11.1
8.7
7.5
5.6
4.4
Chloride
Si/2.52 g
36
28
22
19
14
11
A/g
98
75
57
43
32
25
Methyl Bromide
A/2.52 g
248
188
143
108
82
62
22
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Table E3. APPROXIMATE LIMIT OF DETECTION FOR METHYL CHLORIDE,
METHYL BROMIDE, VINYL CHLORIDE AND VINYL BROMIDE3
Ambient Air Temperature °C (°K)
Methyl
Methyl
Vinyl
Vinyl
chloride
bromide
chloride
bromide
10
138
8
48
5
(50)
(69)
(2.1)
(20)
(1.2)
15.5
178
11
62
6.5
(60)
(89)
(2.8)
(26)
(1.5)
21.1
227
14
79
8.2
(70)
(114)
(3.6)
(33)
(1.9)
26.7
253
18
102
10.5
(132)
(132)
(4.8)
(42)
(2.5)
32.2
357
24
131
28
(90)
(178)
(6.3)
(55)
(6.7)
Values are in ng/m (ppt)
Estimation of L.O.D. based on 2.52 g carbon.
p
Estimation of L.O.D. based on 1.0 g carbon.
23
-------
3.0 Interferences
Because of the unique isotopic clusters for chlorine and bromine in
these compounds the background that is generally observed at their retention
times on a glass capillary column will not interfer with their qualitative
and quantitative analyses.
4.0 Reproducibility
The reproducibility of this method has been determined to be approxi-
mately +20% of the relative standard deviation for the four compounds when
replicate sampling are examined (3). The reproducibility is a function of
several factors. (1) The ability to acurately determine the breakthrough
volume for each compound; (2) The accurate measurement of the ambient air
volume sampled; (3) The percent recovery of the halogenated hydrocarbon from
the sampling carbon cartridge after a period of storage; (4) The reproducibi-
lity of thermally recovering each compound from the carbon cartridge and of
sample introduction into the analytical system; (5) The accuracy and determi-
nation of the relative molar response ratios between the methyl chloride,
methyl bromide, vinyl chloride and vinyl bromide and the external standards
used for calibrating the analytical system; (6) The relative efficiency and
reproducibility of transferring the trapped vapors from the carbon sampling
cartridge to the Tenax GC cartridge prior to analysis in order to remove the
excessive amounts of water using calcium chloride; (7) The reproducibility of
transmitting the sample through the high resolution gas chromatographic
column, and (8) The day-to-day reliability of the ms/comp system (2-4).
The accuracy of analysis is generally +15% of the amount determined from
repeated analysis of the authentic halogenated hydrocarbons. The accuracy of
the analysis is dependent upon the storage period.
5.0 Apparatus
5.1 Sampling Cartridges
The sampling tubes are prepared by packing a 10 cm long x 1.5 cm id
glass tube containing two or four cm of SKC carbon Lot No. 104 with glass
wools in the ends to provide support (3,4). The carbon cartridges are condi-
tioned at 400°C with a helium flow of approximately 30 ml/min for 30 min.
®
The conditioned cartridges are transferred to Kimax culture tubes immediately
24
-------
sealed using Teflon lined caps and cooled. This procedure is performed in
order to avoid recontamination of the sorbent bed (3,4).
Cartridge samplers with longer beds of sorbents may be prepared using a
proportional increased amount of carbon in order to achieve a larger break-
through volume for each compound and thus increasing the overall sensitivity
of the technique. However, it must be noted that the percent recovery of the
halogenated hydrocarbon significantly decreases when the amount of carbon is
increased and/or when an excessive length of storage period is employed (more
than a week).
5.2 Gas Chromatographic Column
A 0.35 mm i.d. x 100 m glass SCOT capillary column coated with OV-101
stationary phase and 0.1% benzyltriphenylphosphonium chloride is used for
effecting the resolution of the four halogenated hydrocarbons. The capillary
column is conditioned for 48 hrs at 230°C at 1.5 - 2.0 ml/min of helium flow.
A Finnigan type glass type jet separator on a Varian MAT CH-7 gc/ms/comp
system is employed to interface the glass capillary column to the mass spectro-
meter. The glass jet separator is maintained at 240°C.
5.3 Inlet-Manifold
An inlet-manifold for thermally recovering methyl chloride, methyl
bromide, vinyl chloride and vinyl bromide trapped on SKC carbon sampling
cartridges is employed and is shown in Figure El (1-3).
5.4 Gas Chromatograph
A Varian 1700 gas chromatograph is used to house the glass capillary
column and is interfaced to the inlet-manifold (Figure El).
5.5 Mass Spectrometry/Computer
A Varian MAT CH-7 mass spectrometer with a resolution of 2000 equipped
with single ion monitoring and mass fragmentography capabilities is used in
tandem with the gas chromatograph (Figure El). The mass spectrometer is
interfaced to Varian 620/1 computer (Figure El).
6.0 Reagents and Materials
SKC carbon Lot No. 104 is from SKC Carbon Company, Boston, MA. All
reagents used are analytical reagent grade and distilled in glass prior to
use.
25
-------
7.0 Procedure
7.1 Cleaning of Glassware
All glassware, sampling tubes, cartridge holders, etc. are washed in
§
Isoclean /water, rinsed with deionized distilled water, acetone and air
dried. Glassware is heated to 450-500°C for two hours to insure that all
organic material has been removed prior to its use.
7.2 Preparation of Carbon
Virgin carbon is packed into glass sampling tubes without further
purification. Used carbon cartridges are not recycled.
7.3 Collection of Methyl Chloride, Methyl Bromide, Vinyl Chloride and
Vinyl Bromide in Ambient Air
Continuous sampling of ambient air is accomplished using a Nutech Model
221-A portable sampler (Nutech Corp., Durham, NC, see Figure El). Flow rates
are maintained at 1 £/min using critical orifaces and the total flow is
monitored through a calibrated rotameter. The total flow is also registered
by a dry gas meter. Concomitant with these parameters the temperature is
continuously recorded with a Meteorology Research Incorporated weather station
since the breakthrough volume is important in order to obtain quantitative
data on these four halogenated hydrocarbons. This portable sampling unit
operates on a 12-volt storage battery and it is capable of continuous operation
up to a period of 24 hours. However, in most cases at the rates which will
be employed in the field. The sampling period will consist of one to two
hours. This portable sampling unit is utilized for obtaining "high volume"
samples. Duplicate cartridges are deployed on each sampling unit and are in
tandem with Tenax GC cartridges. The carbon cartridges serve as a backup to
the Tenax GC cartridge for collecting the more highly volatile constituents
such as these four halogenated hydrocarbons which have a low breakthrough
volume on Tenax GC. A total of four portable sampling units are available
for sampling ambient air surrounding the bromine industry.
In addition to the Nutech samplers, five DuPont personal samplers are
used to sample "low volumes" ambient air as well as long term integrated
samples (12-36 hrs). An identical SKC carbon sampling cartridge is employed
in this case and sampling is conducted in duplicate. The flow rate is
26
-------
balanced between duplicate cartridges using critical orifices to maintain a
rate of 25 or 100 ml/min per cartridge.
7.4 Analysis of Sample
The conditions for transferring methyl chloride, methyl bromide, vinyl
chloride and vinyl bromide from SKC carbon sampling cartridges to Tenax GC
sampling cartridges prior to instrumental analysis is shown in Table E4. A
1.5 x 2 cm bed of calcium sulfate is used to remove the water vapor prior to
retrapping the halogenated hydrocarbon vapors onto the Tenax GC sampling
cartridge.
The instrumental conditions for the analysis of the four halogenated
hydrocarbons on the sorbent carbon sampling cartridge is shown in Table E5.
7.4.1 Operation of the MS/Comp System (Figure El)
The operation of the ms/comp system is identical to as that described
for the Analytical Protocol under Section F entitled, "Sampling and Analysis
for Chlorinated and Brominated Hydrocarbons in Ambient Air".
7.4.2 Quantitative Analysis
The procedure for the estimation of the level of methyl chloride,
methyl bromide, vinyl chloride and vinyl bromide by capillary gas chroma-
tography in combination with mass spectrometry is identical to that described
for the analytical protocol F entitled, "Sampling and Analysis for Chlorinated
and Brominated Hydrocarbons in Ambient Air".
8.0 References
1. Pellizzari, E. D. Development of Method for Carcinogenic Vapor
Analysis in Ambient Atmospheres. EPA Contract No. 68-02-1228,
EPA-650/2-74-121, July 1974, 148 pp.
2. Pellizzari, E. D. Development of Analytical Techniques for
Measuring Ambient Atmospheric Carcinogenic Vapors. EPA Contract
No. 68-02-1228, EPA-600/2-75-076, November 1975, 187 pp.
3. Pellizzari, E. D. Development of Analytical Techniques for Measuring
Ambient Atmospheric Carcinogenic Vapors. EPA Contract No. 68-02-1228,
1976, in preparation.
4. Pellizzari, E. D. Identification of Atmospheric Pollutants by the
Combined Techniques of Gas Chromatography/Mass Spectrometry. EPA
Contract No. 68-02-2262, 1976, in preparation.
Analytical protocol revised 1/31/77.
27
-------
Table E4. PARAMETERS FOR REMOVING WATER AND TRANSFERRING VAPORS TO TENAX GC
Parameters Condition
Inlet-manifold
desorption chamber 295°C
valve 200°C
CaSO, drying tube (1.5 x 2.0 cm) ambient temperature
transfer line ambient temperature
Tenax GC cartridge (1.5 x 6.0 cm) ambient temperature
Desorption time 10 minutes
He purge rate 10 ml/min
28
-------
Table E5. OPERATING PARAMETERS FOR GLC-MS-COMP SYSTEM
Parameter
Setting
Inlet-manifold
desorption chamber
valve
capillary trap - minimum
maximum
thermal desorption time
GLC
MS
100 m glass SCOT-OV-101
carrier (He) flow
transfer line to ms
scan range
scan rate, automatic-cyclic
filament current
multiplier
ion source vacuum
270°C
220°C
-195°C
+180°C
4 min
20-240°C, 4/C°C min
^3 ml/min
240°C
m/e 20 -> 300
1 sec/decade
300 yA
6.0
^4 x 10 torr
29
-------
F. SAMPLING AND ANALYSIS FOR CHLORINATED AND BROMINATED HYDROCARBONS
AND OTHER CHEMICALS IN AMBIENT AIR
1.0 Principle of Method
Chlorinated and brominated hydrocarbons are concentrated from ambient
air on Tenax GC in a short glass tube (1-3). Recovery of the halogenated
hydrocarbons is accomplished by thermal desorption and purging with helium
into a liquid nitrogen cooled nickel capillary trap (1,2,4) and then vapors
are introduced onto a high resolution glass gas chromatographic column
where the constituents are separated from each other (2,5). Characterization
and quantitation of the constituents in the sample are accomplished by mass
spectrometry, either by measuring the intensity of the total ion current
signal or mass fragmentography (2,6). The collection and analysis systems
are shown in Figure Fl.
2.0 Range and Sensitivity
The linear range of the mass spectrometric signals for the halogenated
compounds depends upon two principal features. The first is a function of
the breakthrough volume of each specific compound trapped on the Tenax GC
sampling cartridge, and the second is related to the inherent sensitivity
of the mass spectrometer for each halogenated hydrocarbon and other organics
(2,7). Thus, the range and sensitivity is a direct function of each compound
which is identified. The linear range for quantitation on the gas chromato-
graph/mass spectrometer/computer (gc-ms-comp) is generally three orders of
magnitude. Table Fl lists the overall theoretical sensitivity for some
examples of halogenated hydrocarbons as well as other chemicals which is
based on these two principles (7).
The sensitivity of this technique for the organic compounds vinyl
chloride, vinyl bromide, methyl chloride, methyl bromide and ethylene is
inadequate for the purpose of this study. Alternate methods are suggested.
Tris-(2,3-dibromopropyl)phosphate and decabromobiphenyl ether cannot be
analyzed by this procedure. Bromobutyric acid has not been tested and
therefore its behavior is unknown. We believe that the following compounds
which are listed as emissions by the industry can be adequately analyzed:
benzol, carbon tetrachloride, diphenyl, epibrom, epichlor, ethylene dibromide,
hexane, bromobenzene, dibromopropanol, allyl alcohol, phenol, glycol,
30
-------
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METER
FLOW
/METER
PUMP
NEEDLE
VALVE
carbon
_
Tenax
GLASS
FIBER
FILTER
PLOT
TER
VAPOR COLLECTION SYSTEM
GLASS
JET
SEPARATOR
CARRIER
GAS
TWO
POSITION
VALVE
CAPILLARY
GAS
CHROMATCGRAFH
PURGE
GAS
i
CAPILLARY
TRAP
ANALYTICAL SYSTEM
THERMAL
DESORPTICN
CHAMBER
Figure Fl. Vapor collection and analytical systems for analysis of
organic vapors in ambient air.
HEATED
BLOCKS
EXHAUST
31
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aliphatic alcohols (> C,), tribromoethane, bromophenol, brominated aromatic
ethers (<3Br), fumazone, trimethylene chlorobromide, allyl chloride, 1,2-
chlorobromopropane, dichloropropane, isopropyl chloride and chlorobutyronit-
rile. Many other halogenated hydrocarbons and aromatics can potentially be
assayed if present in ambient air.
3.0 Interferences
Because of the unique isotopic clusters for chlorine and bromine in
the hydrocarbons, the hydrocarbon background generally observed occurring
from either auto exhaust or the petroleum industry will not interfere with
qualitative and quantitative analyses. The potential difficulties with
this technique are primarily associated with those cases where isomeric
forms of a particular halogenated substance cannot be resolved by the high
resolution chromatographic column and the mass cracking pattern of each of
the isomers are identical. Since the complete composition of ambient air
surrounding the bromine industry is not known dismissal of possible inter-
ferences cannot be unequivocally stated.
4.0 Reproducibility
The reproducibility of this method has been determined to range from
±10 to ±30 percent of the relative standard deviation for different substances
when replicate sampling cartridges are examined (5). The reproducibility
is a function of several factors: (1) the ability to accurately determine
the breakthrough volume for each of the identified halogenated compounds,
(2) the accurate measurement of the ambient air volume sampled, (3) the
percent recovery of the halogenated hydrocarbon from the sampling cartridge
after a period of storage, (4) the reproducibility of thermally recovering
a compound from the cartridge and of sample introduction into the analytical
system, (5) the accuracy in the determination of the relative molar response
ratios between the identified halogenated substance and the external standard
used for calibrating the analytical system, (6) the reproducibility of
transmitting the sample through the high resolution glass chromatographic
column, and (7) the day-to-day reliability of the ms-comp system (1-8).
The accuracy of the analysis is generally ±20 percent of the amount
determined from repeated analyses of the authentic halogenated hydrocarbon.
However, the accuracy of analysis is dependent upon the chemical and physical
nature of the compound (2,8).
35
-------
5.0 Advantages and Disadvantages of the Method
The gas chromatograph-mass spectrometer interfaced with a Finnigan
glass jet separator is extremely sensitive and specific for the analysis of
halogenated hydrocarbons. The high resolution gas chromatographic separation
provides adequate resolution of the halogenated hydrocarbons for their
subsequent quantification. The combination of the high resolution gas
chromatographic column and the selection of specific or unique ions re-
presenting the various halogenated hydrocarbons identified in air samples
yields a relatively specific assay method for these compounds (1-8).
Collected samples can be stored up to one month with less than 10
percent losses (2,8). Because some of the halogenated hydrocarbons could
be hazardous to man, it is extremely important to exercise safety precautions
in the preparation and disposal of liquid and gas standards, cleaning of
used glassware, etc. and the analysis of air samples.
Since the mass spectrometer cannot be conveniently mobilized, sampling
must be carried out away from the instrument.
The efficiency of air sampling increases as the ambient air temperature
decreases (that is, sensitivity increases) (8).
The retention of water by Tenax is low, its thermal stability is high
and its background is negligible allowing sensitive analysis (1,2,5,8).
6.0 Apparatus
6.1 Sampling Cartridges
The sampling tubes are prepared by packing a 10 cm long x 1.5 cm i.d.
glass tube containing 6.0 cm of 35/60 mesh Tenax GC with glass wool in the
ends to provide support (2,5). Virgin Tenax is extracted in a Soxhlet
extractor for a minimum of 18 hours with acetone prior to preparation of
cartridge samplers (2,5). After purification of the Tenax GC sorbent and
drying in a vacuum oven at 100°C for 2-3 hr all the sorbent material is
meshed to provide a 35/60 particle size range. Cartridge samplers are then
prepared and conditioned at 270°C with helium flow at 30 ml/min for 30
®
minutes. The conditioned cartridges are transferred to Kimax (2.5 cm x
150 cm) culture tubes, immediately sealed using Teflon lined caps, and
36
-------
cooled. This procedure is performed in order to avoid recontamination of
the sorbent bed (2,5).
Cartridge samplers with longer beds of sorbent may be prepared using a
proportional increased amount of Tenax in order to achieve a larger break-
through volume for each compound and thus increasing the overall sensitivity
of the technique (8).
6.2 Gas Chromatographic Column
A 0.35 mm i.d. x 100 m glass SCOT capillary column coated with OV-101
stationary phase and 0.1% benzyl triphenylphosphonium chloride is used for
effecting the resolution of the halogenated hydrocarbons and other chemicals
(5). The capillary column is conditioned for 48 hours at 230°C at 1.5-2.0
ml/min of helium flow. For highly polar pollutants of interest an 80 m
carbowax 20 M glass SCOT capillary is used.
A Finnigan type glass jet separator on a Varian-MAT CH-7 gc/ms/comp
system is employed to interface the glass capillary column to the mass
spectrometer. The glass jet separator is maintained at 240°C (2.5).
6.3 Inlet Manifold
An inlet manifold for thermally recovering vapors trapped on Tenax
sampling cartridges is employed and is shown in Figure Fl (1,2,4,5).
6.4 Gas Chromatograph
A Varian 1700 gas chromatograph is used to house the glass capillary
column and is interfaced to the inlet manifold (Fig. Fl).
6.5 Mass Spectrometry/Computer
A Varian-MAT CH-7 mass spectrometer with a resolution of 2,000 equipped
with a single ion monitoring capabilities is used in tandem with the gas
chromatograph (Fig. Fl). The mass spectrometer is interfaced to a Varian
620L computer (Fig. Fl).
7.0 Reagents and Materials
All reagents used are analytical reagent grade.
8.0 Procedure
8.1 Cleaning of Glassware
All glassware, sampling tubes, cartridge holders, etc. are washed in
®
Isoclean /water rinsed with deionized-distilled water, acetone and air
37
-------
dried. Glassware is heated to 450-500°C for 2 hours to insure that all
organic material has been removed prior to its use.
8.2 Preparation of Tenax GC
Virgin Tenax GC is extracted in a Soxhlet apparatus for a minimum of
18 hours with acetone prior to its use. The Tenax GC sorbent is dried in a
vacuum oven at 100°C for 2-3 hr and then sieved to provide a fraction
corresponding to 35/60 mesh. This fraction is used for preparing sampling
cartridges. In those cases where sampling cartridges of Tenax GC are
recycled, the sorbent is extracted in a Soxhlet apparatus with acetone as
described for the Virgin material, but the sorbent is further extracted
with a non-polar solvent, hexane, in order to remove the relatively non-
polar and non-volatile materials which might have accumulated on the sorbent
bed during previous sampling periods.
8.3 Collection of Halogenated Hydrocarbons in Ambient Air
Continuous sampling of ambient air is accomplished using a Nutech
Model 221-A portable sampler (Nutech Corp., Durham, NC, see Fig. Fl, ref.
2). Flow rates are maintained at 1 Jtl/min using critical orifices, and the
total flow is monitored through a calibrated rotameter. The total flow is
also registered by a dry gas meter. Concomitant with these parameters, the
temperature is continuously recorded with a Meterology Research Incorp.
weather station since the breakthrough volume is important in order to
obtain quantitative data on the halogenated hydrocarbons. This portable
sampling unit operates on a 12 volt storage battery and is capable of
continuous operation up to a period of 24 hours. However, in most cases at
the rates which will be employed in the field, the sampling period will
consist of 1 to 2 hours. This portable sampling unit will be utilized for
obtaining "high volume" samples. Duplicate cartridges are deployed on each
sampling unit. A total of four portable sampling units are available for
sampling ambient air surrounding the bromine industry. In addition to the
Nutech samplers five DuPont personnel samplers are used to sample "low
volumes" of ambient air as well as long term integrated samples (12-36
hours). The identical Tenax GC sampling cartridge is employed in this case
and sampling is conducted in duplicate. The flow rate is balanced between
38
-------
duplicate cartridges using critical orifices to maintain a rate of 25 or
100 ml/min/cartridge.
For large sample volumes it is important to realize that a total
volume of air may cause elution of halogenated hydrocarbons through the
sampling tube if their breakthrough volume is exceeded. The breakthrough
volumes of some halogenated hydrocarbons are shown in Table F2 (2,4,7,8).
These breakthrough volumes have been determined by a previously described
technique (2). The breakthrough volume is defined as that point at which
50% of a discrete sample introduced into the cartridge is lost. Although
the identity of a compound during ambient air sampling is not known (there-
fore also its breakthrough volume) the compound can still be quantified
after identification by gc/ms/comp once the breakthrough volume has subse-
quently established. Thus the last portion of the sampling period is
selected which represents the volume of air sampled prior to breakthrough
for calculating their concentration. For cases when the identity of the
halogenated hydrocarbon is not known until after glc-ms the breakthrough
volume is subsequently determined.
Previous experiments have shown that organic vapors collected on Tenax
GC sorbent are stable and can be quantitatively recovered from the cartridge
samplers up to four weeks when they are tightly closed in cartridge holders,
protected from light, and stored at 0°C (1,2).
8.4 Analysis of Sample
The instrumental conditions for the analysis of halogenated hydro-
carbons of the sorbent Tenax GC sampling cartridge is shown in Table F3.
The thermal desorption chamber and six-port valve are maintained at 270°
and 200°C, respectively. The glass jet separator is maintained at 240°.
The mass spectrometer is set to scan the mass range from 25-350. The
helium purged gas through the desorption chamber is adjusted to 15-20
ml/min. The nickel capillary trap at the inlet manifold is cooled with
liquid nitrogen. In a typical thermal desorption cycle a sampling cartridge
is placed in the preheated desorption chamber and helium gas is channeled
through the cartridge to purge the vapors into the liquid nitroged cooled
nickel capillary trap [the inert activity of the trap has been shown in
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Table F3. OPERATING PARAMETERS FOR GLC-MS-COMP SYSTEM
Parameter Setting
Inlet-manifold
desorption chamber 270°C
valve 220°C
capillary trap - minimum -195°C
maximum +180°C
thermal desorption time 4 min
GLC 100 m glass SCOT-OV101
50 m glass SCOT-Carbowax 20M 20-240°C, 4/C° min
80-240°C
carrier (He) flow ~3 ml/min
transfer line to ms 240°C
MS
scan range m/e 20 -»• 300
scan rate, automatic-cyclic 1 sec/decade
filament current 300 yA
multiplier 6.0
ion source vacuum ~4 x 10 torr
44
-------
previous studies (5)]. After desorption the six-port valve is rotated and
the temperature on the capillary loop is rapidly raised (greater than
10°/min); the carrier gas then introduces the vapors onto the high resolution
glc column. The glass capillary column is temperature programmed from 20°
to 240°C at 4°/min and held at the upper limit for a minimum of 10 min.
After all of the components have eluted from the capillary column the
analytical column is then cooled to ambient temperature and the next sample
is processed (2).
An example of the analysis of volatile organics in ambient air is
shown in Figure F2 and the background from a blank cartridge in Figure F3.
The high resolution glass capillary column was coated with OV-101 sta-
tionary phase which is capable of resolving a multitude of compounds,
including halogenated hydrocarbons, to allow their subsequent identification
by ms-comp techniques; in this case over 120 compounds were identified in
this chromatogram.
8.4.1 Operation of the MS-COMP System (Fig. F4)
Typically the mass spectrometer is first set to operate in the repeti-
tive scanning mode. In this mode the magnet is automatically scanned
exponentially upward from a preset low mass to a high mass value. Although
the scan range may be varied depending on the particular sample, typically
the range is set from m/e 25 to m/e 300. The scan is completed in approxi-
mately 3 seconds. At this time the instrument automatically resets itself
to the low mass position in preparation for the next scan, and the informa-
tion is accumulated by an on-line 620/L computer and written onto magnetic
tapes or the dual disk system. The reset period requires approximately 3
seconds. Thus, a continuous scan cycle of 6 seconds/scan is maintained and
repetitively executed throughout the chromatographic run. The result is
the accumulation of a continuous series of mass spectra throughout the
chromatographic run in sequential fashion.
Prior to running unknown samples the system is calibrated by intro-
ducing a standard substance, perfluorokerosene, into the instrument and
determining the time of appearance of the known standard peaks in relation
to the scanning magnetic field. The calibration curve which is thus
45
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generated will be stored in the 620/L computer memory. This calibration
serves only to calibrate the mass ion over the mass scanning range.
While the magnetic is continuously scanning the sample is injected and
automatic data acquisition is initiated. As each spectrum is acquired by
the computer each peak which exceeds a preset threshold is recognized and
reduced to centroid time and peak intensity. This information is stored in
the computer core while the scan is in progress. In addition, approximately
30 total ion current values and an equal number of Hall probe signals are
stored in the core of the computer as they are acquired. During the 3
second period between scans this spectral information, along with the
spectrum number, is written sequentially on disks, and the computer is
reset for the acquisition of the next spectrum.
This procedure continues until the entire gc run is completed. By
this time there are from 300-1,000 spectra on the disk which are then
subsequently processed. Depending on the information required, the data
may then either be processed immediately or additional samples may be run,
stored on magnetic tape and the results examined at a later time.
The mass spectral data are processed in the following manner. First,
the original spectra are scanned and the total ion current (TIC) information
is extracted. Then the TIC intensities are plotted against the spectrum
number on the Statos 31 recorder. The information will generally indicate
whether the run is suitable for further processing, since it will give some
idea of the number of unknowns in the sample and the resolution obtained
using the particular glc column conditions.
The next stage of the processing involves the mass conversion of the
spectral peak times to peak masses which is done directly via the dual disk
system. The mass conversion is accomplished by use of the calibration
table obtained previously using perfluorokerosene. Normally one set of the
calibration data is sufficient for an entire day's data processing since
the characteristics of the Hall probe are such that the variation in calibra-
tion is less than 0.2 atomic mass units/day. A typical time required for
this conversion process for 1,000 spectra is approximately 30 min.
After the spectra are obtained in mass converted form, processing
proceeds either manually or by computer. In the manual mode the full
49
-------
spectra of scans from the gc run are recorded on the States 31 plotter.
The TIC information available at this time is most useful for deciding
which spectra are to be analyzed. At the beginning of the runs where peaks
are very sharp nearly every spectrum must be inspected individually to
determine the identity of the component. Later in the chromatographic run
when the peaks are broader only selected scans need to be analyzed.
Identification of resolved components is achieved by comparing the
mass cracking patterns of the unknown mass spectra to an eight major peak
index of mass spectra (9). Individual difficult unknowns are searched by
the use of the Cornell University STIRS and PBM systems. Unknowns are also
identification of unknowns are confirmed by comparing the cracking pattern
and elution temperatures for two different chromatographic columns (OV-101
and OV-17 SCOT capillaries) for the unknown and authentic compounds. The
relationship between the boiling point of the identified halogenated hydro-
carbon and the elution temperature on a non-polar column (the order of
elution of constituents is predictable in homologous series since the OV-
101 SCOT capillary separates primarily on the basis of boiling point) is
carefully considered in making structure assignments.
Mass spectra search programs are operational at the Triangle Uni-
versities Computation Center (TUCC). RTI maintains thrice daily service to
TUCC, which is one-quarter mile distance from the RTI campus. Additional
information about each magnetic tape containing the mass spectra of haloge-
nated hydrocarbons is entered directly into the TUCC job stream using a
remote job entry processing. This is normally done at TUCC using one of
the five terminals located within the Analytical Sciences Laboratory. The
control information contains selected spectrum numbers of instructions to
process entire gc runs. The computer program systems compare simultaneously
either the entire library of 25,000 compounds or some subset of this library.
The complete reports showing the best fits for each of the unknowns is
produced at TUCC and printed out at the high speed terminals located on the
RTI campus of TUCC. Thus, the processing of the mass spectral data obtained
for the halogenated hydrocarbons in the samples collected is processed by
50
-------
one of three routes. Each consists of a different level of effort. The
first level is strictly a manual interpretation process which proves to be
the most thorough approach. The second level is executed when the interpre-
tation at the first level has not yielded conclusive results.
8.4.2 Quantitative Analysis
In many cases the estimation of the level of pollutants by capillary
gas chromatography in combination with mass spectrometry is not feasible
utilizing only the total ion current monitor (see Fig. F2 for example),
since baseline resolution between peaks is not always achieved. We employ
the techniques which have been previously developed under contract whereby
full mass spectra are obtained during the chromatographic separation step
and then selected ions are presented as mass fragmentograms using computer
software programs which allow the possibility of deconvoluting constituents
which were not resolved in the total ion current chromatogram (6). Examples
are depicted in Figures F5 and F6 which represent an ambient air sample
with an TIC profile as in Fig. F2.
In our gc/ms/comp system we request from the Varian 620L dedicated
computer mass fragmentograms for any combination of m/e ions when full mass
spectra are obtained during chromatography. Thus, selectivity is obtained
by selecting the unique ion for that particular halogenated hydrocarbon,
and this is represented versus time with subsequent use of that ion intensity
for quantitation. Also, quantitation with external standards is easily
achieved using the intensity of the total ion current monitor or the use of
a unique mass cracking ion in the mass spectrum of that external standard.
Thus, we use mass fragmentography for the quantitation of halogenated
hydrocarbons in ambient air when the total ion current is inadequate because
of a lack of complete resolution between components in the mixture.
As described previously, the quantitation of constituents in ambient
air samples is accomplished either by utilizing the total ion current
monitor or where necessary the use of mass fragmentograms. In order to
eliminate the need to obtain complete calibration curves for each compound
for which quantitative information is desired, we use the method of relative
molar response (RMR) factors (10). Successful use of this method requires
information on the exact amount of standard added and the relationship of
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RMR (unknown) to the RMR (standards). The method of calculation is as
follows:
A . /Moles ,
(1) RMR = unk unk
unknown/ standard A ../Moles ,
std std
A = peak area, determined by integration or triangulation.
The value of RMR was determined from at least three independent
analyses.
A . /g , /GMW .
unk unk unk
A = peak area, as above
g = number of grams present
GMW = gram molecular weight
Thus, in the sample analyzed:
A . *GMW «g ,
unk unk std
(3) g
unk A »GMW ,-RMR . , ,
std std unk/std
The standard added can be added as an internal standard during sampling.
However since the volume of air taken to produce a given sample is accurately
known, it is also possible and more practical to use an external standard
whereby the standard is introduced into the cartridge prior to its analysis.
Two standards, hexafluorobenzene and perfluorotoluene are used for the
purpose of calculating RMR's. From previous research it has been determined
that the retention times for these two compounds are such that they elute
from the glass capillary column (OV-101) at a temperature and retention
time which does not interfere with the analysis of unknown compounds in
ambient air samples.
Since the volume of air taken to produce a given sample is accurately
known and an external (or internal) standard is added to the sample, then
the weight can be determined per cartridge and hence the concentration of
the unknown. The approach for quantitating ambient air pollutants requires
that the RMR is determined for each constituent of interest. This means
that when an ambient air sample is taken, the external standard is added
54
-------
during the analysis at a known concentration. It is not imperative at this
point to know what the RMR of each of the constituents in the sample happens
to be; however, after the unknowns are identified, then the RMR can be
subsequently determined and the unknown concentration calculated in the
original sample using the RMR. In this manner it is possible to obtain
qualitative and quantitative information on the same sample with a minimum
of effort.
9.0 References
1. Pellizzari, E. D., Development of Method for Carcinogenic Vapor Analysis
in Ambient Atmospheres. Publication No. EPA-650/2-74-121, Contract
No. 68-02-1228, 148 pp., July, 1974.
2. Pellizzari, E. D., Development of Analytical Techniques for Measuring
Ambient Atmospheric Carcinogenic Vapors. Publication No. EPA-600/2-
76-076, Contract No. 68-02-1228, 185 pp., November, 1975.
3. Pellizzari, E. D., J. E. Bunch, B. H. Carpenter and E. Sawicki, Environ.
Sci. Tech., 9, 552 (1975).
4. Pellizzari, E. D., B. H. Carpenter, J. E. Bunch and E. Sawicki, Environ.
Sci. Tech., 9, 556 (1975).
5. Pellizzari, E. D., Development of Analytical Techniques for Measuring
Ambient Atmospheric Carcinogenic Vapors, 1976, in preparation.
6. Pellizzari, E. D., J. E. Bunch, R. E. Berkeley and J. McRae, Anal.
Chem., 48, 803 (1976).
7. Pellizzari, E. D., Quarterly Report No. 1, EPA Contract No. 68-02-
2262, February, 1976.
8. Pellizzari, E. D., J. E. Bunch, R. E. Berkeley and J. McRae, Anal.
Lett., 9, 45 (1976).
9. "Eight Peak Index of Mass Spectra", Vol. 1, (Tables 1 and 2) and II
(Table 3), Mass Spectrometry Data Centre, AWRE, Aldermaston, Reading,
RF74PR, UF, 1970.
10. Pellizzari, E. D., Quarterly Report No. 3, EPA Contract No. 68-02-
2262, in preparation.
Analytical protocol revised 1/24/77.
55
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G. CHLORINE/BROMINE SAMPLING AND ANALYSIS IN AMBIENT AIR
1.0 Principle of Method
Gaseous chloride and bromide (HC1 and HBr) are collected in deionized
water in an impinger. The impinger solution is assayed for total halide by
precipitation of the silver halide and determining the precipitate by
turbidity or nephelometry. Another aliquot is subjected to ion exchange
chromatography to separate chloride and bromide ion. The two fractions are
analyzed by the turbidity of the silver halide precipitate. Confirmation
is obtained for bromide by neutron activation analysis.
2.0 Range and Sensitivity
Samples of ambient air are taken at 2 £/min for a period of 30 min for
a total of 60 £ of air using 20 ml of absorber solution. This period may
be increased to 150 min or a total of 300 S. in the absence of strong oxidants,
The range of the turbidimetric method for total halides is 0.2 pg/ml
to above 40 |Jg/ml in the absorber solution. The ion exchange chromatography
is limited by recoveries and background to 1 pg/ml on the lower limit and
to 5 rag/ml by ion exchange capacity at the upper limit.
Method Range
Total halides (turibidity) 0.2 - 40 |Jg/ml
Ion exchange and turbidity
chloride 1 - 500 |Jg/ml
bromide 1 - 1000 M8/ml
Neutron Activation 0.015 (Jg ~ 1 g/g
3.0 Interferences
Sampling - High concentration of strong oxidants (i.e., C10, 00 ...)
* v — — z j
will oxidize bromide to bromine which is purged from the absorber solution
resulting in low values for bromide. If the oxidant is chlorine then
elevated chloride values would be obtained.
Total Halides - Phosphate
Ion Exchange and Turbidity - None known
Neutron Activation Analysis - Large quantities of sodium or potassium
interfer. Organic bromine is measured as well as inorganic.
56
-------
A.O Precision and Accuracy
Sampling - With the use of syringe needles as critical orifices for
flow control sample volumes can be collected with an accuracy 5% and a
precision of 2%.
Total Halide - The precision of the silver halide turbidity method
ranges from 6 to 1% over the concentration range 1 to 20 (Jg/ml in the
absorber solution. Accuracy of the method depends upon the sample com-
position since the response is slightly halide dependent. Bromine gives
80% of the chloride response for the same weight.
Ion Exchange Chromatography and Turbidity - The precision of the
measurement of chloride and bromide is 5% over the range 1.0 to 100 (Jg/ml
of chloride and 1.0 to 100 [Jg/ml bromide in the impinger solution. The
accuracy depends upon the assessment of recoveries and may introduce errors
of up to 10%.
5.0 Apparatus
5.1 Sample Collection
Midget Impingers
Critical Oriface - 1 in. 21 gauge Becton Dickinson syringe needle.
Critical Oriface Protector - 6 inch drying tube packed with ascarite
(20-30 mesh) retained by glass wool plugs at either end.
Pump - Adequate to produce 15 in Hg at 2 JH/min fitted with a rubber
tubing manifold.
One ounce polyethylene bottles sufficient to ship the collected
impinger solutions.
5.2 Turbidimetric Analysis
Adequate and sufficient storage bottles
1 - 1000 ml volumetric flask
8 - 100 ml volumetric flasks
1 - 15 ml volumetric pipette
1 - 2 ml volumetric pipette
3 - 1 ml volumetric pipettes
1 - 0.5 ml volumetric pipette
Sufficient 1 inch test tubes and 10 mm cuvettes for the number of
samples and standards.
57
-------
Vortex-type test tube stirrer.
Spectrophotometer or nephelometer capable of operating at 360 nnm.
5.3 Chromatography Apparatus
Chromatography Columns - 4 mm x 100 mm with a glass wool plug (thistle
tubes with drawn tips at 10 cm are available).
Pipets - Graduated 2 and 5 ml.
Sample Bottles - 1 oz. sufficient for the collection of fractions.
6.0 Reagents
6.1 Sampling
Impinger Solution - 20 ml deionized water for each sample taken.
6.2 Turbidimetric Analysis
Silver Nitrate Solution (0.5 N) - Place 8.5 g AgNO_ in a 100 ml
volumetric flask and dilute to the mark with distilled or deionized water.
Store in a dark brown bottle.
Nitric Acid (2.5 N) - Dilute 16 ml of concentrated HNO to the mark in
a 100 ml volumetric flask with deionized water.
Isopropanol - Reagent Grade
Stock Standard Chloride Solution - Weigh out 0.1648 g NaCl and place
in a 100 ml volumetric flask. Dilute to the mark with deionized water.
This solution contains 1000 |jg Cl~/ml.
Diluted Chloride Standards - A working standard is prepared by pipeting
10 ml of the stock chloride solution into a 100 ml volumetric flask and
dilute to mark with deionized water. Pipet 0.5, 1, 5, 10 and 20 ml of the
stock chloride standard solution into 100 ml volumetric flasks and dilute
each to the mark with deionized water. These solutions contain respectively,
0.5, 1.0, 5, 10, and 20 M8 Cl"/ml.
6.3 Chromatography
0.1M Sodium Nitrate - Place 8.5 g NaNO in a 1000 ml volumetric flask
and dilute to the mark with deionized water.
0.5M Sodium Nitrate Place 42.5 g NaNO in a 1000 ml volumetric flask
and dilute to the mark with deionized water.
Anion Exchange Resin - AG-1-X10 (BioRad) converted to NC- form by
flushing with 0.5M NaNO. until a negative chloride test is obtained.
58
-------
Dilute Chloride Standards for Chromatography - A working standard is
parepared by pipeting 10 ml of the stock chloride solution (see Section
6.2) into a 100 ml volumetric flask and dilute to mark with 0.1 M NaNCL.
Pipet 0.5, 1, 5, 10, and 20 ml of the stock chloride standard solution into
100 ml volumetric flasks and dilute each to the mark with 0.1 M NaNCL.
These solutions contain respectively, 0.5, 1.0, 5, 10, and 20 |Jg Cl /ml.
Stock Standard Bromide Solution - Weigh out 0.1268 g NaBr and place in
100 ml volumetric flask. Dilute to the mark with deionized water. This
solution contains 1000 |Jg Br /ml.
Diluted Bromide Standards - Prepare as for chloride using the stock
standard bromide solution and making all dilutions with 0.5 M NaNO«.
Silver Nitrate Solution, Nitric Acid, and isotropanol is described in
Section 6.2.
7.0 Procedure
7.1 Sample Collection
Collect samples at 1.5-2 3,/min for 30 min periods. Laboratory evalua-
tions have indicated sampling periods are reliable up to 150 min periods
(300°) except for the displacement of bromide by change oxidants.
7.2 Turbidimetric Method for Halides
Place an aliquot of 3.0 ml of isopropyl alcohol and 0.2 ml 2.5N
nitric acid in each of six 1 inch test tubes. To the first test tube add
1.6 ml of deionized water (the chloride blank). To tubes 2 through 6 add
1.6 ml aliquots of chloride standard at 0.5, 1, 5, 10 and 20 |jg/ml. Mix
using a Vortex type stirrer. Add 0.2 ml aliquot of 0.5N AgNCL to each test
tube and mix the contents on the Vortex mixer. Store the resulting solutions
in the dark for one hour and make nephelometric measurements of the turbidity
at 360 nm. Plot turbidance yjs pg Cl /ml to give a standard curve.
Samples of the impinger solution are analyzed as described for the
standards.
7.3 Ion Exchange Separation of Chloride and Bromide
Chromatographic columns (4 x 70 mm) will be filled to 70 mm with AG-1-
X10 anion exchange resin (BioRad) washed with 20 ml 0.5M NaNC" . Wash the
column with 5 ml of deionized water and add the sample (4 ml) to the column.
Wash with 0.5 ml aliquot of deionized water. Elute the column with 4 ml of
59
-------
0.1M NaNCL and collect for chloride analysis. Elute the bromide with a 2
•J
ml aliquot of 0.5M NaNC- . This fraction is used for the bromide analysis.
Z
Place an aliquot of 3.0 ml of isopropyl alcohol and 0.2 ml 2.5N
nitric acid in each of 12 test tubes. To the first test tube add 1.6 ml of
0.1M NaNO^ (the chloride blank) to the second 1.6 ml of 0.5M NaN03 (the
bromide blank). To tubes 3 through 7 add 1.6 ml aliquots of chloride
standards diluted in 0.1M NaN03 to 0.5, 1, 5, 10, and 20 (Jg/ml. To tubes 8
through 12 add 1.6 ml aliquots of bromide standards dilute in 0.5M NaNO_ to
0.5, 1, 5, 10 and 20 |jg/ml. Mix using a Vortex type stirrer. Add an
aliquot of 0.5 ml of 0.5N AgNCL to each test tube and mix the contents on
the Vortex mixer. Store the resulting solutions in the dark for one hr and
make nephelometric measurements of the turbidity at 360 nm. Plot turbidance
vs |Jg Cl /ml or fjg Br /ml to give a standard curve.
Repeat the same procedure for 1.6 ml aliquots of the chloride and
bromide fractions. Read concentrations from the appropriate standard
curve .
8.0 Calibration Methods
Calibration of the analytical methods will be done using sodium
chloride and sodium bromide as standards. Verification of collection
efficiency and breakthrough will be obtained by volatilizing aliquots
containing known amounts of HC1 and HBr in the air stream entering the
impinger.
9.0 Calculations
9.1 Total Halide (as HC1)
(Jg HC1/M3 =
pg Cl /ml x ml absorber x 36.45
M3 , , 35.45
M sampled
9.2 Ion Exchange Separation of Chloride and Bromide
Gaseous Chlorides
e.g., HC1
Mg HBr/M3 =
[Jg Cl /ml x ml column fraction x ml absorber x 36.45
o o c / c
M sampled x ml aliquot placed on column
Gaseous Bromides
e.g., HBr
60
-------
Mg HBr/M3 =
[Jg Br /ml x ml column fraction x ml absorber x 80.91
3 79.91
M sampled x ml aliquot not placed on column
10.0 Effects of Storage
Glass containers must be avoided for the storage of dilute solutions
of halides as they are adsorbed to the walls. For this reason polyethylene
will be used for storage containers. In any case prompt analysis is highly
desirable to obtain the most accurate results.
11.0 References
1. "Determination of Chlorine and/or Chlorides - Turbidimetric Method",
Adopted January 31, 1975, Texas Air Control Board.
2. R. C. DeGeiso, W. Rieman and S. Linderbaum, Anal. Chem., 26, 1840
(1954).
3. H. D. Axelrod, J. E. Bonelli and J. P. Lodge, Jr., Environ. Sci.
Tech., 5, 420 (1971).
Analytical protocol revised 1/24/77.
61
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H. CHLORINE/BROMINE SAMPLING AND ANALYSIS IN AMBIENT AIR
1.0 Principle of Method
Gaseous chlorine and bromine are collected in alkaline sodium arsenite
*
in an impinger. The halogens are reduced to the corresponding halides and
are not volatile in the alkaline solution. Hydrogen chloride and hydrogen
bromide are removed by passing the air sample through an impinger containing
deionized water prior to the alkaline sodium arsenite. The irapinger solution
is assayed for total halide by precipitation of the silver halide and
determining the precipitate by turbidity or nephelometry. Another aliquot
is subjected to ion exchange chromatography to separate chloride and bromide
ion. The two fractions are analyzed by the turbidity of the silver halide
precipitate. Confirmation is obtained from bromide by neutron activation
analysis .
2.0 Range and Sensitivity
Samples of ambient air are taken at 2 £/min for a period of 30 rain for
a total of 60 £ of air using 20 ml of absorber solution. This period may
be increased to 150 min or a total of 300 $,.
The range of the turbidimetric method for total halides is 0.2 pg/ml
to above 40 |Jg/ml in the absorber solution. The ion exchange chromatography
is limited by recoveries and background to 1 pg/ml on the low level and to
5 mg/ml by ion exchange capacity at the upper limit.
Method Range
Total halides (turbidity) 0.2 - 40
Ion exchange and turbidity
chloride 1 - 500 |Jg/ml
bromide 1 - 500 (Jg/ml
Neutron Activation 0.015 pg - 1 g/g
3.0 Interferences and Problems Anticipated
Sampling - The disposition of chlorine in the impinger train in the
absence of bromide is known. Bromine is purged through the impinger train
unless a large volume (300 £) is sampled. Even then 8 to 23% is found in
the deionized water. High concentration of strong oxidants (i^e. , Cl~, CL
...) oxidize bromide collected in the first impinger to bromine leading to
high bromine values. If the oxidant is chlorine then low chlorine values
are obtained.
-------
Total Halides - Phosphates
Ion Exchange and Turbidity - None known
Neutron Activation Analysis - Large quantities of sodium or potassium
interfer. Organic bromine is measured as well as inorganic.
4.0 Precision and Accuracy
Sampling - With the use of syringe needles as critical orifices for
flow control sample volumes can be collected with an accuracy 5% and a
precision of 2%. Accuracy of sampling is subject to the limitations
described in Section 3.0.
Total Halide - The precision of the silver halide turbidity method
ranges from 6 to 1% over the concentration range 1 to 20 |Jg/ml in the
absorber solution. Accuracy of the method depends upon the sample com-
position since the response is halide dependent.
Ion Exchange Chromatography and Turbidity - Concentration dependent
recoveries result in standard deviations which are 10 and 5% relative at
-2 -2
355 |Jg/ml chloride (10 M) and 790 (Jg/ml (10 M) bromide, respectively, but
30% at 3.5 Mg/ml chloride and 7.9 Hg/ml bromide.
5.0 Apparatus
5.1 Sample Collection
Critical Oriface - 1 in. 21 gauge Becton Dickinson syringe needle.
Critical Oriface Protector - 6 inch drying tube packed with ascarite
(20-30 mesh) retained by glass wool plugs at either end.
Pump - Adequate to produce 15 in Hg at 2 £/min fitted with a rubber
tubing manifold.
One ounce polyethylene bottles sufficient to ship the collected im-
pinger solutions.
5.2 Turbidimetric Analysis
Adequate and sufficient storage bottles
1 - 1000 ml volumetric flask
8 - 100 ml volumetric flasks
1 - 15 ml volumetric pipette
1 - 2 ml volumetric pipette
3 - 1 ml volumetric pipettes
1 - 0.5 ml volumetric pipettes
63
-------
Sufficient 1 inch test tubes and 10 mm cuvettes for the number of
samples and standards.
Vortex-type test tube stirrer
Spectrophotometer or nephelometer capable of operating at 360 nm.
5.3 Chromatography Apparatus
Chromatography columns - 4 mm x 100 mm with glass wool plug (thistle
tubes with drawn tips at 10 cm are suitable).
Pipets - Graduated 10 and/or 20 ml.
Sample Bottles - 1 oz sufficient for the collection of fractions.
6.0 Reagents
6.1 Sampling
Impinger Solution A - 20 ml deionized water for each sample taken and
Impinger Solution B - 20 ml of solution which contains 4 grams NaOH and
0.65 gram NaAsCL in a 1000 ml volumetric flask and dilute to the mark with
deionized water.
6.2 Turbidimetic Analysis
Silver Nitrate Solution (0.5 N) - Place 8.5 g AgNO in a 100 ml
volumetric flask and dilute to the mark with distilled or deionized water.
Store in a dark brown bottle.
Nitric Acid (2.5 N) - Dilute 16 ml of concentrated HNO~ to the mark in
a 100 ml volumetric flask with deionized water.
Isopropanol - Reagent Grade
Stock Standard Chloride Solution - Weigh out 0.1648 g NaCl and place
in a 100 ml volumetric flask. Dilute to the mark with deionized water.
This solution contains 1000 pg Cl /ml.
Diluted Chloride Standards - A working standard is prepared by pipeting
10 ml of the stock chloride solution into a 100 ml volumetric flask and
dilute to mark with deionized water. Pipet 0.5, 1, 5, 10 and 20 ml of the
stock chloride standard solution into 100 ml volumetric flasks and dilute
each to the mark with deionized water. These solutions contain respectively,
0.5, 1.0, 5, 10, and 20 pg Cl"/ml.
6.3 Chromatography
Sodium Nitrate 0.1M - Place 8.5 g NaNO in a 1000 ml volumetric flask
and dilute to the mark with deionized water.
64
-------
Sodium Nitrate 0.5M - Place 42.5 g NaNO in a 1000 ml volumetric flask
and dilute to the mark with deionized water.
Anion Exchange Resin - AG-1-X10 (BioRad) converted to NCL form by
flushing with 0.5M NaNO,, until a negative chloride test is obtained.
o
Dilute Chloride Standards for Chromatography - A working standard is
prepared by pipeting 10 ml of the stock chloride solution (see Section 6.2)
into a 100 ml volumetric flask and dilute to mark with 0.1M NaNO-. Pipet
0.5, 1, 5, 10, and 20 ml of the stock chloride standard solution into 100
ml volumetric flasks and dilute each to the mark with 0.1M NaNO-. These
solutions contain respectively, 0.5, 1.0, 5, 10, and 20 pg Cl /ml.
Stock Standard Bromide Solution - Weigh out 0.1288 g NaBr and place in
100 ml volumetric flask. Dilute to the mark with deionized water. This
solution contains 1000 |jg Br /ml.
Dilute Bromide Standards - Prepare as for chloride using the stock
""'""" I
standard bromide soluion and making all dilutions with 0.5M NaNO«.
Silver Nitrate Solution, Nitric Acid, and isopropanol as described in
Section 6.2.
7.0 Procedure
7.1 Sample Collection
Collect samples at 1.5-2 £/min for 30 min period. Laboratory evaluation
indicated longer sampling periods are reliable and this time period may be
increased to 150 min.
7.2 Turbidimetric Method for Halides
Place an aliquot of 3.0 ml of isopropyl alcohol and 0.2 ml of 2.5N
nitric acid in each of six 1 inch test tubes. To the first test tube add
1.6 ml of deionized water (the chloride blank). To tubes 2 through 6 add
1.6 ml aliquots of chloride standard at 0.5, 1, 5, 10 and 20 ng/ml. Mix
using a Vortex type stirrer. Add an aliquot of 0.2 ml of 0.5N AgNO_ to
each test tube and mix the contents on the Vortex mixer. Store the resulting
solutions in the dark for one hour and make nephelometric measurements of
the turbidity at 360 nm. Plot turbidance vs_ /g Cl /ml to give a standard
curve.
Samples of the impinger solution will be treated as described for the
standards.
65
-------
7.3 Ion Exchange Separation of Chloride and Bromide
Chromatographic columns (4 x 100 mm) will be filled to 70 mm with AG-
1-X10 anion exchange resin (BioRad) equilibrated with 0.5M NaNCL. Wash the
j
column with 5 ml of deionized water and add the sample (3 ml) to the column.
Wash with 0.5 ml aliquot of deionized water. Wash the column with 4 ml
aliquot of 0.1 NaNCL and collect the fraction for the chloride determination.
Elute the bromide with a 2 ml aliquot of 0.5M NaNO . This fraction will be
used for the bromide analysis.
Place an aliquot of 3.0 ml of isorporpyl alcohol and 0.2 ml 2.5N
nitric acid in each of twelve test tubes. To the first test tube add 1.6
ml of 0.1M NaNO- (the chloride blank), to the second 1.6 ml of 0.5M NaNCL
(the bromide blank). To tubes 3 through 7 add 1.6 ml aliquots of chloride
standards diluted in 0.1M NaNO to 0.5, 1, 5, 10, and 20 pg/ml. To tubes 8
through 12 add 1.6 ml aliquots of bromide standards diluted in 0.5M NaNO,,
to 0.5, 1, 5, 10 and 20 |jg/ml. Mix using a Vortex type stirrer. Add an
aliquot of 0.2 ml of 0.5N AgNO- to each test tube and mix the contents on
J
the Vortex mixer. Store the resulting solutions in the dark for one hour
and make nephelometric measurements of the turbidity at 360 nm. Plot
turbidance vs |Jg Cl /ml or pg Br /ml to give a standard curve.
8.0 Calibration Methods
Calibration of the analytical methods will be done using sodium chloride
and sodium bromide as stndards. Verification of collection efficiency and
breakthrough will be obtained using Cl_ and Br~ permeation tubes.
9.1 Total Halogen (as C1.J
Mg C12/M3 =
pg Cl /ml x ml absorber
3
M sampled x
9.2 Ion Exchange Separation of Chloride and Bromide
Chlorine
pg C12/M3 =
pg Cl /ml x ml column fraction x ml absorber
3
M sampled x ml aliquot placed on column
66
-------
Bromine
(Jg Br2/M3 =
}Jg Br /ml x ml column fraction x ml absorber
3
M sampled x ml aliquot placed on column
10.0 Effects of Storage
Glass containers must be avoided for the storage of dilute solutions
of halides as they are adsorbed to the walls. For this reason polyethylene
will be used for storage containers. In any case prompt analysis is highly
desirable to obtain the most accurate results.
11.0 References
1. "Determination of Chlorine and/or Chlorides - Turbidimetric Method",
Adopted January 31, 1975, Texas Air Control Board.
2. R. C. Degeiso, W. Rieman and S. Linderbaum, Anal. Chem., 26, 1840
(1954).
3. H. D. Axelrod, J. E. Bonelli and J. P. Lodge, Jr., Environ. Sic.
Tech., 5, 420 (1971).
Analytical protocol revised 1/24/77.
67
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I. DETERMINATION OF INORGANIC FLUORIDE IN AMBIENT AIR
Adaptation of the Specific Ion Electrode Method for
Measurement of Fluorede Ion in Gaseous Samples
1.0 Principle of Method
Gaseous fluoride and fluorine gas are absorbed in a caustic solution.
A midget impinger is used and the exposed solution returned to the laboratory
for processing.
After proper processing, the sample is treated with a buffer. The
concentration of fluoride in the sample is determined using a fluoride
specific ion electrode.
2.0 Range and Sensitivity
The concentration range for the actual analysis of the sample should
be from 0.1 to 10.0 (Jg of fluoride total in the aliquot taken for the
analyis. Hence, the lower limit of detection in the ambient air will
depend upon the volume of air passed through the absorbing solution.
In general, levels in the low part per billion range of fluoride can
be measured for gaseous samples.
3.0 Interferences
Substances which form stable fluoride complexes such as aluminum
®
silicon and/or iron (III) interfer. Using TISAB buffer up to 5 ppm of
aluminum or ion does not interfer with the determination of 1 ppm F . If
®
higher levels are encountered a tartarate-TRIS buffer TISAB can be used to
eliminate interference.
Cations and most anions do not interfere with the response of the
fluoride elctrode to fluoride. Anions commonly associated with fluoride
— — — ^ — — —^
such as Cl , Br , I , SO, , HCO , NO , PO, and acetate do not interfere
— •*<•
with electrode operation. The OH ion is an electrode interference.
= -3
Some anions, such as CO- or PO, , make the sample more basic, increasing
the OH interference, but are not direct electrode interferences.
4.0 Precision and Accuracy
The Orion Model 801 digital pH/mv meter used for the measurements is
accurate to +0.1 mV which over the nerstian region, 1 to 190 ppm, corresponds
to 0.2%. Preparation of standards, temperature fluctuations represent the
largest sources of error, but should not exceed 2%.
68
-------
5.0 Apparatus
Midget impinger sampling train
1 - Steam distillation apparatus
1 - Evaporation oven
Sufficient and adequate sample storage bottles
-'-v
1 - Specific fluoride ion electrode with accompanying meter
**
1 - Saturated calomel reference electrode
Sufficient number of 50 ml polyethylene beakers for the number of
samples and standards being analyzed.
3 - 1000 ml volumetric flasks
1 - 500 ml volumetric flask
3 - 100 ml volumetric flasks
1 - 15 ml volumetric pipet
Sufficient 10 ml volumetric pipettes for the number of standards and
samples being analyzed.
1 - 1 ml volumetric pipet
1 - 1 ml graduated pipet
6.0 Reagents
All reagents should be ACS reagent grade.
(1) Sodium Citrate Buffer (0.1 M) - Dissolve 35.72 g of sodium citrate
(2Nac.C6Hc.07-11 H-O) in approximately 750 ml of distilled water contained in
a 1000 ml volumetric flask. After the salt is completely dissolved, dilute
to the mark with distilled water and mix thoroughly.
NOTE Buffers for this purpose are available commercially
®
TISAB , a product of Orion Research, is one which
has been used in this laboratory.
(2) Sulfuric Acid - 96.0%.
(3) Sodium Hydroxide.
(a) 1.0 N Sodium Hydroxide - Carefully weigh out 20.0 grams of
sodium hydroxide and place in a 500 ml volumetric flask. Add approximately
475 ml of distilled water and stir until the NaOH is completely dissolved.
Allow the solution to cool and dilute to the mark with distilled water.
However proper use of buffers avoids this interference
*
Combination specific fluoride ion electrode with accompanying meter may
be substituted.
69
-------
(b) 0.01 N Sodium Hydroxide - Place 10 ml of the 1.0 N NaOH in a
1000 ml volumetric flask. Dilute to the mark with distilled water. This
solution serves as the absorbing reagent for the gaseous fluorides.
(4) Standard Fluoride Solution - Dissolve 0.2210 g of sodium fluoride
in distilled water contained in a 1000 ml volumetric flask. Stir until the
-2
NaF is completely dissolved. The resulting solution is 1 x 10 M in F
or 190 ppm.
7.0 Procedure
7.1 Pre-distillation, Preparation of the Sample
The sample from absorption of gaseous fluorides is generally eva-
porated down to a convenient volume of 15-20 ml. This evaporation also
serves to concentrate the fluoride. No other preparation of this sample is
needed prior to the steam distillation procedure. A blank should be run in
parallel with the sample. If the occurance of interferences has been
demonstrated to be low and fluoride is present in significant concentration,
then an aliquot of the sample as received may be taken and the distillation
step omitted.
7.2 Steam Distillation Procedure
Quantitiavely transfer the sample into the distilling flask from its
container using several small quantities of water until the volume is
approximately 30 ml. Using a volumetric pipet, add 15 ml of concentrated
sulfuric acid. Next, add several crystals of silver nitrate. (Pherchloric
acid may be used. However, due to the possible presence of organic carbona-
ceous material, perchloric acid can be extremely hazardous. Satisfactory
results have been obtained using only sulfuric acid).
Place an aliquot of 1.0 ml of 0.1N sodium hydroxide in the distillate
collector to fix the fluoride. Heat the steam generator and the distilling
flask simultaneously with the line between the distilling flask and the
steam generator closed and the steam generator vented to the atmosphere.
Heat the steam generator until steam is emitted into the atmosphere. Heat
the distilling flask to 145°C-140°C and close the atmospheric vent of the
steam generator and open the line to the distilling flask.
As the steam passed through the distilling flask, it will enter the
condenser tube, sweeping with it the fluoride compounds, HF and SiF,.
Both are condensed and collected in a receiving flask. Continue distillation
70
-------
until about 125 ml of condensate has been collected. It is necessary that
the distillation period be of a duration so as to transfer the fluorides
from the distillation flask to the collection flask, but not for such a
long duration that the quantity of fluoride in the collection flask becomes
so dilute that it is below the detection limits of the technique in use.
(If this happens, the fluoride concentration can be increased by slow
evaporation of the excess liquid volume). At this point, the sample is
ready for analysis. The apparatus and glassware are easily contaminated
with fluoride. If there is any possibility that such may have occurred,
distill several 25 ml portions of distilled water checking the condensate
from each run for its fluoride content before distilling any actual samples.
If the samples analyzed have a wide range of concentrations, maintain two
complete sets of glassware, one set for the "low" concentrations of fluoride
and the other for the "high" concentrations of fluoride.
7.3 Detection by Fluoride Ion Selective Electrode
Standard Curve Preparation - Using volumetric pipettes place 0.1, 1.0
and 10.0 ml of the standard fluoride solution in 100 ml volumetric flasks.
These standards contain 0.1, 1.0, and 10.0 |Jg fluoride per ml respectively.
Using 10 ml volumetric pipettes, transfer 10.0 ml of each of the
®
standards to 50 ml polyethylene beakers (TISAB ) and mix thoroughly. Using
the standards according to the manufacturer's instructions span and adjust
the specific ion meter. Sample Analysis - To a 10 ml aliquot of the
prepared sample, add 10 ml of the citrate buffer and measure the millivolts
produced on the meter and compare with the prepared curve.
8.0 Calibration Method
Sodium fluoride will be used to prepare standards for the calibration
of the pH/mv meter as described in Section 7.0. If steam distillation is
used several samples must be distilled to evaluate recovery of fluoride.
An HF permeation tube is available to evaluate the collection efficiency of
the impinger.
71
-------
9.0 Calculations
Gaseous
Mg F~/M3 =
(Cone, of aliquot analyzed) (Total ml in condensate) (Total ml in sample)
2
(M of air) (Aliquot analyzed) (Total ml taken for distillation)
10.0 Effects of Storage
Fluoride reacts with glass, therefore all storage containers must
be plastic. No other special precautions are required.
11.0 References
1. "Determination of Inorganic Fluoride: Adaptation of the Specific
Ion Electrode Method for Measurement of Fluoride Ion in Gaseous
and Vegetative Samples", Adopted November 23, 1971, Texas State
Department of Health, Air Pollution Control Services.
2. Operation Manual for Orion Fluoride Ion Selective Electrode.
Analytical protocol revised 1/24/77.
72
-------
J. ACID MIST SAMPLING AND ANALYSIS IN AMBIENT AIR
1.0 Principle of Method
The acid aerosol is collected by filtration through filter papge. The
collected acids are titrated directly and indirectly to compensate for
neutralization by insolbule bases in the sample.
2.0 Range and Sensitivity
The upper limit is determined by the volume of the buret and titer of
the base used. The lower limit is determined by the sensitivity of the
indicator. For practical purposes this limit is 5 to 10 pg H-SO, per
sample.
3.0 Interferences
Acid gases such as sulfur dioxide, nitrogen dioxide, and carbon dioxide
do not interfere in this method of filtration of acid aerosol. Basic
gases, such as ammonia, may interfere and should be removed prior to filtra-
tion of the sample, if present in appreciable concentration. Particulate
acids such as hydrochloric, phosphoric and nitric acid may be present in
urban air and collected on filter paper. Interference by insoluble bases
is overcome by use of the back titration procedure.
4.0 Precision and Accuracy
Precision and accuracy are dependent upon the precision and accuracy
of the volume measurement of the titrant and the recognition of the end
point. In the low [jg range reproducibility should be 5 to 10% with visual
and point detection. Photometric detection should improve that to 1 to 2%.
5.0 Apparatus
Micro buret
filter paper holder
Pump (Ex. Nutchel Model 221-A, Nutech Corp., Durham, N. C.).
Whatmann No. 1 Filter paper
6.0 Procedure
The acid aerosol is collected by filtration through 1-inch circles of
Whatmann No. 1 filter paper at flow rates up to 30 £/min over periods of 1-
6 hours, depending upon the severity of the existing air pollution.
The filter paper is returned to the laboratory for analysis. The
method of analysis involves titration of the filter papers to pH 7.
-------
Prepare a solution of bromothymol blue in deionized water by adding 4 ml of
a 0.1% solution of the indicator in alcohol to 100 ml of deionized water.
To this solution add sufficient 0.01 N sodium tetraborate to produce a
stable apple-green color (approx. pH 7). Cut the sample filter into two
exactly equal portions, one portion being added to 1-2 ml of this solution
and titrated with the standard tetraborate to the original green color.
Keep a similar beaker containing the same volume of the solution as a
control. Agitate during titration by vigorous swirling. The end point is
reached after about 5 minutes. This end point is shown by a stable green
color identical to that of the control solution.
The amount of acid indicated by this procedure has to be corrected for
water-insoluble bases present in the sample, since some of the acid will
react with these bases. The true amount of acid is found by adding a known
excess of 0.01 N sodium tetraborate (at least 0.1 ml more than the amount
indicated above) to the 1-2 ml of pH 7 solution and then immersing the
second portion of the filter paper in it and titrate the excess with 0.01 N
sulfuric acid.
7.0 Calibration Methods
The titer of the sodium tetraborate is determined against potassium
acid phthalate, a primary standard.
8.0 Calculations
The concentration of acid, calculated as sulfuric acid in micrograms
per cubic meter of air, is as follows:
Mg H2o4 M3 = 98,000 X N X ml
N = normality of sodium tetraborate (0.01 N)
ml - equivalent volume in milliliters of tetraborate solution
to neutralize acid during back titration of half the
filter paper sample
3
V = volume of air sampled (M )
9.0 Effects of Storage
The samples will need to be sealed against acid or basic atmosphere.
Humidity may result in neutralization of sulfuric acid by insoluble bases
in the sample.
74
-------
10. References
I. Arthur C. Stern, Air Pollution, Vol. II, 2nd Edition, 1968, p. 77,
Analytical protocol revised 1/24/77.
75
-------
K. SAMPLING AND ANALYSIS OF VOLATILE HALOGENATED HYDROCARBONS IN SOIL,
SEDIMENT, WATER, VEGETATION AND MILK
1.0 Principle of the Method
Volatile compounds are recovered from an aqueous or solid sample by
warming the sample and purging an inert gas through the warm sample. The
vapors are then trapped on a Tenax cartridge which can be analyzed by
thermal desorption interfaced to GC/MS for the ultimate analysis. The
details of the purge procedure are dictated by the medium being analyzed as
described below.
2.0 Range and Sensitivity
For a typical organic compound approximately 30 ng is required to
obtain mass spectral identification using high resolution glass capillary
GC/MS analysis. Based on a 50 g soil or sediment sample, a limit of detec-
tion of about 0.6 (Jg/kg would be typical. For water and milk, a 100 ml
aliquot is used and the limit is then M).3 |Jg/£. The vegetation sample
size at 5 g permits the detection of compounds at ~6 pg/kg. The dynamic
4
range for a purged sample is ~10 , however, smaller samples may be purged
and the ranged increased commensurately.
3.0 Interferences
Two possible types of interference must be considered: (1) material
present in the sample which physically prevents the effective purge of the
sample, and (2) a material which interferes with the analysis of the purged
sample. In the former case, several techniques have been developed to
handle such problems (e.g., foaming) by diluting and stirring the sample.
The second case is minimized by the use of GC/MS for the analysis since
unique combinations of m/e and retention time can be selected for most
compounds. This permits the evaluation of compounds even though chromato-
graphic resolution is not obtained.
4.0 Precision and Accuracy
The purge and trap technique has been evaluated using six model compounds
which are expected to be typical of volatile halogenated compounds. These
six (1-chloro-l-butene, 1,2-dichloroethane, l-bromo-2-chloroethane, 1,2-
dibromoethane, bromobenzene and m-chlorotoluene) were purged from distilled
water, stream water and soil with recoveries of 60 to 102% for the water
76
-------
samples and 34 to 78% for the soil. Standard deviations for duplicate or
triplicate analyses average 15%.
The precision of the purge step was not separated from the thermal
desorption and apparatus to the GC.
5.0 Apparatus
5.1 Purge Apparatus
Two types of purge apparatus are required such as those shown in
Figure Kl.
5.2 Sampling Cartridges
The sampling tubes are prepared by packing a 10 cm long x 1.5 cm i.d.
glass tube containing 6.0 cm of 35/60 mesh Tenax GC with glass wool in the
ends to provide support (2,5). Virgin Tenax is extracted in a Soxhlet
extractor for a minimum of 18 hours with acetone prior to preparation of
cartridges samplers (2,5). After purification of the Tenax GC sorbent and
drying in a vacuum oven at 100°C for 2-3 hr all of the sorbent material is
meshed to provide a 35/60 mesh size range. Cartridge samplers are then
prepared and conditioned at 270°C with helium flow at 30 ml/min for 30
®
minutes. The conditioned cartridges are transferred to Kimax (2.5 cm x
150 cm) culture tubes, immediately sealed using Teflon lined caps and
cooled. This procedure is performed in order to avoid recontamination of
the sorbent bed (2,5).
5.3 Gas Chromatograpfaic Column
A 0.35 mm i.d. x 100 m glass SCOT capillary column coated with OV-101
stationary phase and 0.1% benzyl triphenylphosphonium chloride is used for
effecting the resolution of the halogenated hydrocarbons and other chemicals
(5). The capillary column is conditioned for 48 hours at 230°C and 1.5-2.0
ml/min of helium flow. For highly polar pollutants of interest an 80 m
Carbowax 20M glass SCOT capillary is used.
A Finnigan type glass jet separator on a Varian-MAT CH-7 GC/MS/COMP
system is employed to interface the glass capillary column to the mass
spectrometer. The glass jet separator is maintained at 240°C (2,5).
77
-------
o
0)
00
0)
T3
C
03
C
0)
•H
13
CU
co
CO
0)
tH
ex
e
OJ
iJ
05
3
4-1
ta
cx
a.
cu
oo
3
P-i
tt
CU
h
60
•H
-------
5.4 Inlet Manifold
An inlet manifold for thermally recovering vapors trapped on Tenax
sampling cartridges is employed and is shown in Figure K2 (1,2,4,5).
5.5 Gas Chromatograph
A Varian 1700 gas chromatograph is used to house the glass capillary
column and is interfaced to the inlet manifold (Figure K2).
5.6 Mass Spectrometry/Computer
A Varian-MAT CH-7 mass spectrometer with a resolution of 2,000 equipped
with a single ion monitoring capabilities is used in tandem with the gas
chromatograph (Figure K2). The mass spectrometer is interfaced to a Varian
620/L computer (Figure K2).
6.0 Materials
6.1 Sampling
Adequate numbers of clean sample containers for the various media to
be sampled. The media and the appropriate containers are listed below:
Soil and sediment - wide mouth, one liter glass bottles with foil
lined caps.
Water - narrow mouth, one liter amber glass bottles with foil lined
caps.
Vegetation - Wide mouth, one liter glass bottles with foil lined caps.
Milk - Tedlar® bags 36 x 36 cm.
6.2 Purge
Tenax cartridges - 16 mm o.d. x 10.5 cm glass tubes filled with six cm
of Tenax with glass wool plugs in each end.
Charcoal cartridges - 16 mm o.d. x 6 cm filled with four cm of charcoal
and glass wool plugs in each end.
Screw cap glass culture tubes.
7.0 Procedure
7.1 Collection of Field Samples
Soil samples are collected by taking cores with a garden bulb planter.
The cores are placed in one liter wide mouth jars and sealed with foil
lined caps. Water samples are collected in one liter narrow mouth amber
jars. Vegetation is collected and stored in one liter, wide mouth jars.
®
Milk is collected in glass and transferred to Tedlar bags and frozen
before shipping.
79
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GLASS
JET
SEPARATOR
MASS
SPECTROM-
ETER
PURG:
GAS
T
TWO
POSITION
VALVE
CESCRPTiCN
CHAMBER
CAPILLARY
GAS f
CH~C.MA7CG~.AFH!
5i_OC;<5
CARRIER
GAS
EXHAUST
CAPILLARY
TRAP
PLCTTE
R
ANALYTICAL SYSTEM
Figure K2. Vapor analytical systems for analysis of organic
vapors in ambient air.
80
-------
7.2 Purge of Volatile Organics
7.2.1 Water Samples
The water sample is cooled to ^4°C and a 100 ml aliquot transferred to
the purge apparatus. The apparatus is assembled as depicted in Figure Kla
including the Tenax GC cartridge (1.5 cm diameter x 6.0 cm length). A
carbon cartridge, 1.5 cm diameter x 4.0 cm length is encountered to the
effluent end of the Tenax cartridge to prevent contamination of the cartridge
by laboratory vapors. The flask is wrapped with heating tape and the
sample heated to 90°C. The sample is purged at 25 ml helium/min and 90°C
for 90 minutes. The loaded cartridge is removed and stored in a culture
tube containing 1-2 g of CaSO, dessicant for at least two hrs. The dessicant
is removed from the culture tube and the dry, loaded cartridge sotred at -
20°C.
7.2.2 Soil and Sediment Samples
The apparatus assembled as depicted in Figure Klb including the Tenax
GC cartridge (1.5 cm diameter x 6.0 cm length). A carbon cartridge, 1.5 cm
diameter x 4.0 cm length is connected to the effluent end of the Tenax
cartridge to prevent contamination of the cartridge by laboratory vapors.
The soil or sediment sample is cooled to ^4°C, 20 g transferred to the 500
ml flask and 450 ml of distilled water added. The mixture is stirred with
a magnetic stirrer, heated to 90° with a heating mantle and purged at 25 ml
helium/min and 90°C for 90 minutes. The loaded cartridge is removed and
stored in a culture tube containing 1-2 g of CaSO, dessicant for at least
two hrs. The dessicant is removed from the culture tube and the dry,
loaded cartridge stored at -20°C.
7.2.3 Raw Milk Samples
The apparatus is assembled as depicted in Figure Klb including the
Tenax GC cartridges (1.5 cm diameter x 6.0 cm length). A carbon cartridge
1.5 cm diameter x 4.0 cm length is connected to the effluent end of the
Tenax cartridge to prevent contamination of the cartridge by laboratory
vapors. The milk sample is cooled to ^4°C, shaken vigorously and 100 ml
diluted with 350 ml distilled water. The pH of the solution is adjusted to
4.0 with sulfuric acid. A glass wool plug is inserted into the center neck
of the flask just above the level of the solution and with the flask in a
81
-------
heating mantle, the solution is heated to 70°C while stirring with a magnetic
stirrer. The sample is purged at 15 ml helium/min and 70°C for 90 minutes.
The loaded cartridge is removed and stored in a culture tube containing 1-2
g CaSO, dessicant for at least two hrs. The dessicant is removed from the
4
culture tube and the dry, loaded cartridge stored at -20°C.
7.2.4 Vegetation Samples (Tentative)
The apparatus is assmbled as depicted in Figure Klb including the
Tenax GC cartridge (1.5 cm diameter x 6.0 cm length). A carbon cartridge,
1.5 cm diameter x 4.0 cm length, is connected to the effluent end of the
Tenax cartridge to prevent contamination of the cartrige by laboratory
vapors. The vegetation sample is cooled to ^4°C. A sample (2 g) is shredded
in 200 ml of cold, distilled water in a blender. The mixture is transferred
to a 250 ml purge flask and a glass wool plug inserted into the center neck
of the flask just above the level of the solution. With the flask in a
heating mantle, the solution is heated to 90°C while stirring with a magnetic
stirrer. The sample is purged at 25 ml helium/min and 90°C for 90 minutes.
The loaded cartridge is removed and stored in a culture tube containing 1-2
g CaSO, dessicant for at least two hours. The dessicant is removed from
the culture tube and the dry, loaded cartridge stored at -5°C.
7.3 Analysis of Sample Purged on Cartridge
The instrumental conditions for the analysis of halogenated hydro-
carbons of the sorbent Tenax GC sampling cartridge is shown in Table Kl.
The thermal desorption chamber and six-port valve are maintained at 270°
and 200°C, respectively. The glass jet separatory is maintained at 240°.
The mass spectrometer is set to scan the mass range from 25-350. The
helium purge gas through the desorption chamber is adjusted to 15-20 ml/min.
The nickel capillary trap at the inlet manifold is cooled with liquid
nitrogen. In a typical thermal desorption cycle a sampling cartridge is
placed in the preheated desorption chamber and helium gas is channeled
through the cartridge to purge the vapors into the liquid nitrogen cooled
nickel capillary trap. After desorption the six-port valve is rotated and
the temperature on the capillary loop is rapidly raised (greater than
10°/rain); the carrier gas then introduces the vapors onto the high resolution
GLC column. The glass capillary column is temperature programmed from 20°
-------
Table Kl. OPERATING PARAMETERS FOR GLC/MS/COMP SYSTEM
Parameter
Setting
Inlet-manifold
desorption chamber
valve
capillary trap - minimum
maximum
thermal desorption time
GLC 100 m glass SCOT-OV101
50 m glass SCOT-Carbowax 20M
carrier (He) flow
transfer line to ms
270°C
220°C
-195°C
+180°C
4 min
20-240°C, 4/C° sin
80-240°C
~3 ml/min
240°C
MS
scan range
scan rate, automatic-cyclic
filament current
multiplier
ion source vacuum
m/e 20 ->• 300
1 sec/decade
300 pA
6.0
-4 x 10~6 torr
83
-------
to 240°C at 4°/min and held at the upper limit for a minimum of 10 min.
After all of the components have eluted from the capillary column the
analytical column is then cooled to ambient temperature and the next sample
is processed (2).
An example of the analysis of volatile organics in ambient air is
shown in Figure K3 and the background from a blank cartridge is Figure
K4. The high resolution glass capillary column was coated with OV-101
stationary phase which is capable of resolving a multitude of compounds,
including halogenated hydrocarbons, to allow their subsequent identification
by MS/COMP techniques; in this case over 120 compounds were identified in
this chromatogram.
7.3.1 Operation of the MS/COMP System (Figure K5)
Typically the mass spectrometer is first set to operate in the repeti-
tive scanning mode. In this mode the magnetic is automatically scanned
exponentially upward from a preset low mass to a high mass value. Although
the scan range may be varied depending on the particular sample, typically
the range is set from m/e 25 to m/e 300. The scan is completed in approxi-
mately three seconds. At this time, the instrument automatically resets
itself to the low mass position in preparation for the next scan, and the
information is accumulated by an on-line 620/L computer and written onto
magnetic tapes of the dual disk system. The reset period requires approxi-
mately three seconds. Thus, a continuous scan cycle of six seconds/scan is
maintained and repetitively executed throughout the chromatographic run.
The result is the accumulation of a continuous series of mass spectra
throughout the chromatographic run in sequential fashion.
Prior to running unknown samples the system is calibrated by introducing
a standard substance, perfluorokerosene, into the instrument and determining
the time of appearance of the known standard peaks in relation to the
scanning magnetic field. The calibration curve which is thus generated
will be stored in the 620/L computer memory. This calibration serves only
to calibrate the mass ion over the mass scanning range.
While the magnet is continuously scanning the sample is injected and
the automatic data acquisition is initiated. AS each spectrum is acquired
by the computer each peak which exceeds a preset threshold is recognized
84
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C3
t-1
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and reduced to centroid time and peak intensity. This information is
stored in the computer core while the scan is in progress. In addition,
approximately 30 total ion current values and an equal number of Hall probe
signals are stored in the core of the computer as they are acquired.
During the three second period between scans this spectral information,
along with the spectrum number, is written sequentially on disks, and the
computer is reset for the acquisition of the next spectrum.
This procedure continuous until the entire GC run is completed. By
this time there are from 300-1,000 spectra on the disk which are then
subsequently processed. Depending on the information required, the data
may then either be processed immediately or additional sampels may be run,
stored on magnetic tape and the results examined at a later time.
The mass spectral data are processed in the following manner. First,
the original spectra are scanned and the total ion current (TIC) information
is extracted. Then the TIC intensities are plotted against the spectrum
number on the Statos 31 recorder. The information will generally indicate
whether the run is suitable for further processing, since it will give some
idea of the number of unknowns in the sample and the resolution obtained
using the particular GLC column conditions.
The next stage of the processing involves the mass conversion of the
spectral peak times to peak masses which is done directly via the dual disk
system. The mass conversion is accomplished by use of the calibration
table obtained previously using perfluorokerosene. Normally on set of the
calibration data is sufficient for an entire day's data processing since
the characteristics of the Hall probe are such that the variation in calibra-
tion is less than 0.2 atomic mass units/day. A atypical time required for
this conversion process for 1,000 spectra is approximately 30 min.
After the spectra re obtained in mass converted form, processing
proceeds either manually or by computer. In the manual mode the full
spectra of scans from the GC run are recorded on the Statos 31 plotter.
The TIC information available at this time is most useful for deciding
which spectra are to be analyzed. At the beginning of the runs where peaks
are very sharp nearly every spectrum must be inspected individually to
determine the identity of the component. Late in the chromatographic run
when the peaks are broader only selected scans need to be analyzed.
-------
Identification of resolved components is achieved by comparing the
mass cracking patterns of the unknown mass spectra to an eight major peak
index of mass spectra (9). Individual difficult unknowns are searched by
the use of the Cornell University STIRS and PBM systems. Unknowns are also
submitted to the EPA MSSS system for identification. When feasible the
identification of unknowns are confirmed by comparing the cracking pattern
and elution temperatures for two different chromatographic columns (OV-101
and OV-17 SCOT capillaries) for the unknown and authentic compounds. The
relationship between the boiling point of the identified halogenated hydro-
carbon and the elution temperature on a non-polar column (the order of
elution of constituents is predictable in homologous series since the OV-
101 SCOT capillary separates primarily on the basis of boiling points) is
carefully considered in making structure assignments.
8.0 Quantitative Analysis
In many cases the estimation of the level of pollutants by capillary
gas chromatography in combination with mass spectrometry is not feasible
utilizing only the total ion current monitor (see Figure K3 for example),
since baseline resolution between peaks is not always achieved. We employ
the techniques which have been previously developed under contract whereby
full mass spectra are obtained during the chromatographic separation step
and then selected ions are presented as mass fragmentograms using computer
software programs which allow the possibility of deconvoluting constituents
which were not resolved in the total ion current chromatogram (6). Examples
are depicted in Figures K6 and K7 which represent an ambient air sample
with a TIC profile as in Figure K3.
In our GC/MS/COMP system we request from the Varian 620/L dedicated
computer, mass fragmentograms for any combination of m/e ions when full
mass spectra are obtained during chromatography. Thus selectivity is
obtained by selecting the unique ion for that particular halogenated hydro-
carbon, and this is represented versus time with subsequent use of that ion
intensity for quantitation. Also, quantitation with external standards is
easily achieved using the intensity of the total ion current monitor or the
use of a unique mass cracking ion in the mass spectrum of that external
standard. Thus, we use mass fragmentography for the quantitation of
89
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halogenated hydrocarbons in ambient air when the total ion current is
inadequate because of a lack of complete resolution between components in
the mixture .
As described previously, the quantitation of constituents in ambient
air samples is accomplished either by utilizing the total ion current
monitor or where necessary the use of mass f ragmentograms . In order to
eliminate the need to obtain complete calibration curves for each compound
for which quantitative information is desired, we use the method of relative
response (RMR) factors (10) . Successful use of this method requires informa-
tion on the exact amount of standard added and the relationship of RMR
(unknown) to the RMR (standards). The method of calculation is as follows:
A . /Moles .
(D RMR = unk unk
unknown/standard A , /Moles ,
std std
A = peak area, determined by integration or triangulation.
The value of RMR was determined from at least three independent
analyses.
A /g /GMW
_ unk unk unk
A = peak area, as above
g = number of grams present
GMW = gram molecular weight
Thus, in the sample analyzed:
A , -GMW , *g ^ ,
_ unk unk °std _
( ' gunk ~ A ,-GMW ,'RMR , , ,
std std unk/std
The standard added can be added as an internal standard during sampling.
However, since the volume or weight of samples for a given analysis taken
is accurately known, it is also possible and more practical to use an
external standard whereby the standard is introduced into the cartridge
prior to its analysis. Two standards, hexafluorobenzene and perfluorotoluene
are used for the purpose of calculating RMR's. From previous research it
has been determined that the retention times for these two compounds are
92
-------
such that they elute from the glass capillary column (OV-101) at a tempera-
ture and retention time which does not interfere with the analysis of
unknown compounds in ambient air samples.
Since the volume or weight of a given sample is accurately known and
an external (or internal) standard is added to the sample, then the weight
can be determined per cartridge and hence the concentration of the unknown.
The approach for quantitating pollutants requires that the RMR is determined
for each constituent of interest. This means that when sample is taken,
the external standard is added during the analysis at a known concentration.
It is not imperative at this point to know what the RMR of each of the
unknown constituents. As the RMR may be determined subsequently and the
concentration calculated in the original sample using the RMR. In this
manner it is possible to obtain qualitative and quantitative information on
the same sample with a minimum of effort.
9.0 Calculations
The g , determined by the RMR technique can be related to the original
sample concentration as follows:
Water and milk iri6
g x 10
ug halogenated hydrocarbon/2 = —?-. ; T-T-T
fa 6 J aliquot taken (£) x purge recovery
Soil, Sediment, Vegetation 6
g , x lu
|jg halogenated hydrocarbon/kg = un
aliquot taken (kg) x purge recovery
Purge recoveries for several compounds and media are given in Table K2.
10.0 References
1. Pellizzari, E. D., Development of Method for Carcinogenic Vapor Analysis
in Ambient Atmospheres. Publication No. EPA-640/2-74-121, Contract
No. 68-02-1228, 148 pp., July, 1974.
2. Pellizzari, E. D., Development of Analytical Techniques for Measuring
Ambient Atmospheric Carcinogenic Vapors. Publication No. EPA-600/2-
76-076, Contract No. 68-02-1228, 185 pp., November, 1975.
3. Pellizzari, E. D., J. E. Bunch, B. H. Carpenter and E. Sawicki, Environ.
Sci. Tech., 9, 552 (1975).
93
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4. Pellizzari, E. D., B. H. Carpenter, J. E. Bunch and E. Sawicki, Environ.
Sci. Tech., 9, 556 (1975).
5. Pellizzari, E. D., Development of Analytical Techniques for Measuring
Ambient Atmospheric Carcinogenic Vapors, 1976, in preparation.
6. Pellizzari, E. D., J. E. Bunch, R. E. Berkley and J. McRae, Anal.
Chem., 48, 803 (1976).
7. Pellizzari, E. D., Quarterly Report No. 1, EPA Contract No. 68-02-
2262, February, 1976.
8. Pellizzari, E. D., J. E. Bunch, R. E. Berkley and J. McRae, Anal.
Lett., 9, 45 (1976).
9. "Eight Peak Index of Mass Spectra", Vol. L (Tables 1 and 2) and Vol.
II (Table 3), Mass Spectrometry Data Centre, AWRE, Aldermaston, Reading,
RF74PR, UF, 1970.
10. Pellizzari, E. D., Quarterly Report No. 3, EPA Contract No. 68-02-2262,
in preparation.
95
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L. SAMPLING AND ANALYSIS OF SEMI-VOLATILE HALOGENATED HYDROCARBONS
IN AIR, SOIL, SEDIMENT, WATER AND BIOTA
1.0 Principle of the Method
Air-borne particulate are collected on glass fiber filters using Hi-
Vol samplers. The glass fiber filter is then subjected to solvent extraction
and analyzed by one of several gc or thin-layer techniques. Other media
such as soil, sediment, water and biota are solvent extracted and with the
exception of biota which is submitted directly to the analytical technique
of choice. The analytical technique is a function of compound to be analyzed.
Techniques were developed specifically for TRIS, Decabrom, Tetrabrom,
Firemaster 680 and brominated phenols. All of these compounds can be
analyzed by gc/ms with multiple ion detection, however, substantially
better limits of detection for TRIS are obtained using glc/ecd for its
analysis. Some biota samples such as milk are purified using gel permeation
before gc/ms analysis. Thin-layer chromatography is also used for the
analysis of TRIS and Decabrom.
2.0 Range and Sensitivity
The range and sensitivity of an analysis for semi-volatile halogenated
compounds depends upon the specific compound and the matrix from which it
is derived. Table LI indicates these parameters for the five example
compounds. Biota samples such as milk, hair, and placenta are very special
cases since they require additional purification for analysis. The high
lipid content of these samples reduces the sensitivity of any of the analy-
tical methods to approximately 0.1 (Jg/8 or higher depending upon the sensi-
tivity of the instrumental method to that particular compounds.
3.0 Interferences
The extent of interference with the gc/ms detection of these compounds
is a function of the molecular weight and principle ions of the compound
under investigation. For compounds such as Decabrom where the molecular
weight is very high and unique isotope clusters are clearly evident, there
is very little problem with interference, however, for a compound such as
Firemaster 680 where the parent ion cluster is relatively weak and a lower
molecular weight must be monitored for low detection limits interferences
become more pronounced. The very low sensitivity of the quadrupole mass
96
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spectrometer to TRIS is further complicated by the fact that the principle
ions are quite common. No apparent background has been observed using the
gc/ecd method for TRIS. Tetrabrom and pentabromophenol are less subject to
interference than Firemaster 680 due to their early elution time and relati-
vely high molecular ion. The thin-layer procedure for Decabrom is subject
to some interference and in particular with the soil extracts. This parti-
cular aspect is the most serious limitation of that approach to analyzing
Decabrom. There is one additional problem with the thin-layer procedure
and that is lack of resolution between Decabrom and polybrominated biphenols.
The thin-layer feature developed for the analysis of TRIS is subject to
interference from other brominated compound but non-brominated compounds
present little interference in this method.
4.0 Precision and Accuracy
For the glc/ms/comp analysis, an estimation of the precision of the
analytical method may be assessed by the standard deviation of response
factors generated from standard samples. Over a nine-day period, 21
separate determinations of the five selected compound yielded at
relative standard deviation of 24%. Actual results are somewhat better
than this since there is day-to-day variation in the instrument response.
By running calibration standards on a daily basis, this element of variation
is removed.
Estimation of accuracy is based upon knowledge of the range of recover-
ies and instrumental accuracy. The standardization of the gc/ms/comp
system was based on three sets of standard mixtures at varying relative
concentration to the internal standard. The variability between these was
no larger than day-to-day instrumental sensitivity and variations. The
recoveries from each of the matrices analyzed were determined for some of
these compounds. These recoveries are summarized in Table L2. With the
exception of EDB in soil, the recoveries were generally 80% or better than
100%.
5.0 Apparatus
5.1 Sampling Apparatus
5.1.1 Air
General Metals Works Model GMWL-2000
High Volume Air Sampling System or equivalent
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5.1.2 Water, Sediment, Soil and Biota
Garden bulb planter
Dipper for obtaining water samples in remote places
5.2 Sample Extraction And Purification
5.2.1 Air
Ultrasonic bath or reciprocal shaker
5.2.2 Water, Sediment and Soil
Reciprocal shaker
Separatory Funnels (250 ml)
Kuderna-Danish Evaporators
5.2.3 Biota
Centrifuge (clinical)
Kuderna-Danish Evaporators (micro)
Virtis homogenizer or equivalent Soxhlet evaporator (250 ml capacity)
High Pressure Liquid Chromatograph with variable wavelength uv
detector, refractive index desirable but not essential.
o
Gel permeation column: pStyragel, 500 A 27 cm in length.
5.3 Extract Analysis
5.3.1 GC/MS/COMP Analysis
GC/MS/COMP system capable of operating in the multiple ion detection
mode GC columns 0.2 cm i.d. x 42 cm packed with 2% OV-101 on Chromosorb
W(HP) [100/120 mesh].
5.3.2 GC/ECD Analysis
Gas chromatograph with electron capture detector (on column injec-
tion) .
Columns:
1. 0.2 cm i.d. x 42 cm glass column packed with 2% SE-30 on
Chromosorb W(HP) (80/100 mesh)
2. 0.2 cm i.d. x 42 cm glass column packed with 3% OV-17/0.5%.
Benzyltriphenyl phosphonium chloride (BTPP Cl) Chromsorb W(HP)
[100/120 mesh].
100
-------
3. 0.2 cm i.d. x 170 cm glass column packed with 3% Carbowax
20M on Chrom G AW/DMCS (100/120 mesh).
4. 0.2 cm i.d. x 42 cm glass column packed with 2% OV-101 on
Gas Chrom Q (100/120 mesh).
5.3.3 TLC/SD Analysis
Developing Chambers
Spotting Apparatus
Scanning densitometer e.g. the Schoeffel SD3000 Spectrodensitometer
6.0 Materials
Authentic samples of the compounds under analysis.
6.1 Sampling
6.1.1 Air
Gelman Type A glass fiber filters 20 x 25 cm
Aluminum Foil
®
Ziphok bags
Mailing Tuber
6.1.2 Water
Narrow mouth 1 £ amber glass bottles with foil-lined caps.
6.1.3 Soil and Sediment
Wide mouth 1 S, glass bottles with foil-lined caps.
6.1.4 Biota
®
Tedlar bags 36 x 36 cm (milk)
Wide mouth 500 ml glass bottles (placenta)
Wide mouth 1 S. glass bottles (hair)
6.2 Sample Extraction
Separatory funnels (250 m£)
Graduated cylinders (100 and 240 m£)
1 £ glass bottles
500 ml round bottom flasks
Other general glassware
Solvents - Toluene, hexane, ethyl ether, acetone (redistilled
or "distilled in glass")
6.3 Analytical Procedures
Carrier Gases
Solvents for TLC
101
-------
7.0 Procedure
7.1 Collection of Samples
7.1.1 Air
Locate a suitable power source for the Hi-Vol sampler. Place a glass
fiber filter in the holder making sure there are no holes in it. Turn on
the sampler and observe the flow rate. If the flow rate is normal for that
sampler (40-60 cfm) record the time and flow rate and continue sampling for
24 hrs. Lower the roof of the shelter to protect from rain, etc. At the
end of the sampling period, observe and record the time and flow rate.
Turn off and remove the filter folding the sample sides together. Wrap the
folded filter in foil, label and roll into a shape which will fit in a
mailing tube.
7.1.2 Soil
Soil samples are collected by taking cores with a garden bulb planter.
The cores are placed in one liter wide mouth jars and sealed with foil
lined caps. The sample is labeled and its location and other pertinent
data recorded on a protocol sheet.
7.1.3 Water and Sediment
Water samples are 1 S, grab samples acquired by filling 1 H amber
narrow mouth bottles by immersion or ladeling depending upon accessibility.
Sediment samples are obtained by coring where the sediment is firm or by
scooping if coring is not possible.
7.1.4 Hair and Placenta
Hair samples are composited at the site in a wide mouth 1 JH bottle.
With the cooperation of the barber, the number of individuals contributing
to the composite is recorded as the sample is added to the jar. A well
filled 1 SL bottle will contain approximately 15 g of hair.
Placenta and cord samples are obtained by supplying an attending
physician with 500 ml or 1 £ wide mouth bottles. Collected samples must be
refrigerated or preferably frozen.
7.1.5 Milk
Milk is collected in 1 £ wide mouth bottles and transferred to 1 £
®
Tedlar bags before being frozen.
102
-------
8.0 Extraction and Purification
8.1 Air Samples
The glass fiber filter samples are carefully cut into 4 x 10 cm segments
taken from the central area of the filter. The segments are then further
cut into narrow strips (~5 mm wide). These are placed in 20 ml vials along
with 10 ml acetone and sonicated in an ultrasonic bath for 30 min. The
extraction can also be accomplished on a reciprocal shaker at ^120 cpm for
2 hrs. An aliquot of the supernatant is drawn off for analysis.
8.2 Water Samples
Two parallel extractions are performed, one, a hexane extraction, for
a volatile fraction such as ethylene dibromide (EDB), and the other, a
toluene extraction, for more polar, less volatile compounds such as decabromo-
biphenyl ether and TRIS.
8.2.1 Hexane Extraction of Water
An aliquot of 100 ml of sample is placed in a 250 ml separatory funnel.
Hexane (10 ml) is added, the funnel stoppered and shaken for 30 minutes.
The phases are allowed to separate for at least 5 minutes. The aqueous
layer is drained into another separatory funnel and the hexane into a 50 ml
Erlenmeyer flask. Repeat the hexane extraction above two additional times
combining the hexane extracts. Dry the hexane extract over Na?SO,. The
extract may be analyzed directly by GC/ECD or the volume reduced to 5 ml in
the K-D apparatus for other analyses.
8.2.2 Toluene Extraction of Water
An aliquot of sample (200 ml) is placed in a 250 ml separatory funnel
and 20 ml of toluene added. The funnel is shaken for 30 minutes and then
allowed to stand for 5 minutes for the phases to separate. The aqueous
layer is drained into another separatory funnel and the toluene into a 100
ml Erlenmeyer flask. The toluene extraction is repeated two additional
times combining the extracts. The extracts are dried over Na.SO,, transfer-
red to a round bottom flask (500 ml) with 5-10 ml toluene wash and evaporated
using a Snyder column to a final volume of 5 ml. All procedures are carried
out under minimum lighting and samples are stored in the dark at 5°C.
103
-------
8.3 Soil and Sediment Samples
Composite 1/2 of top 2.5 cm of soil core and place in 1 H wide mouth
jar with other samples to be composited and cap with foil-lined cap.
Agitate vigorously to produce a homogeneous sample. A 50 g portion of the
composite is then extracted in a 1 £ wide mouth jar with 50 ml of diether
ether (shake for 30 minutes). Decant the ether extract through glass wool
into a Kuderna-Danish (K-D) apparatus and combine with subsequent extracts.
The soil residue is then treated with acetone (40 ml) and shaken for
20 minutes. Toluene (80 ml) is added and shaken for 10 minutes. The
extract is decanted through a glass wool plug into a 500 ml round bottom
flask. The above acetone-toluene extraction is repeated a total of 2 times
and the extracts concentrated by heating the round bottom flask with a 3
ball Synder column attached. The final volume was adjusted to 5 ml. All
procedures are conducted under minimum light and samples are stored in the
dark at 5°C. These extracts are used in several analytical methods described
below.
8.4 Milk Samples
8.4.1 Extraction
Weigh a 10 g sample of well mixed milk. Mix with clean glass wool and
precipitate the proteins by adding 100 ml of acetone. Centrifuge if
necessary to facilitate separation. The acetone is removed and filtered as
are two additional 25 ml acetone washes. The volume of the acetone is
reduced to "^20 ml using a Snyder column. Wash the remaining precipitate
with 2 portions of toluene (10 ml each). The toluene and acetone fractions
are combined. The resulting two phases are separated and the aqueous phase
discarded. The organic phase is dried over sodium sulfate and the volume
reduced to ^5 ml.
8.4.2 Purification
In order to remove the bulk of the butterfat from the extract gel
permeation chromatography is used. Using toluene as a solvent establish
the retention time/volume of the compounds of interest especially the
highest molecular weight compound Decabrom. Using blank milk extract
determines the profile of the butterfat in the extract These retention
volumes may vary somewhat from column to column and even in time if column
104
-------
efficiency changes. The instrument and column are described under 5.2.3.
The absorbance is monitored at 300 nM to avoid the solvent cutoff at ^290
nm. Refractive index is very useful especially for compounds such as TRIS
which have no uv absorbance. Once chromatographic performance has been
established samples containing octachloronaphthalene internal standard
chromatographed using as large an injection as is compatible with resolution
(M).5 ml). Collect the effluent starting before the earliest eluting
compound (Decabrom) and continuing past the last compound (Tetrabrom).
Repeated injections are made until sufficient material has been collected
for analysis. The fractions are combined and the volume reduced for analysis,
8.5 Hair Samples
Weighed samples (^15 g) were soxhlet extracted with toluene for 16 hrs
and the volume reduced to 5-10 ml using a Snyder column to avoid losses.
Aliquots (0.5 ml) were evaporated to dryness and weight to determine as an
internal standard. These aliquots were redissolved and purified using high
o
performance liquid chromatography on a pStyragel (500A) column with toluene
as a solvent. Prior to sample analysis the elution volumes of several
marker compounds were established (Decabrom and Firemaster 680) and these
elution vaolumes were used to select the fraction collected. Two injections
of 50 to 100 pi of extract (^-4-8 rag of hair oil) were made of each sample.
The fractions from each sample were combined and the volume reduced for
submission to GC/MS/COMP analysis. The sample GLC/MS analysis conditions
were used as for the soil and sediment samples.
8.6 Placenta Samples
Weighed samples of tissue (^10 g) were homogenized with 100 ml of
acetone using a Virtis blender. Otherwise the procedure for extraction was
the same as for milk (see 8.4.1). HPLC clean-up is not useful with these
samples.
9.0 Instrumental Analysis
9.1 GC/ECD
Gas chromatography-electron capture was used for the determination of
TRIS and for screening of other compounds. Two columns were used for TRIS,
SE-30 and OV-17 (see section 5.3.2). These columns were also applicable to
other compounds such as Tetrabrom, Firemaster 680 and Bromophenols. The
105
-------
temperature of the column and injector must be optimized for each compound,
however this optimization is extremely important for TRIS. TRIS is subject
to thermal degradation hence the lowest possible injection temperature, on
column injection and minimum column temperature are required. Typical
chromatograms are shown in Figures LI and L2 with the conditions. Since
the SE-30 column may be operated at a lower temperature, it is the column
£ o o
of choice. Both Ni and H detectors have been used successfully in
detecting TRIS. The detection limit is used not to the detector sensitivity
but to column losses.
Hexane extracts of water samples are screened for the possible presence
of EDB and DEC using the Carbowax 20M column (see 5.3.2) and ECD. For EDB,
the column temperature is 90°C, injector 110°C and for DEC 160° and 180°,
respectively.
9.2 GC/MS/COMP
9.2.1 Instrumentation - Finnigan 3300 GC/MS with PDF/12 Computer
The Finnigan 3300 mass spectrometer has a mass range of 1000, with
unit resolution over the entire range. Calibration of the system is routinely
performed with PC-43 for lower mass ranges and tris(perfluoroheptyl)-a-
triazine in the higher ranges.
The PDP/12 computer is on-line with the Finnigan system. Long term
storage of data is on LINC tapes or removable disc packs. The computer can
subsequently treat sotred data in several different ways to facilitate
interpretation: (a) a reconstructed gas chromatogram is routinely made to
obtain retention times; scan number for a given gas chromatographic peak is
obtained by operator interaction with a CRT display; (b) any given mass
spectrum or an entire series of scans are corrected for background signal
(column bleed, septum bleed, etc.); (c) plots of intensities of specific
ions (mass fragmentography) are made from the scan data. This type of
information is often useful, when correlated with retention time data, for
simplifying the identification of particular compounds. Peak areas are
also readily obtainable from these mass chromatograms and can be used to
provide quantitative information; (d) normalized mass spectra are plotted,
using different types of normalization or amplification factors in order to
facilitate identification; (e) hard copy output of normalized data in
106
-------
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Pulse = 100/u sec
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3% SE - 30 on
100/120 mesh
Chromosorb W (HP)
det
= 200° C
» 290° C
Tinj = 215°C
IM2 flow
30 cc/min
,63
2468
Time (min)
Figure L2. Gas liquid chromatography/electron capture detection
of (a) an acetone extract of the Hi-Vol glass fiber filter
sample collected 12/22/76 - 12/23/76 at Michigan Chemical
Corp., El Dorado, AK and, (b) a TRIS standard (0.8 ng) .
108
-------
digital form, with various forms of background correction, is also avail-
able.
The GC system in use on the Finnigan mass spectrometer is a Finnigan
9500.
The basic hardware of the PDP/12 consists of an 8K central processor
fitted with a teletype, random access disc, CRT display and electrostatic
printer/plotter. The interface to the mass spectrometer was custom-designed
and built and consists of both analog to digital as well as ditital to
analog interfaces. The latter involves several unique concepts in interface
design, since by using this system it is possible to put the entire mass
spectral scanning operation under computer control. Since the data acquisi-
tion phase of the spectrometer operation is controlled entirely by the
computer, a large number of different types of acquisition protocols have
been implemented. For example, in the multiple ion detection mode, up to
nine individual peaks can be selected within the entire mass spectral
range, and acquired for varying time intervals as selected by the operator.
In the repetitive scanning mode, scna intervals down to one scan per second
are possible with entire scans recorded either on LING tapes or disc.
All data processing operations are carried out interactively by mans
of programs stored on the small computer.
9.2.2 Operating Parameters for Multiple Ion Detection - Screening
and Quantitation
In order to obtain compact peak of late eluting compounds such as
Decabrom and avoid decomposition of TRIS a short column was utilized. The
column, 45 cm x 0.2 cm i.d. glass column packed with 2% OV-101 on Gas-Chrom
Q was temperature programmed from 220°C to 300° at 12°/min. Table L3
lists the compounds, the ions and the retention times for each. The samples
are run using the "First" ions and as many of the "second" ions as possible.
If ions are found having the correct retention time and ratio of intensities
where more than one ion for a given compound is monitored, further analyses
are performed. If sufficient material is present, the sample is analyzed
in the full scan mode to confirm the identity of the brominated compound.
If too little of the compound(s) is present, then additional MID analyses
are performed selecting additional ions and comparing their intensity
ratios with those of authentic compounds.
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Quantitation was achieved by comparing the computer-calculated integra-
ted area of the brominated compound with the integrated response for a
known amount of octachloronaphthalene. To compensate for differences in
ionization cross-section, the relative molar response of authentic compounds
was obtained.
The calculation of the relative molar response (RMR) factor allows the
estimation of the levels of sample components without establishing a
calibration curve. The RMR is calculated as the integrated peak area of a
known amount of the compound, A° , , with respect to the integrated peak
area of a known amount of standard, A° , (in this case octachloronaphthalene),
according to the equation
R A°/m°leS (AO} (mS)
-
unkunk unk unk Std (Eq.
~
From this calculated value, the concentration of an identified compound in
a sample is calculated by rearranging Equation 1 to give
(Aunk} (msunk) (gstd) (Eq. 2)
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9.3 Thin-Layer Chromatography
9.3.1 Decabrom
Samples and standards are spotted in alternate channels of 20 x 20 cm
scored silica gel G-plates (Brinkman F?t-,). The plate is developed in 10%
toluene:90% hexane. After air drying the plate is can on Schoeffel scanning
densitometer in the reflectance mode. The excitation is optimal at 240 nm
with unfiltered emission. Examples of standards of Decabrom are shown in
Figure L3. Quantitation is obtained by comparing unknowns to standards on
the same plate. Linearity is obtained from 50 to 1000 ng/channel with a
correlation coefficient of 0.996.
9.3.2 TRIS by TIC
Silica gel TLC plates (20 x 20 cm) are prepared by immersing in a
solution of 0.033% fluorescein (acid) in ethanol/acetone 2:1. The plates
are air dried and scored in 1 cm channels. Samples and standards are
spotted in alternate channels and the plate developed in methylene dichloride.
The plates are air dried before spraying liberally with a 1:1 mixture of
glacial acetic acid/30% hydrogen peroxide. The plate is then heated at
^100°C in the hood. The spray and heat operations were repeated. Rose-
pink spots are visible where >1 |jg of TRIS is present. The plate is then
scanned on a Schoeffel scanning spectrodensitometer with emission at 520 nm
and exictation at 380 nM. The spots appear as quenching of the fluorescein
fluorescence. Figure L4 shows examples of chromatograms obtained in this
manner. Quantitation is obtained by comparing peak areas of unknowns to
standards on the same plate. Linearity extends from 0.2 to 5 pg TRIS per
spot.
113
-------
Figure L3. Thin layer chromatograms of Decabromobiphenyl ether on
silica gel fluorescence quench mode: a. 500 ng Decabrom,
b. 200 ng Decabrom, c. 100 ng Decabrom.
114
-------
70
60
50
40
30
20
10
Excitation: 380 nm
Emission'- 520nm
Slits 2x3 mm
Silica Gel treated with
Fluorescsin developed in
methylene chloride.
TLC SCAN IN FLOURESCENCE QUENCH MODE
TRIS
TRIS
Figure L4. Thin layer chromatogram of tris(2,3-dibromopropyl)-
phosphate on fluorescein impregnated silica gel,
solvent: methylene chloride. Scan in fluorescence
quench mode. a. 3.7 yg TRIS, b. 0.44 yg TRIS.
115
-------
M. OZONE MEASUREMENTS
INSTRUMENTATION
Ambient ozone concentrations were measured using a Bendix Model 8002
chemiluminescent ozone analyzer. The Bendix Model 8002 ozone analyzer (S/N
301469-1) is an EPA Designated Reference Model (RFOA-0176-007) and was
operated on the 0-0.5 ppm range with a 40-sec time constant. The principle
of operation of this instrument is based on the flamess gas-phase chemilumi-
nescent reaction between ethylene and ozone. The reliability, stability,
specificity, and precision of ozone measurements by this reference method
have been adequately demonstrated in numerous studies and described in the
literature.
CALIBRATION
Dynamic multipoint calibration of the Bendix analyzer was accomplished
by use of an ultraviolet ozone generator that was referenced to a NBS-SRM
(NO in nitrogen) by gas phase titration with excess ozone. Normal gas
phase titration could not be used, due to failure of the NO analyzer that
A
is required for this procedure. A complete description of this procedure
is provided separately. Primary dynamic calibrations were performed on the
analyzer prior to and at the conclusion of the monitoring program. Daily
zero and span checks were also performed by the instrument operator to
assure adequate instrument performance on a daily basis.
116
-------
CALIBRATION PROCEDURE USING GAS PHASE TITRATION WITH EXCESS 03
Major equipment required: Stable ozone generator
NO concentration standard
Ozone Analyzer
Strip chart recorder, and
Bubble flowmeter or wet test meter
1. Principle
1.1 The calibration procedure is based upon the rapid gas phase
reaction between ozone (0~) and nitric oxide (NO) in accordance with the
following equation: (1)
NO + 03 -» N02 + 02
The quantitative nature of this reaction is such that the amounts of NO and
0- reacted are equivalent. Nitric oxide is added to 0_ in a dynamic system,
and the chemiluminescent 0« analyzer being audited is used as an indicator
of changes in 0_ concentration. The decrease in 0~ response indicator of
O *3
changes in 0., concentration. The decrease in 0~ response observed on analyzer
is equivalent to the concentration of NO added. By measuring this decrease
in response and the initial response, the 0- concentration can be determined.
Additional 0» concentrations are generated by a dilution technique. The
dynamic system is designed to produce locally high concentrations of
0_ and NO in the reaction chamber, with subsequent dilution, to insure
complete NO reaction with relatively small chamber volumes. Errors can result
if flow conditions in the dynamic calibration system are not correct. Erro-
neous results can also occur if the analyzer response is non-linear.
2. Apparatus
Figure Ml a schematic of a typical GPT apparatus, shows the suggested
configuration of the components listed below. All connections between
components in the calibration system downstream from the 0_ generator
should be glass or Teflon. Additional information regarding the assembly
of a GPT calibration apparatus is given in Reference (2).
2.1 Air flow controllers. Devices capable of maintaining constant
air flow within +2%.
117
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2.2 NO flow controller. A device capable of maintaining constant NO
flow within +2%. Component parts in contact with the NO must be of a non-
reactive material.
2.3 Air flowmeters. Properly calibrated flowmeters capable of measur-
ing and monitoring air flows within +2%.
2.4 NO flowmeter. A properly calibrated flowraeter capable of measur-
ing and monitoring NO flows within +2%. (Rotameters have been reported to
operate unreliably when measuring low NO flows and are not recommended.)
2.5 Pressure regulator for standard NO cylinder. This regulator must
be non-reactive internal parts and a suitable delivery pressure.
2.6 Ozone generator. Capable of generating a stable level of 0_ at
the flow rates required (see 4).
2.7 Reaction chamber. A glass chamber for the quantitative reaction
of NO with excess 0_. The chamber should be of sufficient volume (VD )
J Ku
such that the residence time (t_J is as specified in 4.
K
2.8 Mixing chamber. A glass chamber of proper design to provide
thorough mixing of reaction products and diluent air. The residence time
is not critical when the dynamic parameter specifications given in 4 are
met.
2.9 Output manifold. The output manifold should be constructed of
glass or Teflon of sufficient diameter to insure a minimum pressure drop at
the analyzer connection. The system must have a vent designed to insure
atmospheric pressure at the manifold and to prevent ambient air from enter-
ing the manifold.
3. Reagents
3.1 NO concentration standard. Cylinder containing 50 to 100 ppm NO
in N . The cylinder must be traceable to a National Bureau of Standards NO
in N Standard Reference Material (SRM 1629). The cylinder (working
standard) should be recertified on a regular basis as determined by the
local quality control program. (See Reference (2).
119
-------
3.2 Zero Air. Air, free of contaminants which will cause a detect-
able response on the 0« analyzer or which might react with either NO or 0~
in the gas phase titration. A procedure for generating zero air is given
in Reference (2).
4. Dynamic Parameter Specifications
4.1 The residence time (tR) in the reaction chamber and the gas flows
(F- and FKfJ (see Figure 1) must be adjusted according to the following
relationships:
PR = [03] x tR = 1.5 ppm-minutes
[°3]RC = [°33OUT
VRC
'R-^* FNO
where
PD = Dynamic specifications, determined empirically, to insure com-
ix
plete reaction of NO, ppm-minutes
[00]D_ = 0- concentration in the reaction chamber, ppm
j KL j
tR = Residence time in the reaction chamber, minutes
[0«]-IJT = 80% URL concentration of 0,. at the output manifold, ppm
FT = Total flow at the output manifold, scm /min
1 3
F^ = Ozone generator air flow, scm /min
FWD = NO flow, scm /min
Vno = Volume of the reaction chamber, scm .
KL
4.2 These parameters may be selected according to the following
sequences:
(a) Determine FT, the total flow required at the output manifold
(FT = analyzer(s) demand plus 10% to 50% excess).
(b) Determine [Oo]rmT as the 80% URL (upper range limit) concentra-
tion required at the output manifold.
120
-------
(c) Determine F.m as
NO
0.8 x [03]OUT x FT
NO - [NO]STD
where:
[NO] _n = Concentration of the undiluted NO standard, ppm.
o iU
(d) Select a convenient or available reaction chamber volume. Ini-
tially, a trial V may be selected to be in the range of approximately 300
3
to 1500 scm .
(e) Computer Fn as
V
[°3]OUT X FT X \C
FQ = 1.5 NO
(f) Compute t^ as
K
VRC
- F0 + FNO
(g) Compute Fn as
F = F - F - F
*D *T 0 *NO
where:
3
FD = Diluent air flow, scm /min.
(h) If F_ turns out to be impractical for the desired system, select
a reaction chamber having a different VD and recompuete F and Fn. For a
KL U u
more detailed discussion of these requirements and other related considera-
tions as well as example calculations, reference to Reference (2). A pro-
cedure for the initial checkout of the GPT system and the dynamic parameter
specifications given above is also included in Reference (2).
5. Procedure
5.1 Assemble a dynamic calibration system such as shown in Figure 1.
5.2 Establish the dynamic parameters as indicated in 4. Use a bubble
flowmeter or wet test meter to measure flow through the generator (F~) and
121
-------
total flow out (FT). Record FO and FT on the data sheet. Record generator
flow controller setting on the data sheet.
5.3 Insure that all flowmeters are properly calibrated under the
conditions of use against a reliable standard such as a soap-bubble meter
or wet-test meter traceable to NBS. All volumetric flow rates should be
corrected to 25°C and 760 torr. Flow rates measured with a wet test meter
or bubble flowmeter should be corrected for water vapor pressure. The
corrected flow rate can be determined as shown below.
F
m
= 7
C
where:
F = flow rate as measured with a bubble flowmeter or wet test meter
m
P. = ambient air pressure
PM = water vapor pressure
POTr. = standard pressure 760.0 torr at 29.92" Hg
u 1JJ
T. = ambient temperature °K
T _n = standard temperature °K = 298
O 1JJ
Fp = corrected flow rate.
A detailed discussion on proper calibration of flowmeters is given in
Reference (2).
5.4 Precautions must be taken to remove 0 and other contaminants
from the NO pressure regulator and delivery system prior to the start of
calibration to avoid any conversion of the standard NO to N0~ . Failure to
do so can cause significant errors in calibration. This problem may be
minimized by (1) carefully evacuating the regulator, when possible, after
the regulator has been connected to the cylinder and before opening the
cylinder valve; (2) thoroughly flushing the regulator and delivery system
with NO after opening the cylinder valve; (3) not removing the regulator
from the cylinder between calibrations unless absolutely necessary. Further
discussion of these procedures is given in Reference (2).
5.5 Allow sufficient time for the 0., analyzer to warmup and stabilize.
Adjust the diluent air and 0 generator air flows to obtain the flows
122
-------
determined in step 4.2. Record the 0» generator air flow (Fn) , £>„ generator
flow control setting and total flow out (FT). The total air flow (F_ +
F^ + F = F_) must exceed the demand of the analyzer under calibration to
insure that no ambient air is pulled into the manifold vent. Advance the
recorder chart a couple of inches from the last ambient air trace and allow
the 0_ analyzer to sample zero air until a stable response is obtained.
Record the unadjusted recorder response (Z ) for calibration zero air and
for interval zero. Record analyzer response to internal span.
5.6 Adjust the 0 generator to generate an 0., concentration of approxi-
mately 80% of the URL as measured on the 0 analyzer. When the response
has stabilized, record as I0,,.
oU
5.7 Turn the NO flow on and ajust until the 0» analyzer response has
«J
been decreased by 75-80 percent of its original value. For example, if
IOA = 80% of URL, the NO flow should be adjusted to give a resultant
ou
analyzer response of 16-20% of the URL. When the resultant response has
stabilized, record as I.
5.8 Measure the NO flow and record as F-, . Record the cylinder NO
concentration and flow control setting on the data sheet.
5.9 Calculate the exact NO concentration from:
rN01 FNO X [NQ1STD
[NO] =
TIO 0 D
where:
[NO] = Diluted NO concentration, ppm
5.10 Calculate the 0 concentration from:
[03]ouT > ir—r^ s x [NO]
(l X F°+ F° ) -
V80 FNO + F0 + FD/
-------
where:
0 concentration, ppm
I0rt = Original 0 analyzer response, % chart
ou j
I = Resultant 0. analyzer response after addition of NO, % chart
(10) is usually small and may be ignored by using equation
(11).
5.11 Record calculations on the data sheet.
Remove the NO flow. The 0^ analyzer response should return to its
original value. Record the unadjusted response Ion. Calculate the percent
ou
audit error and record the PAE.
R(% chart - Z )
8° = -t
where:
PAE = Percent Audit Error
R = Full Scale Range
% chart = Percent chart recorder response to 0
[0-Jon = GO concentration, ppm, generated at 80% URL
j ou j
ZTJ = % recorder response for zero offset.
5.12 Adjust the dilution blow control to give an 0 concentration of
•J
60% URL. Using a soap-bubble meter or wet-test meter, measure the new
total air flow at the outlet of the calibrator. Record the total air flow
(F, ) , NO flow control setting and dilution flow control setting.
where:
[0 ]fi = 60% URL 0 concentration, ppm
[0 ] = 80% URL 0 concentration, ppm
F- = original total air flow, cm /minute
FI = total air flow upon dilution, cm /minute
Record calculations and the recorder response (Ifin) on the data sheet.
124
-------
5.13 Calculate the percent audit error and record the PAE.
R(% chart - Zp)
(PAE)6Q
5.14 Readjust dilution flow to give the original total air flow (F«).
5.15 Adjust the UV lamp setting on the 0 generator to give an CL con-
centration of approximately 40% of the URL and repeat the RGPT procedures
(steps 5.6 through 5.13) substituting I,_ for !„ .
5.16 Adjust the dilution flow to give a total on 0 concentration of
20% URL. Using a soap bubble meter or wet-test meter, measure the total
air flow at the outlet of the calibrator. Record the total air flow (F,.,)
on the data sheet. Calculate the diluted C- concentration (lO-Jonl from:
0.8 x [03]QUT x FT
ND '
V
To 1 v- f v V
L 3JOUT T RC F.Tri
— NO
FQ = 1.5
VRC
'NO
PR - [°3]RC X TR
= F - F - F
D t 0 NO
-------
[NO] =
FNO X [NO]STD
FNO + F0 + FD
[0,]
OUT
x [NO]
- 1
F0 + FD
C°3]GEN
[°]
F0 + FD
3JOUT V F
0
[°3]OUT " [°33GEN I FQ +. FT
126
-------
SECTION B: ATMOSPHERIC DISPERSION MODELING
-------
ATMOSPHERIC DISPERSION MODELING
>
An assessment of both long and short-term dispersion patterns was
made to assist in developing sampling strategies and in understanding
I
the vegetation damage indicated by the analyses of infrared photographs
of the study area. The long-term assessment used the Climatological
Dispersion Model (CDM) and the short-term assessment used the Point-
Multiple Model (PTMPT) of EPA's UNAMAP Library. These models use known
area and point emissions and observed meteorological conditions (of
wind speed, wind direction, and stability category) to estimate the
concentration which would occur at selected sampling locations. The
CDM considers area and point emissions (annual average) of one or two
pollutants. The computations are made independently of one another.
In this application, emission rates for various materials at each of
the three bromine extraction plants in the vicinity of El Dorado,
Arkansas were obtained through the Project Officer. The hydrogen sulfide
emissions inventory was thought to be the most realible, so H^S was
chosen as one pollutant for modeling. An ideal, non-reactive gas which,
hypothetically, was emitted in equal amounts from each of the three
plants, was also selected for modeling. While none of the inventoried
emissions were uniform from plant to plant, the latter choice gives some
insight into the meteorological impacts and the source distribution
impacts on estimated concentrations.
Meteorological data for El Dorado were obtained through the National
Climatic Center, Asheville, N. C. Those data classify the frequency of
occurrence of six wind speed categories, sixteen wind direction
categories and five atmospheric stability categories on the basis of
hourly weather observations made between January 1950 and December 1954.
The frequency of occurrence of wind direction and speed (for all categories
of atmospheric stability) was developed and is shown in Figure Bl.
North-northeasterly winds and southerly winds are the most predominant.
Northwesterly winds are infrequency but strong; southeasterly winds are
generally light.
The CDM requires six stability categories—four of which are
characteristic of daytime conditions, and two which characterize nighttime
123
-------
Wind
Speed
(kt)
>21 I
17->21 I
11-16 T"
7-10 T
4-6 1
0-3
Frequency
of
Occurrence
/— 6%
1 - 5
T1-*
/ -'
1 2
1 ^
-- 1 (8
— o 3-
(9
(7.5) 3.8%
(7.9) 3
(7.0) 6.
(8.3)
57.
6% (6.5)
6.0% (6.0)
2% (5.4)
( ) Average Speed
U = 6.6 kt
ANNUAL WIND ROSE
El Dorado, Arkansas
1950 - 1954
Figure Bl
129
-------
conditions. The fourth category of the data available from NCC is
characteristic of stable conditions during night and day. This fourth
category was subdivided into a stable-day and a stable-night category.
Since winds are generally higher in daytime than at night, the stable-day
category included 40 percent of the occurrence of winds of the lower
wind speed categories (<_ 7 kt) and 60 percent of the occurrence of winds
in the remaining wind speed categories regardless of their direction.
In this way, a new fourth category (stable-day), a new fifth category
(stable-night), and a new sixth (the available fifth, very stable-night)
category were developed. Source characteristics assumed for the
pollutants are given in Table Bl. An average air temperature of 15°C
and mixing depths of 450 m (night) and 1491 m (day) were assumed.
Average annual concentrations and average concentrations for
September to November were estimated by the model at 2 km intervals on
a square grid encompassing the three plant sites and the surrounding
area. Isopleths of equal concentration were drawn from those estimates.
These analyses were then drawn as overlays of the USGS maps portraying
the vegetation damage. Visual inspections showed no discernable rela-
tionship of the concentration distribution to the vegetation damage.
Indeed, that damage occurred most frequently along power line rights of
way and railroad tracks, both of which are periodically cleared of
vegetation.
The CDM was also run to model a single point source of unit emissions
for both the Fall and Annual stability-wind relationships. Those results
showed the preparedness of higher concentrations along the north-south axis
and displaced slightly to the west of the source. In the Fall season, the
concentrations tend to be larger because of slower wind speeds. .(Figures B1,B2)
The PTMPT model was run for a single source of unit emission and the
observed meteorology for May 10, 1976 as a sample date. This day picked
from readily available data as characteristic of conditions which could
occur during the early fall. Stability was estimated using Turner's method.
Calm winds were assigned a random direction and an 0.5 m/s speed to overcome
the model's inability to treat calm conditions.
130
-------
Table Bl. Source Characteristics
Source Emission Rates Source Height Exit Exit
tons/year Height Diameter Velocity Temperature
PI P2 (m) (m) (m/s) (C)
1 10.23 1.0 10 2 5 50
2 0.404 1.0 10 2 5 50
3 13.43 1.0 10 2 5 50
131
-------
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Figure 32. Annual Average concentration (yg/iu ) of an inert pollutant
emitted at a rate of 1 gm/sec in the El Dorado, Arkansas
vicinity. Open circle indicates source. Overall scale
dimensions are 25 km x 25 km.
132
-------
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Figure B3. Average concentration for autumn (yg/m ), of an inert
pollutant emitted at a rate of 1 gm/sec in the
El Dorado, Arkansas vicinity. Open circle indicates
the source. Overall scale dimensions are 25 km by
25 km.
133
-------
An array of 24 receptor poiats was developed. Eight points were
established at 45-deg intervals, beginning at North at a 1 km radius from
the emitter. Eight points were similarly established as the 2 kin radius
but were rotated 15 degrees clockwise from North. The last eight points
were established at a 4 km radius, rotated 15 degrees counterclockwise
from North. This arrangement of receptors was designed to intercept at
least some portion of an effluent plume.
The PTMPT model runs were unsatisfactory at estimating the source
impact at the chosen receptor locations. Generally, the plume is barely
detectable at two receptor points and make a strong impact at one receptor
The summation of hourly impacts to give a distribution of the daily
average pollutant gives a very distorted view of the real impact. This
fault lies a) in the sampling network used, and b) in the model.
It does strongly indicate that sampling in the immediate vicinity of an
emitter can be extremely sensitive to wind direction changes.
134
-------
SECTION C: METEOROLOGICAL DATA
135
-------
METEOROLOGICAL DATA (JULY 18-AUGUST 12, 1977)
Date Time
7/18/77 0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
Temperature
75
76
76
74
74
74
78
84
88
92
94
95
98
98
99
98
97
94
91
87
85
82
80
78
Dew
Point
72
72
72
72
72
71
74
73
72
71
71
72
70
67
68
68
67
69
71
71
71
71
71
71
Pressure
1017.9
1017.1
1017.9
1017.9
1018.3
1018.6
1019.3
1019.6
1019.6
1019.3
1018.9
1018.6
1017.7
1017.1
1016.0
1016.1
1015.8
1016.1
1015.8
1016.1
1016.8
1016.8
1017.1
1017.1
Wind
Direction (°)
„
—
—
—
—
—
—
—
—
—
090
040
090
080
090
120
100
130
150
180
—
—
—
—
Speed
„
—
—
—
—
—
—
—
—
—
05
05
10 ...
Ql S
10 yi3
10
07
10
09
05
04
—
—
—
—
136
-------
SECTION C (cont'd)
Date Time Temperature
7/20/77 0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
76
76
76
77
77
77
77
80
83
85
85
87
76
80
82
85
84
83
82
80
79
78
77
75
Dew
Point
72
73
73
73
73
73
73
75
75
75
75
75
71
74
75
76
74
74
75
75
74
74
72
72
Pressure
1016.0
1016.0
1016.0
1016.0
1016.6
1016.8
1017.6
1017.9
1017.9
1018.2
1017.9
1017.9
1017.9
1017.2
1017.2
1016.4
1016.4
1016.8
1016.4
1016.4
1017.2
1017.2
1017.9
1017.9
Wind
Direction (°)
__u n^
—
170
180
150
—
190
230
260
290
—
100
100
190
120
130
200
190
130
—
—
—
—
—
Speed
— ._
—
04
04
04
—
05
04
05
06
—
07
06
05
05
07
05
04
04
—
—
—
—
24 hr precipitation - 0.13 inch
(continued)
-------
SECTION C (cont'd)
Date Time
7/21/77 0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
Temperature
(°F)
75
76
76
76
76
76
76
78
80
85
89
91
84
82
88
90
89
88
86
84
81
79
79
78
Dew
Point
72
74
74
73
73
73
73
75
76
76
76
77
75
76
76
74
76
77
77
76
76
75
75
75
Pressure
1018.3
1018.3
1017.9
1018.3
1019.0
1019.6
1020.0
1019.9
1020.0
1020.4
1020.3
1019.6
1018.6
1018.9
1017.7
1017.4
1017.0
1016.7
1016.7
1017.4
1017.7
1017.7
1018.2
1017.9
Wind
Direction (°)
130
130
160
170
170
200
190
200
220
260
210
210
010
350
350
100
120
120
120
130
—
—
—
—
Speed
03
03
08
04
04
04
03
05
05
07
08
06
08
10
05
05
04
04
05
04
—
—
—
—
24 hr rainfall - 0.67 inch
(continued)
138
-------
SECTION C (cont'd)
n*f-Q T-™ Temperature
Date Time ^OF.
7/22/77 0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
78
78
77
77
76
76
79
83
88
91
94
96
92
97
97
96
95
89
91
86
82
81
80
79
Dew
Point
75
75
74
74
73
73
75
76
76
75
74
73
73
72
76
74
74
73
78
75
75
76
75
74
Wind
Pressure _. . /ON
Direction ( )
1017.9
1017.5
1017.5
1017.9
1018.2
1019.0
1019.0
1019.4
1019.0
1019.0
1018.6
1018.2
1017.4
1016.4
1016.1
1015.4
1015.1
1015.5
1015.8
1016.1
1016.9
1016.8
1016.8
1016.8
„
—
—
—
—
—
—
300
010
020
310
300
230
—
300
—
320
030
170
—
—
—
210
—
Speed
m _n
—
—
—
—
—
—
04
04
04
06
06
10
—
08
—
06
04
09
—
—
—
04
—
24 hr rainfall - 0
(continued)
139
-------
SECTION C (cont'd)
Date Time
7/23/77 0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
Temperature
(°F)
78
78
77
76
76
77
80
85
88
91
94
96
96
98
98
99
95
89
85
84
84
82
81
80
Dew
Point
74
74
74
73
74
73
75
76
76
76
76
76
77
74
74
72
77
76
79
77
76
77
77
76
Pressure
1016.9
1016.5
1016.5
1016.5
1016.9
1017.7
1018.0
1018.0
1018.3
1018.3
1017.4
1017.1
1016.4
1015.4
1015.4
1015.1
1015.4
1014.9
1015.8
1015.9
1015.9
1015.5
1015.8
1016.1
Wind
Direction (°)
._
—
—
—
—
—
—
—
—
130
200
040
030
320
—
240
070
—
—
—
—
—
—
—
Speed
—
—
—
—
—
—
—
—
03
07
04
05
05
—
04
10
—
—
—
—
—
—
—
24 hr rainfall - trace
(continued)
140
-------
SECTION C (cont'd)
Date Time
7/24/77 0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
Temperature
(°F)
80
80
80
79
79
78
81
84
85
91
94
96
99
98
92
88
86
83
82
81
80
80
79
78
Dew
Point
77
76
76
76
76
76
77
79
79
79
79
79
79
74
77
76
75
76
77
77
76
76
75
75
Wind
Pressure ^ . . /0-,
Direction ( )
1015.8
1015.8
1015.4
1015.0
1015.4
1016.5
1016.1
1016.5
1016.5
1016.0
1016.0
1015.4
1014.7
1013.7
1013.7
1013.3
1014.3
1014.7
1015.1
1015.1
1015.1
1015.4
1015.1
1014.7
__
—
—
—
—
—
180
210
220
180
110
180
220
310
200
200
180
120
130
100
120
120
160
—
Speed
„
—
—
—
—
—
04
05
05
04
05
07
06
08
07
10
05
10
04
05
05
04
04
—
(continued)
141
-------
SECTION C (cont'd)
Date Time
7/25/77 0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
Temperature
(°F)
78
78
77
77
78
78
81
84
90
93
95
99
101
100
86
83
85
85
84
83
81
80
80
79
Dew
Point
74
74
74
74
74
75
76
78
78
77
76
75
75
77
79
76
80
79
78
78
77
76
76
75
Pressure
1014.4
1014.4
1014.4
1014.5
1014.9
1015.2
1015.9
1016.2
1016.6
1016.2
1015.8
1015.4
1014.8
1014.0
1014.8
1014.0
1014.1
1014.1
1013.8
1014.8
1015.2
1015.8
1014.2
1015.4
Wind
Direction (°)
190
200
—
—
—
170
200
230
250
270
240
190
190
180
100
170
170
170
170
140
130
220
—
—
Speed
05
04
—
—
—
05
06
08
08
10
06
08
07
07
15 (G22)
07
05
06
07
03
04
03
—
—
24 hr precipitation - 0.17 inch
(continued)
142
-------
SECTION C (cont'd)
Date Time
7/26/77 0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
Temperature
(°F)
78
79
77
75
75
75
75
78
79
84
87
91
91
92
92
92
90
86
85
82
80
79
79
79
Dew
Point
75
76
72
72
72
72
73
74
74
75
75
79
75
75
75
76
78
76
76
77
77
77
77
77
Wind
Pressure _. . „ . ,0>
Direction ( j
1016.4
1017.4.
1017.8
1016.5
1016.]
1016.5
1017.9
1019.0
1019.4
1019.4
1019.0
1018.5
1018.5
1017.8
1017.4
1016.9
1016.9
1016.9
1016.9
1016.1
1016.9
1017.7
1018.1
1017.8
050
060
050
—
260
100
050
360
320
060
070
040
050
030
010
030
010
050
070
120
—
010
020
040
Speed
10
13
15
—
09
05
04
05
04
07
06
08
05
08
09
07
11
12
06
05
—
06
04
04
24 hr precipitation - 0.29 inch
(continued)
143
-------
SECTION C (cont'd)
Date Time
7/27/77 0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
Temperature
(°F)
78
78
77
77
75
75
75
75
76
80
83
87
90
78
76
75
76
76
77
77
76
76
76
77
Dew
Point
76
76
76
75
73
73
73
73
73
74
75
75
75
74
71
-
-
-
77
77
76
76
76
77
Pressure
1017.8
1017.2
1017.2.
1016.8
1017.2
1017.6
1018.3
1018.3
1018.6
1018.3
1017.9
1017.2
1015.6
1017.3
1016.9
1015.8
1015.0
1015.0
1015.4
1015.4
1015.8
1016.2
1016.2
1016.2
Wind
Direction (°)
030
030
030
030
050
—
—
010
00
—
—
—
210
030
250
250
—
—
—
—
—
—
350
360
Speed
04
05
04
06
05
—
—
04
00
—
—
—
05
12
03
04
—
—
—
—
—
—
05
04
24 hr precipitation - 1.15 inches
(continued)
144
-------
SECTION C (cont'd)
Date Time
7/28/77 0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
Temperature
(°F)
77
77
77
76
76
76
77
78
81
83
81
81
80
85
85
86
85
85
84
81
80
79
79
78
Dew _, Wind
_ . Pressure _. . /0>,
Point Direction ( )
77
77
77
76
76
76
77
78
81
80
80
80
80
80
80
-
-
-
-
-
-
-
-
1017.2
1016.2
1015.8
1015.8
1016.2
1016.8
1016.8
1017.4
1017.6
1017.9
1017.9
1018.3
1018.3
1017.5
1017.1
1016.5
1016.2
1015.5
1015.5
1015.8
1015.8
1016.7
1017.2
1016.5
__
—
350
310
310
320
—
230
—
260
270
220
180
210
240
180
230
180
140
—
170
—
170
—
Speed
__
—
04
04
04
04
—
05
—
04
04
05
05
06
05
04
05
05
03
—
03
—
03
—
24 hr precipitation - 0.11 inch
(continued)
145
-------
SECTION C (cont'd)
Date Time
7/29/77 0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
Temperature
(°F)
79
79
78
-
78
78
79
81
83
84
-
-
-
88
89
89
87
86
83
82
80
79
78
76
Dew
Point
_
._
_
_
_
_
_
_
_
_
_
75
74
72
75
76
76
76
74
73
72
71
Pressure
1016.8
1016.5
1016.5
1016.5
1016.8
1016.8
1017.3
1017.5
1017.5
1017.9
1017.5
1017.3
1016.9
1016.1
1015.5
1015.5
1015.5
1015.8
1015.8
1015.8
1016.4
1016.9
1016.5
-
Wind
Direction (°)
__
—
—
—
—
—
190
190
210
210
240
230
230
250
190
270
200
010
—
—
—
—
210
210
Speed
__
—
—
—
—
—
04
05
05
07
07
09
07
06
05
05
06
04
—
—
—
—
05
05
(continued)
146
-------
SECTION C (cont'd)
Date Time
7/30/77 0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
Temperature
(°F)
75
75
75
74
74
74
76
81
80
76
75
75
77
80
80
80
81
81
80
79
77
77
77
77
Dew
Point
71
71
71
70
71
70
71
73
72
72
71
71
73
74
73
74
74
75
75
75
74
74
74
74
Pressure
1015.8
1015.8
1015.4
1015.8
1016.2
1016.5
1016.9
1016.9
1017.3
1017.9
1017.9
1017.6
1016.9
1015.5
1015.2
1014.9
1014.9
1014.5
1014.1
1013.5
1014.1
1014.5
1014.5
1014.5
Wind
Direction (°)
__
—
—
—
—
—
180
230
240
230
210
200
190
160
180
200
—
—
—
—
—
—
—
—
Speed
__
—
—
—
—
—
05
07
07
08
04
04
05
06
05
05
—
—
—
—
—
—
—
—
24 hr precipitation - 0.10 inch
(continued)
147
-------
SECTION C (cont'd)
Date Time
7/31/77 0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
Temperature
(°F)
76
76
76
76
76
76
77
82
83
85
84
82
77
80
86
90
90
89
82
80
78
77
77
76
Dew
Point
74
74
74
74
73
72
73
75
72
72
70
69
69
73
70
69
71
71
75
75
74
73
73
72
Pressure
1014.1
1013.3
1013.3
1013.7
1014.5
1016.0
1016.0
1015.7
1015.7
1016.0
-
1016.2
1016.5
1015.1
1014.1
1013.8
1013.8
1013.4
1014.5
1014.5
1015.1
1015.5
1015.9
1015.5
Wind
Direction (°)
__
—
200
230
230
250
270
220
—
220
260
260
290
230
250
250
230
210
—
—
—
—
—
—
Speed
__
—
04
06
04
03
04
07
—
07
05
06
08
07
06
06
05
04
—
—
—
—
—
—
24 hr precipitation - 0.09 inch
(continued)
148
-------
SECTION C (cont'd)
r. . ,_ . Temperature
Date Time % .
V c )
8/1/77 0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
75
75
75
74
72
71
71
74
74
75
78
82
84
84
82
81
82
82
79
75
72
71
71
70
Dew
Point
72
72
72
69
68
66
66
67
67
67
67
74
67
67
69
70
70
70
71
71
69
68
68
67
Wind
Pressure _. . _. /tM
Direction ( J
1015.1
1015.5
1015.9
1016.2
1019.0
1020.0
1017.9
1015.9
1017.2
1018.3
1018.3
1017.9
1017.5
1017.3
1016.5
1016.2
1016.2
1016.2
1016.2
1016.5
1016.8
1017.1
1017.1
1017.2
T||_
340
340
340
270
260
230
—
030
010
020
020
350
030
030
—
100
—
—
—
—
—
—
—
Speed
__
04
05
13
15
09
11
—
12
05
06
07
09
07
04
—
05
—
—
—
—
—
—
—
(continued)
149
-------
SECTION C (cont'd)
Date Time
8/2/77 0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
Temperature
(°F)
69
68
69
68
68
68
70
73
79
82
86
85
88
90
90
90
90
88
79
74
72
69
68
66
Dew
Point
67
66
66
65
66
66
67
69
69
70
70
69
69
65
64
64
61
62
66
66
65
64
63
62
Pressure
1016.9
1016.5
1016.2
1016.2
1016.9
1016.9
1017.2
1017.6
1017.2
1016.9
1017.2
1017.2
1016.6
1015.8
1015.2
1014.9
1014.9
1014.9
1014.9
1015.0
1015.5
1015.9
1015.9
1016.2
Wind
Direction (°)
._
—
340
350
—
350
010
340
120
030
040
050
030
040
040
080
040
040
—
—
—
—
—
—
Speed
..
—
04
05
—
04
05
03
04
05
04
05
07
07
05
07
06
05
—
—
—
—
—
—
(continued)
150
-------
SECTION C (cont'd)
Date Time
8/3/77 0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
Temperature
<°F)
65
63
63
62
63
63
67
74
81
84
86
89
90
91
92
92
92
91
82
74
72
70
69
68
Dew
Point
61
60
60
60
60
60
63
65
63
61
63
64
64
64
61
62
62
64
68
68
66
65
64
64
Wind
Pressure . ,„>
Direction ( J
1016.2
1016.2
1016.2
1016.2
1016.2
1016.5
1016.9
1016.8
1017.2
1017.5
1017.5
1017.2
1016.1
1016.1
1015.5
1015.1
1014.8
1014.8
1015.6
1016.0
1016.6
1017.0
1016.6
1016.1
-im^ni
070
040
060
050
090
040
070
100
130
—
—
—
—
—
—
Speed
_im a_
—
—
—
—
—
—
—
—
05
05
08
06
07
05
07
07
04
—
—
—
—
—
(continued)
151
-------
SECTION C (cont'd)
Date Time
8/4/77 0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
Temperature
(°F)
67
67
66
66
66
65
70
75
81
86
88
90
90
90
92
92
90
90
86
83
80
78
77
77
Dew
Point
63
63
63
62
62
52
66
69
71
71
70
69
68
69
67
66
67
68
68
70
72
71
71
71
Pressure
1015.9
1015.5
1015.1
1014.8
1015.5
1017.2
1017.9
1018.2
1017.9
1017.5
1017.5
1017.2
1016.5
1015.9
1015.9
1015.1
1015.1
1015.1
1015.5
1015.9
1016.7
1017.5
1017.9
1017.8
Wind
Direction (°)
__
—
—
—
— .•
—
—
080
180
150
140
090
040
070
090
150
150
130
140
130
160
130
130
140
Speed
«_
—
—
—
—
—
—
04
04
04
05
06
08
05
08
09
08
06
06
07
04
05
05
06
(continued)
152
-------
SECTION C (cont'd)
Date Time
8/5/77 0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
Temperature
(°F)
76
75
76
76
77
77
78
79
82
82
85
86
88
87
88
75
76
76
75
74
74
73
73
73
Dew
Point
71
71
72
72
72
72
73
73
74
73
73
71
72
71
71
71
72
72
72
72
71
71
71
71
Pressure
1017.2
1017.5
1017.5
1017.5
1018.2
1019.3
1020.0
1020.3
1020.3
1020.3
1019.9
1019.1
1018.8
1018.0
1017.2
1019.3
1018.6
1018.6
1019.0
1019.6
1020.0
1019.6
1019.6
1019.6
Wind
Direction (°)
140
140
140
140
160
160
160
170
160
150
150
160
140
090
130
200
170
160
190
—
090
—
120
120
Speed
06
05
05
06
05
05
07
07
09
08
09
06
06
06
08
10
05
07
04
—
04
—
04
04
24 hr precipitation - 0.25 inch
(continued)
153
-------
SECTION C (cont'd)
Date Time
7/19/77 0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
Temperature
(°F)
77
76
76
75
74
74
75
75
76
79
80
84
88
89
90
91
85
80
79
77
77
77
76
76
Dew
Point
71
71
71
70
70
70
70
72
73
74
75
76
75
74
74
73
71
72
73
73
73
73
72
72
Pressure
1016.8
1016.5
1016.5
1016.8
1016.8
1017.2
1017.8
1018.2
1018.2
1018.2
1017.8
1017.5
1017.1
1015.8
1015.4
1014.8
1015.1
1015.1
1015.1
1015.5
1015.5
1015.9
1016.3
1016.3
Wind
Direction (°)
„
—
—
—
—
—
100
—
—
—
350
070
060
150
—
320
060
100
080
—
—
—
—
—
Speed
«._
—
—
—
—
—
04
—
—
—
05
04
03
04
—
06
08
06
05
—
—
—
—
—
24 hr precipitation - 0.19 inches
(continued)
154
-------
SECTION D: HOURLY OZONE CONCENTRATIONS IN EL DORADO, ARKANSAS
155
-------
HOURLY OZONE CONCENTRATIONS IN EL DORADO, ARKANSAS
Site Location: Arkansas Chemical - El Dorado, Arkansas
Charts
Time:
Date
Hour
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
Read by:
7/22/77
_
-
-
—
—
-
-
-
-
-
-
-
—
-
—
C
c
C
0.032
0.027
0.040
0.027
0.012
0.008
Mark Saeger
Central
7/23/77
0.010
0.008
0.005
0.003
0.003
0.003
0.003
0.008
*
0.030
0.040
0.035
0.042
0.045
0.047
0.047
0.042
0.045
0.035
0.012
0.010
0.017
0.008
0.003
Standard
7/24/77
0.003
0.008
0.005
0.000
0.000
0.003
0.003
0.005
0.015
*
0.040
0.047
0.060
0.065
0.060
0.057
0.052
0.047
0.042
0.037
0.020
0.022
0.027
0.020
Time
7/25/77
0.012
0.017
0.015
0.012
0.010
0.008
0.008
0.012
0.025
*
0.050
0.057
0.060
0.062
0.062
0.052
0.042
0.037
0.037
0.035
0.027
0.010
0.012
0.012
7/26/77
0.010
0.005
0.017
0.052
0.042
0.032
0.040
0.035
0.030
*
0.027
0.032
0.035
0.042
0.040
0.047
0.037
0.020
0.015
0.025
0.030
0.022
0.012
0.010
7/27/77
0.010
0.012
0.005
0.005
0.005
0.000
0.005
0.005
0.008
*
*
0.020
0.022
0.032
0.035
0.037
0.032
0.030
0.027
0.015
0.010
0.012
0.010
0.005
- Instrument not on-line.
C - Initial calibration.
* - Zero/span.
156
-------
Date
Hour
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
7/28/77
0.003
0.000
0.000
0.003
0.003
0.008
0.008
0.010
0.012
0.022
**
**
**
**
**
0.037
0.040
0.042
0.042
0.035
0.015
0.008
0.000
0.000
7/29/77
0.005
0.003
0.005
0.000
0.000
0.003
0.003
0.010
0.015
*
0.022
0.030
0.040
0.050
0.050
0.050
0.050
0.050
0.027
0.017
0.015
0.022
0.020
0.022
7/30/77
0.022
0.012
0.008
0.008
0.010
0.008
0.005
0.010
0.017
*
0.027
0.027
0.030
0.030
0.030
0.032
0.027
0.025
0.020
0.017
0.012
0.003
0.003
0.005
7/31/77
0.005
0.003
0.003
0.005
0.008
0.008
0.008
0.005
0.012
0.022
0.030
0.030
0.025
0.027
0.035
0.035
0.040
0.040
*
0.010
0.005
0.000
0.000
0.000
8/01/77
0.000
0.000
0.000
0.000
0.010
0.037
0.040
0.037
0.035
0.017
0.020
0.015
0.018
0.028
0.028
0.025
*
0.023
0.018
0.018
0.005
0.003
0.000
0.000
7/02/77
0.000
0.000
0.000
0.000
0.000
0.003
0.000
0.003
0.008
0.028
0.038
0.043
0.035
0.030
0.038
0.033
0.033
0.025
A
0.023
0.015
0.005
0.000
0.003
* - Zero/span.
** - EPA audit.
157
-------
Date
Hour
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
8/03/77
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.025
0.087
0.082
0.072
0.062
0.062
0.067
0.065
0.057
*
0.055
0.027
0.017
0.008
0.008
0.003
8/04/77
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.003
0.017
0.037
0.045
0.047
0.045
0.057
0.055
0.057
0.067
*
0.052
0.045
0.037
0.027
0.027
0.025
8/05/77
0 022
0.020
0.020
0.022
0.025
0.022
0.020
0.017
0.020
0.022
0.025
0.033
0.035
0.035
0.032
0.035
0.037
*
0.027
0.027
0.022
0.015
0.003
0.012
8/06/77
0.015
0.013
0.010
0.008
0.003
0.000
0.000
0.003
0.015
0.025
0.030
0.032
0.032
0.030
0.030
0.030
0.025
*
0.025
0.015
0.005
0.003
0.003
0.000
8/07/77
0.005
0.005
0.000
0.003
0.003
0.000
0.000
0.005
0.012
0.017
0.022
0.022
A
0.020
0.022
0.027
0.030
0.035
0.032
0.027
0.020
0.008
0.008
0.008
8/08/77
0.005
0.003
0.003
0.000
0.000
0.000
0.000
0.003
0.015
0.025
0.035
0.035
0.035
0.037
0.037
*
0.040
0.040
0.032
0.020
0.010
0.017
0.022
0.027
* - Zero/span.
158
-------
Date
Hour
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
8/09/77
0.025
0.012
0.005
0.003
0.008
0.005
0.000
0.005
0.015
0.025
0.030
0.035
0.042
0.045
0.045
*
0.045
0.042
0.032
0.020
0.010
0.003
0.000
0.000
8/10/77
0.003
0.003
0.003
0.005
0.003
0.000
0.000
0.003
0.008
0.017
0.022
*
0.040
0.045
0.045
0.047
0.042
0.047
0.077
0.065
0.047
0.040
0.042
0.035
8/11/77
0.030
0.022
0.017
0.022
0.015
0.008
0.005
0.008
0.017
0.027
0.030
0.030
0.035
0.035
0.042
0.047
*
0.045
0.040
0.035
0.030
0.022
0.025
0.017
8/12/77
0.017
0.017
0.015
0.010
0.010
0.010
0.010
0.005
0.012
0.017
0.022
0.027
0.032
0.032
0.020
0.027
A
0.037
0.040
0.040
0.032
0.027
0.022
0.015
* - Zero/span.
159
-------
TECHNICAL REPORT DATA
/Please read Instructions on the reverse before completing} j
1. REPORT NO.
EPA-560/6-78-002
2.
4. TITLE AND SUBTITLE
Environmental Monitoring Near Industrial Sites:
Brominated Chemicals
7. AUTHOR(S)
E. D. Pellizzari, R. A. Zweidinger and M. D. Erickson
9. PERFORMING ORGANIZATION NAME AN
Research Triangle Institute
Post Office Box 12194
Research Triangle Park, Nor
12. SPONSORING AGENCY NAME AND ADC
Office of Toxic Substances
U. S. Environmental Protect!
Washington, DC 20460
ID ADDRESS
th Carolina 27709
RESS
on Agency
3. RECIPIENT'S ACCESSION NO.
5. REPORT DATE
June 1978
6. PERFORMING ORGANIZATION CODE 1
8. PERFORMING ORGANIZATION REPORT NO.
Task II Final Report
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
EPA 68-01-1978
13. TYPE OF REPORT AND PERIOD COVERED
Final - 7/19/77 - 17/16/77
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
Sampling and analysis was designed to determine ambient concentrations of
ethylene dibromide and other brominated chemicals near production facilities in
El Dorado and Magnolia, AK. A characterization was made of the environmental
matrices - air, water, soil, sediment and biota - for the presence and levels
of ethylene dibromide, vinyl bromide and other related chemicals surrounding
the bromine industry.
17. KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
18. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
b. IDENTIFIERS/OPEN ENDED TERMS
19. SECURITY CLASS (This Report)
UNCLASSIFIED
20. SECURITY CLASS (This page/
UNCLASP TFTFTl
c. COS ATI Field/Group 1
1
1
21. NO. OF PAGES
Part II - 165
22. PRICE I
EPA Form 2220-1 (Rev. 4-77)
PREVIOUS EDITION IS OBSOLETE
-------
INSTRUCTIONS
1. REPORT NUMBER
Insert the hPA report number as it appears on the cover of the publication.
2. LEAVE BLANK
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10. PROGRAM ELEMENT NUMBER
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To be published in, Supersedes, Supplements, etc.
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(a) DESCRIPTORS - Select from the Thesaurus of Engineering and Scientific Terms the proper authorized terms that identify the major
concept of the research and are sufficiently specific and precise to be used as index entries for cataloging.
(b) IDENTIFIERS AND OPEN-ENDED TERMS - Use identifiers for project names, code names, equipment designators, etc. Use open-
ended terms written in descriptor form for those subjects for which no descriptor exists,
(c) COSATI FIELD GROUP - Field and group assignments are to be taken from the 1965 COS ATI Subject Category List. Since the ma-
jority of documents are multidisciplinary in nature, the Primary Field/Group assignments! vili be specific' discipline, area of human
endeavor, or type of physical object. The application(s) will be cross-referenced with secondary Field/Group assignments that will follow
the primary posting(s).
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EPA Form 2220-1 (Rev. 4-77) (Reverse!
-------