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                    <text>Item D Number

°2264

Author

Smith R

-

Corporate Author
Report/Article Title Typescript: Chemical Data on Air Samples Collected in
and near the Binghamton State Office Building
(February, March 1985) Before and After the HVAC
System is Returned to Normal, July 17,1985

Journal/Book Title
Year

000

°

Month/Day
Color
Number of biages

D

19

Descriptor! Notes

Thursday, September 20, 2001

Page 2264 of 2293

�CHEMICAL DATA ON AIR SAMPLES COLLECTED IN AND NEAR THE BINGHAMTON
STATE OFFICE BUILDING (FEBRUARY, MARCH 1985) BEFORE AND AFTER
THE HVAC SYSTEM IS RETURNED TO NORMAL

R. Smith, P. O'Keefe, K. Aldous, D. Hilker, G. Eadon

July 17, 1985

Wadsworth Center for Laboratories and Research
New York State Department of Health
Albany, New York 12201

�INTRODUCTION

Air samples were collected and analyzed for chlorinated dibenzofurans
(CDFs), chlorinated dibenzodioxins (CDDs) and chlorinated biphenylenes
(CBPs) to study the effect of BSOB IIVAC system operating mode on BSOB indoor
and outdoor concentrations.

This report describes sampling, analytical

procedures and results for the determination of these analytes in air
samples collected (1) on 2/15/85 at 3 outdoor locations near the BSOB prior
to venting of the HVAC, (2) on 2/22/85 at the same locations after venting
and (3) on 3/29/85 at the mechanical room mixing boxes on floors 6 and 14
inside the building after venting.

Because Prof. C. Rappe of the University

of Umea, Sweden, had produced evidence suggesting detectable contamination
in an earlier outdoor air sampling, the outdoor samples were collected in
duplicate, extracted, and split for independent analysis by Prof. C. Rappe.
•»*,

Results of the last sampling prior to the return of the IIVAC system to
normal (September 1984

samples) showed a mixture of Cl4~Cle CDFs

in air from the 6th and 14th floor mixing boxes (similar to that previously
found in building air) at concentrations of 47-260 pg/m3 total TCDFs and
29-185 pg/m3 total penta-CDFs ( )
1.

At that time C. Rappe found traces of

.sAe*to;al'.:Cl4-Cl&lt;'CDFs in a single sample (September, 1984) of
outside air at concentrations of approximately 0.1 pg/m3/isoraer
12378/12348 0.14 pg/m-* uncorrected for recovery) ( )
1.
;

(e.g.

To confirm these

preliminary findings it was necessary to repeat the outdoor air anlyse%
improving detection limits if possible.

�METHODOLOGY

Air Sample Collection
Sample were collected using a two-stage sampling device (0.3

fi particu-

late filter, silica gel adsorbent cartridge) specifically designed to
collect PCDDs and PCDFs ( )
2.

In the laboratory the 140°

activated 25 mm x

' *"
*'

45 mm silica gel cartridges were spiked with

13

C 2,3,7,8-TCDD,

2,3,7,8-TCDF, and l »C 1,2,3,7,8 penta-CDF internal standards.

17

C1

The

sampling device was then assembled and wrapped in foil for transport.

At

the site, samples were taken by drawing 80. M3 of air through the sampler at
approximately 20 L/min using a 1.5 CFM Gast vacuum pump.
the intact device was wrapped in foil and transported

After sampling,

at room temperature to

the laboratory for analysis.
Sample Extraction, Compos it ing_, and Splitting
The particulate-containing filter was placed in the associated
adsorbent cartridge and subjected to Soxhlet extraction with 80 ml benzene
for 16 hrs (samples found to contain large amounts of water were extracted
with acetone then benzene).

The duplicate sample extracts to be combined

(e.g. 50363 + 50364) were concentrated if necessary, combined, (as sample
#50744) and split 50/50.

Sample extracts to be mailed to Umea, Sweden were

cotacentrated to 100 (iL, transferred to 2 mm i.d: Pyrex capillary tubes, tfcer
the volume was reduced to just dryness under vacuum (exchanged standards
were similarly handled).
for transport.

The capillary tubes were then sealed and packaged

The sample extracts to be analyzed by WCL R were

additionally spiked with

1!

C OCDD and handled as follows:

�Sample Clean-up
The benzene extract was passed through a 22 nun i.d. chromatography
column packed bottom to top with 4 mm Na2S04J 4 mm K Silicate,
4 mm silica gel, 30 mm 44% H2S04 silica gel, 4 mm silica gel,.
40 mm NaaC03, 50 mm silica gel and 4 mm NaaS04 followed
by hexane solvent.

The sample in 50% benzene/hexane was then cleaned up
***•
using a microprocessor controlled sequence of acidic alumina, PX-21 carbon,
and neutral alumina chromatography followed by concentration to 100 uL for
storage in sealed glass capillaries. Just prior to GC/MS analysis, the
samples were concentrated to 4 uL under vacuum.

The extract at this stage

contains all Cl4-Clg CDFs and CDDs.
Capillary GC/LRMS
A portion of the sample extract (0.8 to 1.8 uL) was injected onto
either a 60 m 0.25 mm i.d. SP2330 or 50 m 0.2 mm i.a. DB5 fused silica GC
capillary column, head pressure 20 psi, directly interfaced to a

,

Hewlett-Packard 5970 Mass Selective Detector. The MSD was used in the El
mode with a 235 C source temperature and unit resolution.

Data acquisition

was accomplished using the single ion monitoring mode with m/e values and
chromatographic conditions shown in Table 1.
Calculations
&lt; 'Kif results were calculated by integrating a single ion chromatographic peak (e.g. 2,3,7,8-TCDF) and by summing total area counts for groups
of observed peaks (e.g., TCDFs).
it

TCDFs and TCDDs were quantitated by an

isotope" dilution internal standard method (eq. 1) which inherently corrects
for any recovery losses.

Detection limits were similarly calculated,

substituting nearby MS noise in arbitrary counts (e.g. 1000 area counts)
incorporating a detection limit factor of 2.5.

�l = XC2 A1/A2

C

Where

C

(eq

= the calculated concentration of native CDF (or CDD) in
pg/m3.

X

=

a theoretical mass spectral response factor that corrects
"*"
13
for differences in isotope abundances (1 for
C-TCDD,

2.5 for

37

Cl-TCDF; a measured, response factor may

also be used.
C

= the known concentration of added, isotopically labeled CDF
(or CDD) in pg/m 3 .

A1 = the measured area under the ion chromatographic peak due
to native CDF or CDD (e.g. TCDF at m/z 306) in arbitrary
counts.
A

= the measured area under the ion chromatographic peak to

.^

isotopically labeled standard (e.g. TCDF at m/z 312) in
arbitrary counts.

Response factors relative to the internal standards were also obtained for
congener groups by running native standards along with internal standards.
.sllserc:

poitse factors were applied to the quantitation of Hexa CDFs to Octa

CDF and Penta CDDs to Octa CDD.
Standards
[D1*-C] 2,3,7,8-TCDD (KOR Isotopes, Cambridge, MA) has been used for
air sampler recovery experiments.

The sample cleanup procedure has been

evaluated using all 22 TCDDs, OCDD (Analabs, North Haven, CT) 2,3,7,8-TCDF
(NIEOS),

37

C1 penta-CDF mixture of isomers purified by RPLC (KOR), OCDF

�(Analabs), and 2367-TC BP (academic source).
tation included J C 12 2,3,7,8-TCDD (KOR) and

J7

Internal standards for quantiC1 4 2,3,7,8-TCDF

(KOR) purified by RPLC, i»C 1,2,3.7,8 penta-CDF and

13

C OCDD.

Quality Assurance

The following measures ensure the quality of this analysis.

Various

*v

blanks are run concurrently with samples and strict criteria for the
identification of each compound class are observed.

An isotopically labeled

internal standard is added to each sample prior to sampling or analysis to
provide both a qualitative check and accurate quantitation when sample
recovery data is variable.
Blanks
Four types of blanks were run:

(1) a system blank prior to the use of

any glassware to ensure no carryover from prior samples; (2) a method
blank, run simultaneously and using the same standards, solvents,
adsorbents, and glassware as the actual samples; (3) isotopically-labeled
standards; and (4) benzene blanks to check for GC and syringe

carryover.

Precision
The best measure of precision is obtained from replicate samples.
is commonly within 20%.

This

The recovery of the internal standard available for

each sample will provide a measure of precision; however, this is based on
external standardization (requiring manipulation and accurate measurement of
sample volumes of 1 to 4 fil) and is known to be less precise than internal
standardization.

�Criteria for Detection
To be detected as a PCDD or PCDF isomer in a sample all of the
following conditions must be met:
1.

co-elution on GC with appropriate standard if available.

2.

response at a minimum of two ions corresponding to H, M+2;
response must be in proper ratio +20%; response at additional
fragment iofis such as M-COC1 for greatest reliability when
sensitivity permits.

3.

adequate recovery of all internal

standards.

4.

acceptable QC blanks and spikes.

5.

negligible mass spectral interference.

�RESULTS

Table 2 contains the data generated by the New York State Department of
Health from outdoor air samples collected prior to (February 15-18) and after
(February 22-25) returning the building's HVAC system to normal operations.
Table 3 contains the data generated from indoor air samples collected on the
6th and 14th floors on March 29-April 1.
or
DISCUSSION
The outdoor air data both before and after returning the HVAC system to
normal operation contains no evidence for the presence of any

3
tetrachlorodibenzofuran isomer (detection limit 0.06-0.15 pg/m ) or any
o

pentachlorodibenzofuran isomer (detection limit 0.2-0.5 pg/m ). (Doctor C.
Rappe's analysis of splits of these samples yielded results consistent with
•j
this data (not detected at about 1 pg/m /isomer). (Personal Communication,
written report to follow). Since tetra and pentachlorofurans are by far the
most abundant compounds among the furans, dioxins and biphenylenes within the
BSOB, detection of any such BSOB-induced contamination of the outdoor air in
either the pre-venting or current post-venting mode of operation is clearly
beyond the capacity of present-day analytical techniques.
The indoor air data of Table 3 demonstrates the presence of tetra-,
penfca--, and hexachlorofurans in detectable concentrations; Hepta- and
octachlorofurans, tetra- and penta-chloro-biphenylenes and tetra-, penta-,
hexa-, hepta-, and octachlorodibenzodioxins were all below limits of detection.
There are many cross comparisons possible among the data produced by WCL&amp;R
from the September 1984 and the March 1985 samplings. Dibenzodioxins (tetra
through octachloro), hepta and octachloro furans, and pentachlorobiphenylenes
were not detected in either sampling; tetrachlorobiphenylenes, barely above the
limit of detection in 1984, were not detected in 1985, consistent with the

�subsequently discussed decrease in overall concentrations. As Table 4
demonstrates, the patterns observed in the tetra through hexachlorofurans (the
only compounds present above detection limits during both samplings) are
generally maintained.

Thus, for the 6th floor, the ratio total TCDF:total

PeCDF:total HxCDF was 1:0.37:0.13 in 9/84 versus 1:0.60:0.14 in 4/85; the
corresponding 14th floor ratios were 1:0.60:0.09 and 1:0.42:0.14.

For the 6th

*3f

floor, the ratio 2378-TCDF/total TCDF was 0.07 in 9/84 and 0.06 in 4/85; the
corresponding 14th floor ratios were 0.05 and 0.06. The largest
2378-substituted PeCDF peak (actually a mixture of 12378 and 12348-PeCDF)
constituted 15% of total PeCDF on the 6th floor in 9/84, and 9% in 4/85. The
corresponding values for the 14th floor are 15% and 16%.
The most important difference between the two data sets is the significant
decrease in concentrations of tetra through hexa CDFs in the April sampling
(Table 4 . Thus, for example, total TCDF concentration (averaged over the 6th
)
and 14th floors) decreased by a factor of 2.6; the corresponding factors for-total PeCDF and total HxCDF were 2.9 and 2.0.

These decreases in concentration

as well as improvements in detection limits for 2367-tetrachlorobyphenylene and
12367-pentachlorobiphenylene result in a recalculated "2378-TCDD equivalent"
•3

concentration of &lt;4.1 pg/nr3 in April, 1985 versus &lt;11 pg/m
(Tabl«= 5).

o

in November,1984

�REFERENCES

1

Aldous, K., Hilker, D., O'Keefe, P., Smith, R. and Eadon, G., Chemical data
on air and wipe samples collected from the Binghamton State Office
Building-September 1984, New York State Department of Health Report.

2

Eadon, G., Aldous, K., Hilker, D., O'Keefe, P. and Smith, R., Chemical data

on air samples from the Binghamton State Office Building, New York State
~»**
Department of Health Report.

�TABLE I

fj A 7 A.

t~-\ r. y ij 7 s T 7 T H Nr

R»y. i .

i - W n y —54

1 0 3 0 / 5 t o r e M e t h o d •' ME f H : 5 I N ' 5 H : M
Description

B I H

:

2378 iii^MLYSIG O'v 2330 6C "•'"' i'M

A G Q' U I 5 I T I 0 W

solvent deiaY
Group
I n f I np 5
stari Tine

8,00

el'l volts

1
2
fi
tQ
(0.00 0.00

3
5
0.00

13 Jun 85

i &amp; r V ^ an

800 reiAtive
4
5
't
5
0.00 0.00

resulting voirage 2200

B
8
0.00

7
t

low MS Resolution NO

T E M P' E R ft T U R. E

Level
i

75.00

P R Q 6 R f\ M

etjuiiibrat ion tine

initial
tEmp
75

6
I

S
i

t0
f

cycles per second ].4

i o n A"
i
2
3
4
5
5
ri'' 2 303 = '30 305 : 50 31 t = 90 339. 6^j 341 , 85 351 * 90
Dwell
100
100
(00
t00
'0
(0
(00

rim tine

HETH-'BINGH.M

,&amp;
0.50

i n i t i a l • Rate
tine
ODC/Min)
1.00
50.0

.

H E A T E D

Z 0 N E 5 •

sPiitless o-n tine

final
. tEnp
235

final
tine
75,00

3,50
total
i,ne
r."i,Z0

3
]

' »i
^j
6

actual
(Standby;
"5
Inj Fort B1
250
Detector ri

Betpt
75
250
Off

Linit
300
250
425

actual
Inj Fort A
Transfer Line

235

Setpt
Off
235

'unit
259
300

�TABLE I (continued)
D A T A

A C Q U I S I T I O N

R e v .1 . 3

1-Nov-S4

l o a d / s t o r e Method : METH:BINGIN.M
Description : CONGENER GROUP ANALYSIS FOR BINfi INDOOR AIR SAMPLES
1 .Ml
] 4. (a®
14,88
47.88
B8 . 88
95.88

'v'a! ves Spi. i t i e s 5 O f f
Group i
liass Spec On
Group 2
""*
firoup 3
Stop 'Run

S I M

A C Q U I S I T I O N

s o l v e n t ; d e l a Y 14.88

ft OP
- 4 . -, „ {.

a loi I

e'1 v o l t s

CD

bro u p
Ions

, 2
3

15

A ••?

Ii'its

l O W MS rveauiU t ion

1 3 Jun 85

rxrx

888 r e l a t i v e

3
15
on.

2:87 pro

4
4

-

5
4 '

•
G
20

riETH:6INGIN.M

r e s u l t i n g v o l t a g e 2488
7

8

3

18

7 C*

*^ C\

^ •**

"* 0

rtrK

IMU

L;yi_i63 p6f

tjeLuliu w . o

1
ion ft
3 •
4
5
G
7
8
3
!0
en / Z 2 78.80 2 72 . $v3 286.88 288.88 304.88 386.88 31 2.88 328. 8G J22.88 334.88
&lt; rxrx
1 88
100
188
108
108
Dwell
1 lt)W
1 88
1 88
1 88
1 88

ion ft
Owe 1 1

ft of
C {

-1 p }

i '
i
1 *.

13

i t)0

1 88

Group
Ions

!
IS

CO'

n ma

1 4 ww

I 1
1 88

rt

n

•

14

15

1 88

1 8.8

3

4

in

4

i r-

4

5
4

4 .

G

•"! r*

iivj

low MS R e s o 1 u tion NO

7

n

3

18

28

28

20

20

c y c l e s per second 1 .8

r
ion S
1
2
7&gt;
4
S
B
7
3
r!
.fi//: 304.88 386.88 328.88 322.88 348.88 342.88 3b2.88 ,3GB. 88 358.88
Dwell
188
180
188
180
100
!80
108
188
180

Gr'oup
ft of Ions .
start Time

' 1
IS
1 A

.Ti ft A'?

2

3

W
15

4
4

5
4

G
20

7
28

8
28

3
20

18
28

C* "i C rt rt "i — .

low MS Resolut ion NO

cycles per second 3.6

ion
ft
1
2
3
4
5
R
7
8
310
oi/'7 356.88''358.88 374.08 376.00 390.80 392.88 408.88 410.88 424.88 426.88
Dwell
100
180
100
100
100
100
180
180
100
100
ion
ft
1 1 . 1 2
13
14
IS
m / Z 4 4 4 . 8 8 4 4 6 . 0 0 468.88 462.08 472.00
Dwell
108
188
100
180
100
- . . ,.•--.--•; «;»
.

~~~i?i' - .+ it.•-•««• -•'•*-&lt;- -' '

-

�TABLE I (continued)

T E M P E R A T U R E
rUn time

Level
1
2 '
3
.5
5
B

95.00

eQui1ibration time

initial
tEmp '
190

.

P R O G R A M

S,

H E A T E D

0.50

initial
Rate
*" time. . &lt; G C / M i n &gt;
1.00
5.0
.
5.0
'
5.0
5.0
5.0

Z O N E S

s P l l t l e s s on t i m e

f i na I
tEmp
n ^ .'T.
(. i. «
"i -7 rjC.»)D

250 ".
270
300

t o t a1
t iPit?.

f i na I
t T Pit-IE) . 88
*1

i

i ~? r\ ^
/_ k&gt; . V ) V J

^K i*^

•? "? r* rx
J ,J . V VJ

r\ ni

r~ t

/ . VtVI

* r\

T
r*^
/ . V.I W

24.00

r\ni

r&gt; f . vj w

t n , v J vj

B5 . 00
nt-

'

Him

da . ww

7
8

Oven (Standby &gt;
Tnj P.irt B
Detector A

actual
1355
258
—

Setpt Limit
190
300
2B0. ' 250
Off
425

actual
InJ Port A
Transfer Line

278

Setpt
Off
275

Llf-ilt
250
300

�TABLE I (continued)

D A T A

Rev.

A C Q U I S I T I O N

1.3

1-Nov-84

load/store Method : METH:BINGIN.M
Description : CONGENER GROUP ANALYSIS FOR BINS INDOOR AIR SAMPLES
1.88
14.88
14.88
47.88
G8.88
95.03

X&gt;B-S"

Valves Splitlesa Off
Group '
Mass Spec On
Group 2
-~
Group 3
Stop Run

SIM

ACQUISITION

solvent; d e l a Y 14.88
Group
ft oP Ions

13 Jun 85

eM v o l t s

CD

"1

•raw 47

4
4

-L)

3

15

888 r e l n t i v e

"
7

L,

15

f*- Ft

Cn

2:87 pw

.5
4

M£TH:BINGIN.M

r e s u l t i n g v o l t a g e 2468
G
20

7
28

-

3
28

8
28

18
20

i~*r\

low MS -Resolut ion NO

cycles per second 8 .6

ir«
n
n
ri
2
It
1
3
4
b
o
/
o
3
10
f'i/Z 270 . 88 272 . 28B .88 288.88 304.80 306.88 312.88 328.88 322.88 334.88
88
Dwell
188
1 08
'1 08
1 88
188
188
108
180
108
i 00

ion

ion *

11

1I ^
-?

12

* ^H
I

•

15

I'M / Z 348.88' j 4 2 00 352 .88 35G.88 358.88
.
Dwell
108
1 88
1 80
t 88
1 r» r*
WW
Group
ft oP Ions

GO
R

]

i

15
r*. r\

3
15

4
4

5
4

B
28

7
28

8
28

3
28

18
20

A »-j

low 1-is Resolution NO

cycles per second I .0

.ion it
1
2
3
4
5
f
i
7
f
i
S
•r-t/Z 304.88 306.80 320.88 322.88 348.88 342.88 35Z-.88 3L!,, v)8 358.88
Dwell
180
100
108
100
100
180
100
1(^8
180

GiTuup

ft oP Ions
,
i
start

1
15

7.
3

"CQ
15

4
4

5
4

,G
20

"1
1

n
O

rx
D

&lt; rx
1 K.I

28

20

20

28

T 1

i i pie

low ma R e s o l u t ion NO

c y c l e s per second 8 .6

ion i t ,
I
2
3
4
5
G
7
8
310
ci/Z 356.88 358.88 374.08 376.OH 390.00 392.08 408.08 410.00 424.88 426.08
Dwell
100
188
100
100
180
100
188
100
100
180
ion «
I!
12
13
14
IS
Pi/Z 444.08 446.80 463.00 462.08 472.00
Dwell
100
180
180
IflW
100

.

•;&gt;.

�TABLE I (continued)

T E M P E R A T U R E
rUn t i m e

Level
1
2
3

.'

95.00

eQui 1 i brat, ion t i m e

initial
tEmp
190
.

initial
•** tli&gt;m
1.00
.

4
M

•Fi
B

P R O G R A M

S,

H E A T E D

0.50

Rate
(OC/Min)
5.0
5.0 ..
5.0

s P l i t l e s s on time

firm I
, . tErop
7.20
235
2 5 0 ''

r~
r\
D . W

(Standby)
Tnj Port B
Detector
ft

actual
i 30
Z50
—

&gt;~i "7 c\
£. f V/

5.0

•

300

Set.pt Liroit
'l951
300
250750
Off 425

Z O N E S

InJ Port A
Trans far' Line

final
tTr-ie
I B . 00
7.00
. ' ' 1 o . 5) w
'

1.88

. total
time
23.00
33.00
54.00

'"J n. r\
( . V.'W

r r"
ni -T
O a . Vlfl

24.00

35.08

actual
--278

Setpt
Off
275

Llrolt
ZR0
,300

�TABLE I (continued)

A T A

A, r. 0

ij 7

s

Method

1 0 ? d _•

7 7
:

T fi N

&lt; I?v .

i j 3

1 ~M n v - fi 4

NPTr-i r fi T W G I i . H

L"25cr i n t ion : 2375 ANALYSIS C'iy 2339 6G COLUMN

5 I I'l

A G' Q' U' I 5 I T 1 0 N

solvent deiaY
Group
!i of Ions
start Time

8,00

ef'l volts

t
'2
6
18
t&amp;.M 0.00

3
5
0.00

l a Jun 85

i5)'M3 am

600 relative

i'iETH'-BINGH.M

resulting voltage 2

4
5
' 6
4
5'
6
0.00 0.00 0.00

7
t

1

cycles per second 1.4

low "is Resolution txQ

i o n Jt
4
i
n ' Z 303 = ^0 305 •. 9 ? 3 i ? , 90 339 . 65 34 i .85 35 1 . 90
Dwell
.'(00
100
100
100
100
100

T E M F* E R A T U R E
run time
Level
1

75 . 00

P' R 0G R A M

0.50

eOui i ibrat ion time

initial
' tEmp
75

initial
time
',0
(0

H EA TED

&amp;

Ra t e
&lt;QC/Min&gt;
50.0

Z O N E S

split less on time

final
tump
235

f ina i
1 1r'ie
75,00-

0. 50

tot ai
time
73 . i^0

H

Oven (Standby)
Inj Fort B
Detector A

actual
75
250
—-

Setpt
7
5
250
Off

Limit
300
253
425

actual
Inj Fort A
Transfer Lino

235

Setpt
Off
235

Limit
250
300

�TRBLE 3. Indoor Rir Sariples Collected HIthin the Binghanton State Office Building Cpg/H35

F U R R N
LOCflTION

Vol HS

Recov.

Sanpla *

23P8 Te

Total To

.
231P8 Pe

123P8 Pe+
Racov.
13318 Pe Total P«
K

March 29-fipril 1
Floor &amp;-HVHC

77. (,

581
00

25
.

38

92

0.1

3

20

10,

Floor 6-Hl»fiC

PP.6

582
00

32
.

59

51

0.5

2?
.

12

6

??

583
00

38
.

61

10

1.6

1.1

2?

*.

Control CSpike?

0

5080-4

180

Control

0

5 8 0 ND CO. 23
05

Blank

0

5129P ND CO. 25

Floor H-HVRC

50
56

- •

198

SPIKE LEVEL

ND CO. 35

65 ND CO. 35
90

330

-

«

ND C0.25

-

*

ND CO. 25

-

5

618

D I0 X IN
LOCRTIOM

Vol H3

Sanple *
2 P Te
38

Total Ta

Recov.
Z

PeCDD

March 29~flpril 1
Floor 6-HVflC

PP.6

50801

NO CO. 35

Floor 6-HVHC

P.
P6

582
00

ND CO. 35

P?

50803

ND CO. 15

Floor 11-HUnC

5,

15?

82

-

ND C0.15

?2

ND CO. 15

55

ND CO. 55

8?

ND CO. 25

Control CSpi ke?

0

581
00

Control

0

5 8 0 ND CO. 25
05

100

ND CO. 25

Blank

0

5 2 ? ND CO. 25
19

103

ND C . 5
02

SPIKE LEVEL

?9

198

8

�o

Table 4.

Comparison of Polychlorinated Dibenzofuran Concentrations (Pg/m ) in Air
Samples

2378

" 4
-89
49

12378
12348 23478 Total
-Cl
"C15
~C15
5.0 ND(1)C , 33
2.9
31
0.5

2.0
ND(0.6)C

12C
6.9C

NA
ND(0.7)

NA
ND(1.5)

215
64

20.0
4.4

1.4
1.6

130
27

3.5
ND(0.7)

20
9.1

NA
ND(l.O)

NA
ND(2. 1)

150
57

13.0
3.7

1.2
1.1

83
29

16
8.0

NA
ND(l.O)

NA
ND(2. 1)

Total
C1

6th Floor
,
Sept., 1984?
April, 1985

6.0
2.8

14th Floor
Sept., 1984b 10
April, 1985° 3.8

123478
cl

" c

Total

Total

cl

~ c
0

Total
"C1P
o—

GRAND AVERAGE

Sept., 1984
April, 1985

8. 0
3. 3

2.9
1.2

(a) ND indicates not detected (limit of detection); NA = not analyzed for
(b) Average of two samples unless specifically indicated
(c) Based on measurement in one sample

�. * .&gt;' • /

Table 5.

Calculation of Average "2,3,7,8-TCDD Equivalents Due to Various
Dibenzofurans, Dibenzodioxins and Biphenylenes for 6th and 14th
Floor Air Samples

Best Estimate
of Average
Concentration
Equivalents"

X

Relative Activity of
Compound Class vs .
Dibenzodioxins

X

X

1/3

X

X

1/3

X

Relative Activity
Due to Chlorine
Substitutions

=

"2,3,7,8TCDD

2,3,7, 8-TCDF
3.3 pg/m3

1

= 1 . 1 pg/m3

X

1

= 1 . 6 pg/m3

1/3

X

1/30

=

X

1

X

1

=

&lt;0.4 pg/m3

X

1

X

1

=

&lt;0.5 pg/m3

X

1

X

1/30

=

&lt;0.07 Pg/m3

1

X

1

=

&lt;0.2 pg/m3

1

X

1

-

&lt;0.2 pg/m3

'

12378, 12348,
23478-PeCDF
4.8 pg/m3
HEXA CDFs
8.0 pg/m3
2

0.04 pg/m3

2378-TCDD
&lt;0.4 pg/m3
12378-PeCDD

&lt;0.5 pg/m
HEXA CDDs
&lt;2.1 pg/m3

2367-Tetrachlorobiphenylene
&lt;0.2 pg/m3

X

12367-Pentachlorobiphenylene

&lt;0.2 pg/m

X

Total

(a)

&lt;4. 1 pg/m3

Since standards are not available to allow quantitation of all
2378-substituted hexa CDFs, it is conservatively assumed that 1/2 of the
"total hexa CDF" is 2378-substituted.

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&lt;p&gt;For more about this collection, &lt;a href="/exhibits/speccoll/exhibits/show/alvin-l--young-collection-on-a"&gt;view the Agent Orange Exhibit.&lt;/a&gt;&lt;/p&gt;</text>
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              <text>2264</text>
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              <text>Series IV Subseries II</text>
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              <elementText elementTextId="23945">
                <text>Smith, R.</text>
              </elementText>
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                <text>P. O'Keefe</text>
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                <text>K. Aldous</text>
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              <elementText elementTextId="23952">
                <text>Typescript: Chemical Data on Air Samples Collected in and near the Binghamton State Office Building (February, March 1985) Before and After the HVAC System is Returned to Normal, July 17, 1985</text>
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              <elementText elementTextId="23954">
                <text>BSOB</text>
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              <elementText elementTextId="23955">
                <text>ambient air sampling</text>
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        <src>https://www.nal.usda.gov/exhibits/speccoll/files/original/acd6fa44b38089188cb031e79efe0a0f.pdf</src>
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                  <elementText elementTextId="63616">
                    <text>Item D Number

02237

Author

Eadon, G.

Corporate Author

Center for Laboratories and Research, New York State

ROpOPt/APtlClO Titlfl Typescript: Chemical Data on Air Samples From the
Binghamton State Office Building

Journal/Book Title
Yoar

Month/Day
Color
Number of Images

1983

J"i y n
D

14

Descriptor) Notes

Thursday, September 20, 2001

Page 2237 of 2293

�Chemical Data on Air Samples
From the Binghamton State Office Building

G. Eadon, K. Aldous, D. Hilker, P. O'Keefe and R. Smith

11 1933
DIRECTOR
HEALTH
Center for Laboratories and Research
New York State Department of Health
Albany, New York

12201

�Abstract
Air samples collected at 15 distinct locations and/or times within
the Binghamton State Office Building have been analyzed for various
chlorinated dibenzofurans, dibenzodioxins and biphenylenes.

The average

2,3,7,8-TCDF concentration from twelve locations sampled when the
building's internal air circulation system was operative was 15.0 +
3.6 pg/m .

Samples collected at six locations under similar

conditions and analyzed using a cleanup methodology designed to recover
the full range of compounds of interest had "total TCDF" and total Penta
O

CDF" concentrations of 143 + 24 pg/m
respectively.

O

and 42 + 10 pg/m ,

"Total hexa CDF" was measured at 4.8 + 3.5 pg/m

three samples collected under these conditions.

in

"Total TCDD"

concentrations at two locations were 1.0 and 1.3 pg/m , while "total
Penta CDD" concentration was &lt; 0.5 pg/m

at both locations.

Measurement of 2,3,7,8-TCDD at two locations gave concentrations of 0.3
&lt;
3
and 0.5 pg/m . "Total tetrachlorobiphenylenes" were estimated at 0.3,
0.5 and 1.3 pg/m

at three locations and "total pentachloro-

biphenylenes" at 1.5 and 2.6 pg/m

in two locations.

A methodology used with apparent success to calculate the
"2,3,7,8-TCDD equivalent" concentration in a sample of soot collected in
the BSOB was applied to this data to estimate that the overall activity
present in the air was ca. 14 pg/m

"2,3,7,8-TCDD equivalents."

�3
The air of the Binghamton State Office Building (BSOB) was sampled
for various chlorinated dibenzofurans, dibenzodioxins and biphenylenes
in November 1982 (Smith et al., 1983), February 1983 (Smith et al.,
1983a) and April 1983 (Smith et al., 1983b).

Detailed descriptions of

the method development and validation, analytical methodologies and
quality control data have already been provided; the intent of this
paper is to summarize the results obtained from the analysis of BSOB air
and to use that data to calculate the approximate "2,3,7,8-TCDD
equivalent concentration" (Eadon et al., 1982) that these results
correspond to.
Chemical Data
Table 1 contains the analytical data generated during the three
samplings of BSOB air.

The samples collected in 11/82 were obtained

with the internal air circulation system inoperative? therefore, these
results will not be referred to in subsequent discussions.

Samples

collected at 12 different locations on 2/83 and 4/83 had average
2,3,7,8-TCDF concentrations of 15.0 + 3.6 pg/m
represent one standard deviation).

(error limits

The relatively small standard

deviation for this large data set for 2,3,7,8-TCDF demonstrates that the
compound is fairly uniformly distributed from floor to floor.

Since

this compound's relevant physical and chemical properties are similar to
those of the other analytes discussed in this paper, it is possible that
they too are rather uniformly distributed.

The more limited data set

contained in Table 1 for other classes of compounds is consistent with
this proposal.

�4
Because 2,3,7,8-TCDF concentrations were determined using an
internal standard technique, all data are considered accurate.

However,

it is believed that "total TCDF" and "total penta CDF" data produced
from the 11/82 and 2/83 samplings may underestimate the actual
concentrations of these compounds; for example, during analyses of the
2/83 samples, it was observed that only two of three penta CDF standards
were adequately recovered during cleanup of spiked samples (Smith et
al., 1983a).

The methodology used in the cleanup of the 4/83 samples

was modified to permit recovery of a broader range of compounds.

These

data now provide the most reliable estimate of the concentrations of the
remaining compounds and groups of isomers of interest and will therefore
be used in subsequent discussions.
Six locations sampled on 4/83 exhibited an average "total TCDF"
o

concentration of 148 + 24 pg/m

and a "total Penta CDF"

concentration of 42 «_ 10 pg/m . Total Hexa CDF averaged 4.8+3.5
+
—
pg/m

at three of the locations.

In three samples collected at two •

locations, "total TCDD" averaged 1.2 + 0.2 pg/m3 and 2,3,7,8-TCDD
3
3
averaged 0.4 + . 1 pg/rn ; "total Penta CDD" was &lt; 0.5 pg/m . Since
no quantitative standards were available for the biphenylenes, only
estimates of their concentrations were generated.

However, three

locations exhibited "total tetrachlorobiphenylene" concentrations of
roughly 0.3, 0.5 and 1.3 pg/m 3 , and two locations exhibited "total
pentachlorobiphenylene" concentrations of 1.5 and 2.6 pg/m .
Several interesting comparisons can be made between the data
produced from these air samples and those produced from soot samples

^

�5
collected from above the ceiling panels on various BSOB floors (Eadon
et al. , 1982).

In 12 soot samples, the ratio of tetra CDFrpenta CDF:

hexa CDF was 1.2 + 0.2:1:0.5 ± 0.2.

The corresponding relationship

produced from the air data summarized above is 3.5 + 0.6:1:0.11 + .02.
This increase in the relative concentrations of the less chlorinated
and thus more volatile congeners suggests that the air contamination may
not be predominantly due to suspended soot particles but may instead be
true vapor-phase material.

Consistent with this hypothesis, when the

particulate material collected using a 0.3 u glass fiber filter was
analyzed separately from the silica cartridge portion of the air
sampling apparatus, only minor amounts of PCDFs were detected.

&gt;For

example, three samples in which the glass fiber filter and silica
cartridge were analyzed separately, the ratio of "total TCDF" in the two
collection media was 0.04 + .01 (Smith et al., 1983a, 1983b).
Air samples collected simultaneously with those used for PCDF
analysis exhibited PCB concentrations of 0.16 + .02 ug/m
(Versar, 1983).

This concentration corresponds to a PCB:"total TCDF"

ratio of 1200; the ratio in soot was 50.

Here, too, the relative

concentration of the more volatile component has been markedly enhanced.
Calculation of "2,3,7,8-TCDD Equivalents"
The assessment of the biological activity of a complex mixture of
chlorinated dibenzofurans, dibenzodioxins, and biphenylenes is
complicated by the lack of definitive knowledge of the toxicities of
most of the individual congeners, by the inability to accurately analyze

�6
all congeners and by the possibility of synergistic or antagonistic
interactions among these compounds.

The most straightforward approach

to this problem is to utilize the techniques of animal toxicology to
compare the biolgoical activity of the mixture to that of a reference
compound.

This approach, when applied to a representative sample of

soot taken from the BSOB led to the conclusion that the acute oral
LD,-n in guinea pigs of the soot was equivalent to that of an inert
matrix containing 58 ug/g of 2,3,7,8-TCDD (Badon et al. , 1982).
Because of the differing chemical composition of the contaminants
present in the air and in the soot, this number has little direct
applicability for estimating the biological activity of compounds
present in the air. Further, the concentrations present in the air are
so low that performing further animal toxicology experiments to estimate
the air's biological activity is impractical.
An alternative approach to this problem is to utilize available
Si

analytical and toxicological data together with necessary assumptions .
and approximations to estimate the number of "TCDD equivalents" due to
particular contaminants, and then summing the overall activity over the
range of toxic compounds.

Although such an approach is obviously only

an estimate, it is notable that, when applied to the soot sample used in
the animal toxicology experiments, it produced an estimate of the "TCDD
equivalent" concentration that agreed remarkably well with the animal
toxicology experimentation. (44 ug/g calculated vs. 58 ug/g observed).
The important conclusion was reached that the acute oral LD

of the

soot could be estimated without the necessity of postulating major
synergistic or antagonistic effects (Eadon et al.r 1982).

�7
Use of chemical data to "predict" the 2,3,7,8-TCDD equivalent"
concentration of the BSOB air is complicated by the fact that no animal
toxicology data is available on the effects of inhalation of these
compounds.

As a consequence, it is necessary to assume that acute oral

guinea pig LD^s can be used to relate the air's overall activity to
2,3,7,8-TCDD.

Another complication is that only limited data is

available on the acute oral guinea pig LD,_0s of dibenzodioxins and no
such data is available on biphenylenes or dibenzof urans other than
2,3 ,7,8-TCDF.

The following assumptions will therefore be made about

the LDcns of these compounds:
(1) The ratio of the LD

s Of a particular PCDP congener and

2,3,7,8-TCDF or of a particular polychlorinated biphenylene congener and
2 ,3 ,6,7-tetrachlorobiphenylene will be the same as the ratio of the
LD5Qs of the corresponding PCDD congener and 2,3,7,8-TCDD.

There is

presently very little experimental data to support this assumption.
\

(2) The LD5Qs of PCDFs , PCDDs and polychlorinated biphenylenes
lacking chlorines on at least one of the four lateral positions will be
sufficiently high that their influence can be ignored in this
calculation.

This assumption is based on the LD5Qs in guinea pigs of

2,8-diCDD, 2 ,3 ,7-triCDD, and 1 ,2,4,7, 8-penta-CDD.

All have LD5Qs more

than 450 times higher than that of 2,3 ,7,8-Tetra CDD itself (Table II).
(3)

Introduction of a single additional chlorine substituent on a

2,3 ,7,8-substituted PCDD or PCDF congener or a 2,3 ,6,7-substituted
polychlorinated biphenylene congener has essentially no effect on the
congener's guinea pig LDcn.

This assumption is based on comparison of

the LD5Qs of 2,3,7,8-TCDD and 1,2,3 ,7, 8-penta-CDD (Table II).

�8
(4)

Introduction of two additional chlorine substituents on a

2,3 ,7 ,8-chlorinated PCDD or PCDP congener or a 2 ,3 ,6 ,7-substituted
polychlorinated biphenylene congener raises its LD5Q by a factor of at
least 29 .

The assumption is based on comparison of the LD^s of

1,2,3,4,7,8-, 1,2,3,6,7,8-, and 1 ,2 ,3 ,7 ,8,9-hexa CDD and 2,3 ,7 ,8-tetra
CDD (Table II).
(5)

The LDcns of compounds with more than 6 chlorines will be
DU

sufficiently large that their influence can be ignored in this
calculation.

This assumption is based on comparison of the LD5Qs of

1,2,3,4,6,7,8-hapta CDD and 2,3 ,7 ,8-teura CDD (Table

II).

These assumptions require that attention be focused only on
2,3 ,7,8-substituted tetra, penta and hexa-substituted PCDDs , PCDFs and
biphenylenes . Measurements of 2,3,7,8-TCDF concentrations at 12
different locations with the internal air circulation system operative
2
gave average concentrations of 15.0 Hr 3.6 pg/m ; since the data in
Table II indicate that the LD5Q of 2 ,3,7,8-tetra CDF is about three •
times that of 2,3 ,7,8-TCDD, the equivalent in terms of acute oral guinea
pig toxicity to a 2 ,3 ,7,8-TCDD concentration is 5 pg/m

(Table III).

Measurements at 6 different locations all taken with the interval air
circulation system operative and using an optimized analytical
methodology yielded total penta CDFs of 42 +_ 10 pg/m .

Based on

earlier soot data, it is conservatively assumed that the most toxic
isomers (1,2,3,7,8- and 2,3 ,4 ,7 ,8-penta CDF) together constitute 50% of
the penta CDFs and that their LD5Qs equal that of 2,3,7,8-TCDF; thus,
o

the penta CDFs contribute 7.0 pg/m

of 2,3,7,8-TCDD equivalents.

Hexa-CDFs were present at total concentrations of 4.8 pg/m
samples.

in three

Based on dioxin studies, the most toxic hexa substituted

�9
dioxins are ca 1/30 as toxic as 2,3,1,8-TCDD; to account for the
differing toxicities of 2,3,7,8-TCDD and 2,3,7,8-TCDF it will be
concluded that the hexa-CDFs contribute less than 0.1 pg/m

TCDD

equivalents, a negligible number in comparison to the contributions of
the tetra- and penta- CDF.
The PCDDs themselves also make only a small contribution to the
"TCDD equivalent" concentrations present in the air of the BSOB.

ThusA
o

2,3,7,8-TCDD was present at an average concentration of 0.4 pg/m ,
corresponding to a contribution of 0.4 pg/m

TCDD equivalent.

Total

Penta CDD was below detection limit (0.5 pg/m ; and therefore can make
only a negligible contribution to the "TCDD equivalent" concentration.
Total tetrachlorobiphenylenes were roughly 'estimated at 0.7
pg/m . If the conservative assumptions are made that the toxic 2,3,6,7
congener constitutes 50% of the mixture and that biphenylenes are as
toxic as

the corresponding dioxins, the tetrachlorinated biphenylenes
^

contribute 0.4 pg/rn3 "2,3,7,8-TCDD equivalents."
Pentachlorobiphenylenes averaged 2.1 pg/m .
are made, this corresponds to 1.1 pg/m

If similar assumptions

"2,3,7,8-TCDD equivalents."

Insufficient sample was available to attempt a measurement of
hexa-biphenylenes; however, in view of the factor of 30 estimated
difference in toxicity between tetra and hexa substituted compounds, the
hexa-biphenylenes

are unlikely to be major contributors to the "TCDD.

equivalents" in the BSOB air.
Based on these calculations, the concentration of "2,3,7,8-TCDD
equivalents" in the BSOB air is estimated at 13.5 pg/m ; ca. 90% of
this estimated activity resides in the tetra and penta CDF isomers
(Table

III).

�10

Conclusions
The concentrations of the principal compounds of concern in the air
of the BSOB have been measured.

These experiments have provided

evidence suggesting that the contamination in the BSOB air is fairly
uniformly distributed throughout the working space of the building in
floors 3-17 and is in the gas phase, rather than particulate bound.
Based on the results of chemical analysis, literature-derived acute oral
guinea pig LDggS and a variety of assumptions, it was estimated that
the air contains ca. 14 pg/m3 "2,3,7,8-TCDD equivalents."

�References
Eadon, G., Aldous, K., Frenkel, G., Gierthy, J., Hilker, D.,
Kaminsky, L., O'Keefe, P., Silkworth, J., and Smith, R. (1982).
Comparison of Chemical and Biological Data on Soot Samples from the
Binghamton State Office Building, New York State Department of Health
Report.
Smith, R.M., Hilker, D., O'Keefe, P., and Aldous, K. (1983).
Determination of TCDFs and TCDDs in Air Samples from the Sixteenth Floor
of the Binghamton State Office Buildng, New York State Department of
Health Report, March 16, 1983.
Smith, R.M., Hilker,

D., O'Keefe, P. .and Aldous, K. (1983a).

Determination of Tetra-Hexa CDFs and Tetra CDDS in Air Samples from the
11,14,16, and 17th Floors of the Binghamton State Office Building, New
York State Department of Health Report, May 16, 1983.
Smith, R.M., Hilker, D., O'Keefe, P. and Aldous, K. (1983b).
Determination of Polychlorinated Dibenzofurans, Dibenzodioxins and
Biphenylenes in Air Samples from the 3rd, 5th, 7th, and 9th Floors of.
the Binghamton State Office Building, New York State Department of
Health Report, in preparation.
Versar New York Inc. (1983).

Determination of the Ratios of Toxic

Chemicals in the Air in the BSOB: PCB Analysis, Versar New York Report,
May 23, 1983.

�Table I Concentrations of Polychlorinated Dibenzofurans, Dibenzodioxins, and Biphenylenes
Determined 1n 11/82, 2/83, and 4/83 Samplings of the BSOB1'2
"TOTAL PENTACDF"
"TOTAL TCDF"
2,3,7,8-TCDF
LOCATION3
DATE
16th, NE
16th, SE
16th, NW
16th, SW
17th, NW
16th, NW
14th, NW
14th, NE
llth, SE &amp; NW
11th, NW
llth, NW

11/82
11/82
11/82
11/82
2/83
2/83
2/83
2/83
2/83
2/83
4/83

14 pg/m3
13 pg/m3
9.2 pg/m3
7,0 pg/m3
11.5 pq/m3
16 pq/m3 11 pq/m3
14 pg/m3
16 pg/m3
23 pq/m3

97
78
55
52
71
118
92
185
133
76

pg/m3
pg/m3
pg/m3
pg/m3
pg/m3
pg/m3
pg/m?
.pg/m3
pg/m3 .
pg/m3

9th, SE
9th, NW

4/83
4/83

14 pq/m3
16 pq/m3

150 pq/m3
14^5 pq/m3

7th, NW
5th, NW
3rd, NW
5th, NE
AVERAGE
CONCENTRATION

4/83
4/83
4/83
4/83

11
11
16
20

pq/m3
pg/m3
pq/m33
pq/ffi

121 'pq/m'
126 pq/m3
151 pq/m3
195 pq/m3

15.0+ 3-6 pg/m3

148+24 Pg/W3

OTHER

"TOTAL TCDD" &lt;1,2 pg/m3
"TOTAL TCDD" &lt;1.3 pg/m3
"TOTAL TCDD" &lt;1,3 pg/m3
17
21
21
13
19
16

pg/m3
pg/m3
ps/ni3
pg/m3
pg/m3
pq/m3

.,

"TOTAL TCDD" 1.0 pq/m3; 2,3,7,8-TCDD 0.3 pq/m3
"TOTAL PENTACDDs" &lt;0.5 pg/m3} "PENTACHLOROBIPKENYLENES 2.5 pq/m3
"TOTAL HEXACDF" 3.7 pg/m3
"TOTAL TCDD" 1.3 pg/m3-, 2,3,7,8'TCDD 0.5 pg/m3
""OTAL PENTACDDs" &lt;0.5 pg/m3} "PENTACHLOR03IPHENYLENES 1.4 pg/m3
"TETRACHLOROBIPHENYLENES" 0.5 pg/m3
"TOTAL HEXACDF" 2,0 pg/m3. 5th. MW; 8.7 pg/m3 'Sth, 'NE
"TETRACHLOROBIPHENYLENES" 1,3 pq/m3
"TETRACHLOROBIPHENYLENES" 0.3 pc;/m3
"TOTAL HEXACDF"4,8i3..5Pg/ni3; "TOTAL TCDD" 1.2 + 0.2 pg/m3
2,3,7,8^TCDD 0.4 + ,1 pg/m3-, "TOTAL PENTACDD" &lt;0.5 pg/m3
"TETRACHLOROBIPHENYLENES" 0.7 +0,5 pg/m3
"PENTACHLOROBJPHENYLENES" 2,1 +, .5 pg/m3

l

Undf!r]incd data were collected with tho building's internal circulation system operative and analyzed using most current methodology. These results are considered to be the most reliable indicators of the building's current condition and are therefore the basis of all subsequent calculations and discussions.
* "^abstracted8 (Sml"!! e^af^T' 8n?lyt1cB] Pro«.dur«» an£i Witty control/quality assurance procedures are detailed in the papers from which these data
3

Average concentrations calculated using underlined (best) values only; error limits equal one standard deviation,

�Table II. Influence of Structure and Chiorination Pattern on Guinea Pi a
Oral LD5Qs (Male, Hartley, 200-250g)
Compound

LD5Q(ug/kg)

2,3,7,8-Tetra CDD
2,3,7,8-Tetra CDF
1,2,3,7,8-Penta CDD
1,2,3,4,7,8-Hexa CDD
1,2,3,7,8,9-Hexa CDD

2.5a
5-10b
3.1C
73C
60-100C

1,2,3,6,7,8-Hexa CDD
1,2,3,4,6,7,8-Hepta CDD

1,2,4,7,8-Penta CDD
2,3,7-TH CDD
2,8-Di CDD

70-100°
&gt; 600C

1,125C
29,444C
730,000°

a

J.B. Silkworth, D. McMartin, A.P. DeCaprio, R. Rej, P. O'Keefe and L. Kaminsky (1982),
Acute toxicity in guinea pigs and rabbits of soot from a polychlorinated biphenylcontaining transformer fire, Toxicol.Appl. Pharmacol. 65, 425-39.
J.A. Moore, E.E. McConnell, D.W. Dalgard, and M.W. Harris (1979). Comparative
toxicity of three halogenated dibenzofurans in guinea pigs, mice and rhesus
monkeys. NY Acad. Sci. 320, 151-163.

C

E.E. McConnell, J.A. Moore, J.K. Haseman, and M.W. Harris (1978). The comparative
toxicity of chlorinated dibenzo-p-dioxins in mice and guinea pigs. Toxicol. Appl.
Pharmacol. 44, 335-356.

�Table III. Calculation of "2,3,7,8-TCDD equivalents," Due to Various
Dibenzofurans, Dibenzodioxins and Biphenylenes
Relative Activity of
Relative Activity
Compound Class
Due to Chlorine
vs. Dibenzobioxins X
Substitution
=

Best Estimate
of Concentration

X

2,3,7,8-TCDF
15 pg/m3

X

1/3

X

1

5 pg/m3

Penta CDFs
42 pg/m3
2a

X

1/3

X

1

7 pg/m3

Hexa CDFs 3
4.8 pg/m
2a

X

1/3

X

1/30

X

1

X

1

0.4 rg/m3

1,2,3,7,8-Penta CDD
&lt; 0.5 pg/m3
X
2a

1

X

1

&lt; 0.3 pg/m3

2,3,6, 7-Tetrachl orobi phenyl ene
1
0.7 pg/m3
X
2a

X

1

0.4 pg/m3

1 ,2,3,6,7-Pentachlorobiphenylene
1
2.1 pg/m3
X
2a

X

1

2,3,7,8-TCDD
Q.c. pg/m3

=

=

"2,3,7,8-TCDD
equivalents"

&lt; 0.1 pg/m3

&gt; 1 pg/m3

ca. 14 pg/m3

When isomer-specific data are unavailable, it is assumed that 1/2 of the "total"
value corresponds to 2,3,7,8-(dibenzodioxins and dibenzofurans) or 2,3,6,7(biphenylene) substituted compounds.

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                    <text>Ram D Number

02227

Author

Smith, R.M.

Corporate Author
ROpOrt/ArtlGlB TitlO Typescript: Determination of Tetra-Hexa CDFs and
Tetra-CDDs in Air Samples from the 11,14,16 and
17th Floors of the Binghamton State Office Building,
May 16, 1983

Journal/Book Title
Year

000

°

Month/Day
Color
Number of Images

D

50

Descriptor Notes

Thursday, September 20, 2001

Page 2227 of 2293

�Determination of Tetra-Hexa CDFs and Tetra-CDDs in
Air Samples from the 11, 14, 16 and 17th Floors
of the Binghamton State Office Building

R. M. Smith, D. Hilker, P. O'Keefe and K. Aldous
Laboratory for Organic Analytical Chemistry

New York State Department of Health

5/16/83

RECEIVED
MAY 2 3 1983
DIRECTOR
PUBLIC HEALTH

�INTRODUCTION

Analysis of air samples taken from the 16th floor (NE, SE, NW,
and SW Corners) of the Binghamton State Office Building (March 16,
1983 NYS report) showed concentrations of from 7 to 16 pg/m3 2,3,7,8
TCDF and 52-102 pg/m3 total TCDF. Penta-CDF appeared to be lower in
concentration, detected in only one sample out of four at a total
concentration of 22 pg/m1. 2,3,7,8 TCDD, found at 0.26-2.2 ppm
levels in soot samples analyzed after the transformer fire, was not
confirmed in air samples from the 16th floor at concentrations of &lt;1.3
pg/m3, although a signal at m/e 322 was detected.
In the present study it was necessary to analyze additional air
samples to:

1.

determine the floor-to-floor variation of PCDFs in

air.
2.

re-analyze samples to determine the precision
of sampling and analysis.

3.

separately analyze the particulate and adsorbed
gaseous PCDFs.

4.

combine samples for greater sensitivity for both
PCDFs and TCDDs.

Using silica gel adsorbent cartridges containing labelled
2,3,7,8 TCDD,

13

C

37

C1 OCDD, J'C1 2,3,7,8 TCDF and •7C1 penta-

CDF (3 isomers), 50 m3 air were collected. They were then combined
as necessary prior to clean-up and analysis by SP 2330 capillary
GC/SIM high resolution mass spectrometry.

It is important to note

that while the analysis has been validated and is quantitative for
2,3,7,8 TCDD, 2,3,7,8 TCDF, OCDD and OCDF, certain non-2,3,7,8

�3
substituted TCDD (and presumably PCDF) isomers have been found to be
removed in the clean-up process.
EXPERIMENTAL
Samples for analysis
PCDFs
Floor 16, analyzed in our preliminary study of PCDFs in air, was
sampled as a repeat analysis.

Duplicate samples were taken on the

14th and 17th floor for which previously obtained full-scanning HRMS
PCDF in soot (dust) data is available. For 17th floor samples, the
glass fiber particulate filter «.3u) was analyzed separately from the
silica gel gaseous adsorbent cartridge.

To obtain greater

sensitivity, particularly for the higher chlorinated PCDFs, a combined
sample from the llth floor was analyzed.

Duplicate 10 pg/m3 2,3,7,8

TCDF-fortified background air samples (NSA 6S, DOB 1) along with a
background air sample (DOH 2) and a solvent blank were also analyzed
as part of normal quality control procedures.
TCDDs
To obtain adequate sensitivity, four 50 m3 samples were
extracted, combined and analyzed (in duplicate) for TCDDs, injecting
nearly the entire sample in a single injection.

A combined solvent

blank and a 1 pg/m3 2,3,7,8 TCDD-fortifitfd background air sample were
also analyzed.
Sampling Procedures
Generally, each BSOB sample taken on a given date was identified
by a number specifying the floor, a letter specifying the corner of
the building, another number indicating replicates and finally a
letter P for particulate or G for gaseous, e.g. 17C2G.
In addition to the internal standards used in our earlier study
(60 pg "C 2,3,7,8 TCDD, 5000 pg » 7 C1 OCDD and 1200 pg » 7 C1
2,3,7,8 TCDF), 24000 pg of "Cl penta-CDF (3 unspiked

�isomers) in benzene was deposited directly onto the silica gel
(activated at 140 C) trapping adsorbent prior to sampling. The 2
stage sampling apparatus, assembly, transport and sampling has been
described in the March 16, 1983 NYS report.
Extraction
(See March 16, 1983 NYS report)

16 hr benzene soxhlet

extraction. Internal standards were added to 17C1P and 17C2P prior to
extraction.

Native 2,3,7,8 TCDD and 2,3,7,8 TCDF were added to

fortified samples prior to extraction.
Sample Clean-up
(See March 16, 1983 NYS report)

The microprocessor controlled

clean-up was a sequence of basic alumina, PX-21 carbon, and neutral
alumina followed by a single concentration to 5-10 joL for GC/MS
injection.
Capillary GC/HBMS
In summary:

2 \iL of sample extract was injected onto a 0.3 mm x

60 m SP 2330 GC capillary interfaced directly into MS-50 via a fused
silica SP 2330 butt-joint transfer line.
3 min, 60°/min to 190°,

The GC program was 70° for

2.5°C/min to 240° hold.

Kratos MS-50 mass

spectrometer was used in the El mode (70 ev), approx. 10,000
resolution (10% valley), source 250°C, DS-55 data system, with
multiple peak monitoring mode as follows:
For PCDFs (m/e)
1st Injection:

304, 306 - M, M+2 of Tetra CDF
312 - TCDF internal std
340 - M+2 of penta CDF

�2nd Injection:
(optional)

338, 340 - M, M+2 of penta CDF
348 - penta CDF internal std
374 - hexa CDF

For TCDDs
1st Injection:

320, 322 - M, M+2 of TCDD
334 - TCDD internal std.

Calculations
(See March 16, 1983 NYS report for details)

Internal standard method

of calculation C^ - X Cz A1/Aa.
TCDDs:

individual scans at m/e 322 are summed across a single
peak (for 2,3,7,8 TCDD) or a range of observed peaks (for
total TCDDs). The area under the resulting mass profile
is then ratioed to that of the

iS

C 2^3,7,8 TCDD

internal standard at m/e 334.
TCDFs:

individual scans at m/e 306 are summed across a single
peak(for 2,3,7,8 TCDF) or a range of observed peaks (for
total TCDFs). The area under the resulting mass profile
is then ratioed to that of the

J7

C1 2,3,7,8 TCDF

internal standard at m/e 312.
penta-CDFs:

individual scans at m/e 340 are summed across a range of
observed peaks for total penta CDFs. The area under the
resulting mass profile is then ratioed to that of the
1T

C1 2,3,7,8 TCDF internal standard.

factor of 1 is assumed.

The

J7

A response

C1 penta CDF internal

standards were monitored in a 2nd injection of several
samples and not used for quantitation.

�hexa-CDFS:

individual scans at m/e 374 are summed a range of
observed peaks for total hexa CDF. The area under the
resulting mass profile is then ratioed to that of the
37

C1 2,3,7,8 TCDF internal standard.

A response

factor of 1 is assumed.
RESULTS AND DISCUSSION
In general, air samples taken from the 11, 14, 16 and 17th floors
of the Binghamton State Office Building were found to contain complex
mixtures of tetra-, penta and possibly hexa CDF isomers as shown by
the high resolution (HR) single ion chromatograms in figure 1 for
floor 11. Tetra-CDFs were predominant on all floors, having
concentrations of from 76 to 185 pg/m3 total TCDF as given in Table
1. Figures 5-12 are HR single ion chromatograms showing the presence
of a mixture of TCDF isomers in all samples (except particnlate) from
floors 11, 14, 16 and 17.

Figures 13 and 14 show a

2378-TCDF-fortif ied sample and solvent blank. A more complete, set of
data including HR mass profiles is shown in figs. 17-26 for samples
11C (combined) and 16C1.

When intepreting these chromatograms it is

important to note that isomer patterns may be distorted as all isomers
are not recovered through the sample clean up.

The 2,3,7,8 isomer was

found in all samples at concentrations of from 0.8 to 23 pg/m3.

For

floor 17, the glass fiber particulate filter (17C1P, 17C2P) was
analyzed separately from the silica gel adsorbent cartridge (17C16,
17C2G). The entire mixture of TCDFs was found on the adsorbent and
little or none in the particulate section O.3 |i) of the sample trap
(figs. 8-10, 15-16).

�Penta CDFs, which were more abundant than tetra CDF in the original
soot, were found in all non-particulate air samples however at lower
concentrations of from 6.6 to 24.4 pg/m3 (Table 2). A possible
.explanation for this is the lower volatility of penta compared to
tetra CDFs. High resolution single ion chromatograms and mass profile
data for penta CDFs in samples 11B3 + 11B4 + 11C1, 17C1G, 17C1P, and a
solvent blank are shown in figures 27-30. A typical 2nd injection of
a sample to acquire data on hexa (and penta) CDFs is shown for sample
11B3 + 11B4 + 11C1 in figures 31-34. No hexa CDF could be confirmed
at a detection limit of approximately 5 pg/m3.
To obtain adequate sensitivity for TCDDs, four 50 m3 BSOB air
samples were extracted and combined to form a single sample prior to
clean up and analysis. The SP2330 capillary GC/HRMS results for a
combined llth floor air sample (analyzed in duplicate), a solvent
blank, and a background air sample fortified to 0.82 pg/m3 with
native 2,3,7,8 TCDD are given in Table 3. Because only a small amount
of sample 11C6" + 11C7 + 11C8 + 11C10 was injected, the signal/noise
for that sample was weak (a wide peak was also observed, hence
asignificant concentration). The HR single ion chromatograms and mass
profiles for a combined BSOB air sample 11C1 + 11C2 + 11C4 + 11C5
(figs. 35-37) showed 226 pg 2,3,7,8 TCDD equivalent to 0.94 pg/m3 air
(also possible traces of other TCDDs). A quality control (120 m3
Albany air) sample fortified with 98 pg native 2,3,7,8 TCDD to
0.82 pg/m3 air was analyzed and found to have a concentration of
1.3 pg/m3. A solvent blank was similarly analyzed and found to
contain an rather high 47 pg 2,3,7,8 TCDD equivalent to
0.39 pg/m3 air.

�CONCLUSIONS

Analysis of air samples for a complex mixture of PCDDs and PCDFs at
concentrations in the parts per quadrillion range had never been attempted
prior to these studies.

Although considerable progress has been made in the

development and application of the necessary analytical techniques, several
problems remain unresolved.

The concentration of 2,3,7,8-TCDD in the air of

the BSOB could not be accurately determined in this group of samples due to
the presence of very low concentrations of interfering compounds in the
blank.

It is clear, however, that the concentration of 2,3,7,8-TCDD is

below 1.5 pg/m3, consistent with an earlier report from the laboratory.

A

second problem relates to the lack of labelled quantitative PCDF standards
(for congeners other than 2,3,7,8-TCDF). Quantitative analysis of a
congener without an internal standard is difficult, since recoveries are not
accurately known. In the present instance, when even unlabelled standards
of the range of compounds sought are unavailable, and certain congeners are
demonstrably poorly recovered, the difficulty is even more acute.

Thus,

calculations of "total TCDF'' and "total PCDF" may underestimate actual
concentrations of these mixtures.

Attempts will be made to further address

these problems in future analyses.
Nevertheless, these data permit some important conclusions regarding
the PCDD/PCDF concentrations,in the BSOB. The concentration of 2,3,7,8-TCDF
measured in six locations varied from 9.9 to 23 pg/m3.

The ratio of tetra

CDF to penta and hexa CDF is clearly higher in these air samples than

�-9-

in the soot samples analyzed earlier.

Coupled with the observations that

the bulk of both 2,3,7,8-TCDF and "total TCDF" was found in the silica gel
cartridge rather than in the particulate material, this result suggests that
these compounds are predominantly in the gas phase.

Finally, these

experiments confirm that 2,3,7,8-TCDD is present at concentrations well
below those of 2,,3,7,8-TCDF in these air samples.

�-10INDEX TO FIGURES

PCDFs

Figure

1.

Tetra, penta and hexa CDFs - floor 11 example

2.

Standards - Tetra, penta, hexa CDFs

3.

1

Tetra CDFs

2-4

ion chromatograms - comparison of floors 11, 14,
16, and 17

5-12

fortified sample

13

solvent blank

14

comparison of particulate vs. adsorbed - floor 17

examples:

sample 11C1 + 11C2 + 11C4 + 11C5
sample 16C1

4.

18-20
21-26

Penta CDFs
example:

sample 11B3 + 11B4 + 11C1

comparison of particulate vs. adsrobed - floor 17
solvent blank
5.

15-16

27
28-29
30

Hexa CDFs (2nd injection}

example:

sample 11B3 + 11B4 + 11C1 (hexa + penta)

31-34

TCDDs
1.

Sample 11C1 + 11C2 + 11C4 + 11C5
solvent blank

35-37
38

�Table 1.

TETRA-CDFs

Volume •
m3

Flocr/sa-Dlsi)

Concentration
of 2378 TCDF
(pg/m3)

Detectionlimit
(pg/m3)

Ion®
ratio (%)
304/306

Relative
retention
time

TCDF
recovery

Total
TCDF
(pg/m3)

Detection
limit
(pg/ir.3)

ratio (%)
304/306

Ratio
2273/'tot = l {%)

61 . 5

11

0.4

78

1.0

97

92

0.8

83

12

14 A3

63.0

14

0.3

73

1.0

157

185

0.3

72

8

16 Cl

62.4

16

0.4

74

1.0

88

118

2.7

77

14

17 C1G

62.1

12

1.7

84

1.0

26

79

5

89

15

17 C1P

62.1

08
.

0.7

70

1.0

78

3.9

2.7

89

21

17 C2G

59.8

9

0.3

78

1.0

71

59

4

73

15

17 C2P

59.8

09
.

04
.

126

10
.

74

ND

5

92

—

11 B3 + 11 B4 +
11 Cl

184.5

16

0.5

84

1.0

41

133

3.7

78

12

11 Cl + 11 C2 +
11 C4 + 11 C5

240.8

23

0.3

80

1.0

42

76

4

73

30

0

ND

0.2

—

—

110

ND

1.9
110

20

14 Cl

Solvent blank

-

DOH2 background air

49.1

1.9.

0.6

68

1.0

74

9.5

2.5

NSA 6S 10.0 pg/m3
2378 TCDF
Fortified backcrour.d air

41.8

9.9

0.4

79

1.0

120

10.2

2.1

DC-HI 8.1 pg/nr3
2378 TCDF
Fortified background air

51.6

1.2

80

1.0

75

16.8

2.0

10.0

97

90

(J/e.g. 14A3 is 14th floor,.N cqsT building corner, 3rd sample taken on that date.
&amp;&gt; Theoretical ion ratio = 78%.
(3 Recovery variation (vs. external standard) is probably due to the volume measurement and manipulation of small (5-10
volumes prior to injection.

60

�Table 2

PENTA CDFs

£)
lon^-'
ratio (%)
338/340

Total
Pen ta -CDF
(pg/m3 )

Detection
Limit
(pg/m3)

14C1

20.6

2.4

14A3

12.7

1.6

16C1

21.2

1.2

17C1G

24.4'

7.4

17C1P

ND

2.0

6.6

1.3

0.78

2.9

2.1

0.23

11B3 + 11B4
+11C1

19.2

1.5

0.62

11C1 + 11C2
+11C4 + 11C5

16.4

2.3

Solvent blank

ND

1.3

DOH2 background

ND

2.0

Floor/Sample

17C2P
r

(V Recovery of three -^Cl Penta CDF internal standard isomers
was calculated to be 80%, 91% and &lt;10% for sample 17C2G
(other samples were similar).
(£/ Multiple ions were checked on a 2nd injection for several
samples.

�Table 3

Air
volume (m )

m/e 322
area (counts)

pg
found

11C1 -f- 11C2 + 11C4 + 11C5

241

1040165

226

11C6 + 11C7 + 11C8 + 11C10

241

529026

372

Floor/sample

/
\
/ pg/m3 \
!
/
i
i
j

0.94

Solvent blank 2 + 3

DOH 3 + 4 background air
fortifie^i with 98 pg
native TCDD (=0.82 pg/
m3)

0
20 for calcs.)
120

47

706423

150

^^s^

\

0.39

\

296261

\ 'j

.T
7

/*

1.5 X
/

!

13C
TCDD
recovery (%)

GC rela-ive
re --:•.- ;icr.
ri.-.e

0.66

90

i ^p.

29

0.84

58

l.CO

17

0.60

112

1.00

. 13

0,89

78

1.00

Detection
limit (pg)

12

'

Ratio®
320/322

•

\ 1.3 /
\
/
\

/

\Js' Both BSOB air samples appeared to contain small amounts of several other TCDD isomers as evidenced by a simultaneous response at other
retention times for m/e 319.8964 and 321.8935; however, additional ana-lysis is needed for verification.
(^Theoretical Ratio = 0.78

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�</text>
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                  <text>&lt;p style="margin-top: -1em; line-height: 1.2em;"&gt;The Alvin L. Young Collection on Agent Orange comprises 120 linear feet and spans the late 1800s to 2005; however, the bulk of the coverage is from the 1960s to the 1980s and there are many undated items. The collection was donated to Special Collections of the National Agricultural Library in 1985 by Dr. Alvin L. Young (1942- ). Dr. Young developed the collection as he conducted extensive research on the military defoliant Agent Orange. The collection is in good condition and includes letters, memoranda, books, reports, press releases, journal and newspaper clippings, field logs and notebooks, newsletters, maps, booklets and pamphlets, photographs, memorabilia, and audiotapes of an interview with Dr. Young.&lt;/p&gt;&#13;
&lt;p&gt;For more about this collection, &lt;a href="/exhibits/speccoll/exhibits/show/alvin-l--young-collection-on-a"&gt;view the Agent Orange Exhibit.&lt;/a&gt;&lt;/p&gt;</text>
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              <text>Series IV Subseries II</text>
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              <elementText elementTextId="23516">
                <text>Smith, R.M.</text>
              </elementText>
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                <text>D. Hilker</text>
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                <text>P. O'Keefe</text>
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                <text>Typescript: Determination of Tetra-Hexa CDFs and Tetra-CDDs in Air Samples from the 11, 14, 16 and 17th Floors of the Binghamton State Office Building, May 16, 1983</text>
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                <text>BSOB</text>
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                <text>ambient air sampling</text>
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                <text>laboratory protocol</text>
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                <text>dioxin</text>
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  <item itemId="3190" public="1" featured="0">
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                  <elementText elementTextId="63601">
                    <text>Item D Number

02224

Author

Smith, P.M.

Corporate Author
RapOrt/ArtlClB TltlO Typescript: Determination of TCDFs and TCDDs in Air
Samples from the Sixteenth Floor of the Binghamton
State Office Building, March 16, 1983

Journal/Book Title
Year
Month/Day
Color
Number of Images

D

20

Descriptor! Notes

Thursday, September 20, 2001

Page 2224 of 2293

�•v. YXi;^
««ijts~&gt;~&gt;- O -^ "

Determination of TCDFs and TCDDs in Air Samples from the
Sixteenth Floor of the Binghamton State Office Building

R.M. Smith, D. Hilker, P. O'Keefe, K. Aldous
Toxicology Institute
New York State Department of Health

March 16, 1983

RECEIVED
APR

8 1983

DIRECTOR
PUBLIC HEALTH

�INTRODUCTION
Prior

to building cleanup, analysis of soot samples from ceiling

panels on floors 1-17 of the chemically contaninated Binghamton State
Office Building (1,2) showed that most samples contained PCBs (28-23000
ppra total) and a complex mixture of tetra- to octa- PCDF isoraers (average

concentration in ppra was: Cl.=33, Cl =40&gt; Cl,=18, Gl-.=6, C10 &lt;
H

j

o

/

o

1-3). The PCDDs were not detected by the less sensitive full scan HUMS
method used.

2,3,7, 8 TGDD was then determined in several samples by

HPLC/GC SIM techniques and was present at concentrations of 0.26-2.2 ppm.
This data corellated well with the results of a biologically based cell
keratinization assay (CKA) which screens for "2,3,7,8 TGDD-like
activity".
It was then necessary to analyze several air samples from a cleanedup section of the building (16th floor was available first) and investigate the sensitive analytical methods necessary to determine PCDFs and
,PCDDs at low (e.g. pg/m ) concentrations in air. The results would also
show whether building clean-up efforts were proceeding satisfactorily for
re-entry.

3
Approximately 50 ra of air were sampled and analyzed for total
(gaseous and particulate) PCDF and PCDD using capillary GC/SIM high resolution mass spectroraetry.

Tetra-corapounds were investigated first.

Isoraer specificity was provided solely by a SP-2330 capillary column
which resolves many but not all of the TCDD and TCDF isoraers.

All 38

possible TCDF isoraers have only recently been synthesized and identified
(3) but are not yet unavailable to our laboratory. All 22 TCDD isorners
howMVrjr are available in our laboratory.

�EXPERIMENTAL
Laboratory Volatilization and Trapping Studies
Experiments using

14
C radiolabeled 2,3,7,8-TCDD demonstrated that

it can be volatilized (from 33% at 25° to 97.4%

at 280°C)J transported

in an air stream and trapped by 8 g of 30-70 mesh silica gel.

The appara-

tus is shown in Figure 1.

At the high air flow rates required for samplo
ing (e.g. 20 liter/min = 57.6 M /48 hrs) the trapping efficiency was
found to be dependent on temperature and volume of air.

Overall TCDD

trapping and elution efficiency ranged from 70 to 100% depending on the
experimental conditions employed.
breakthrough
of air.

A three day laboratory study of TCDD
3
showed 78% was trapped and recovered from a 74.3 M sample

Qualitative analysis by HPLC and GC identified

the trapped

material as 2,3,7,8 TCDD.
For field use, the glass "cartridge" containing silica gel was
housed in a rugged teflon housing, sealed with fluoroelastoraer Viton "o"
rings and preceded by a glass microfiber air particulate filter (EPM
2000, 0.3u) as shown in Figure 2.

A similar "cartridge" design for col-

lection of large volumes of semivolatiles has been described in the literature ( )
4 . Tests of the trapping efficiency of the field sampler by
liquid scintillation counting showed a 70% recovery for 2,3,7,8-TCDD
volatilized at 280°.

This was identical to that found in the lab

experiments.

Samples for Analysis
To investigate the variation of concentration with location, four
sampling sites on the (cleaned, air uncirculated) 16th floor were chosen
-3-

�for analysis.

The first group of 4 samples consisted of 3 samples

(duplicate for PCDF, 1 for CKA) from site A, the northeast corner of the
floor, and 1 sample (for PCDF) from site B, the southeast corner.
were simultaneously sampled for independent analysis.

PCBs

The second group

of samples taken 1 week later consisted of 3 samples from site C, the NW
corner, and 1 from site D, the SW corner.

A solvent blank, a background

air sample taken at Albany,, NY, and 2 TCDD and TCDF fortified air
samples were also analyzed as part of normal quality control procedures.

Sampling Procedures
Prior to sampling, internal standards (10 jiL mixed 190 pg/pL
37

C1 2,3,7,8 TCDF, 17.1 pg/pL

13

C 2,3,7,8 TCDD and 714 pg/nL OCDD)

in cyclohexane were deposited directly on the 140° activated silica gel
trapping adsorbent contained in the pyrex thimble.
was added to the sampler for CKA.

No internal standard

The thimble was plugged with glass
•o

wool, placed inside its teflon housing, and the entire apparatus was
assembled as shown in Figure 2.

To check for breakthrough during actual

sampling, an additional silica gel adsorbent stage was added in series.
It was spiked and analyzed

separately.

The open ends of each sampling train were'then secured with aluminum foil and the samplers were transported to the Binghamton sampling
site.
The sampling was conducted by Versar.

Each sampler was clamped in a

vertical position and connected to a 1.5 CFM Cast vacuum pump (using
rubber tubing) via a flowmeter which constantly monitored the air flow.
Tne sampling rate was adjusted to 23 L/min.

After approximately 50 M

3

�had been sampled, the pumps were turned off, the samplers were wrapped in
foil, and returned to the laboratory for clean-up and GC/HRMS analysis.

Extraction
The Pyrex thimble containing silica gel, internal standards, and
adsorbed compounds was removed from each sampler and its exterior was
washed with benzene to remove any handling residue.

The corresponding

glass fiber filter containing collected particles was then folded and
placed inside the Pyrex thimble, thus combining the sections.

The

thimble was then placed in a Pyrex soxhlet apparatus charged with 75 ml
distilled-in-glass benzene and conticmously extracted for 16 hrs.

Two of

the background samples (NSA IS, NSA 2S) were spiked with unlabeled TCDF
and TCDD prior to extraction.

Sample

Clean-up

The extracted sample was cleaned up prior to GC/MS to remove PCBs
and non-planar aromatics and isolate the Cl, to Cla PCDFs and PCDDs.
Each sample was directly injected onto a pre-programmed automatic cleanup system that provides sequential multi-solvent chromatography on basic
alumma, PX-21 adsorptive carbon, and neutral alumina (Figure 3 .
)

Only a

single concentration step was needed i.e. to concentrate the sample to
10 ul prior to GC/MS injection.

Capillary GC/High Resolution Mass Spectrometry
A portion (typically &lt; 2 pi) of the. purified extract was injected
onto a 60 m^t^r capillary gas chromatography column (0.3 ram i.d.) coated
_ c __

�with 15% SP2330.

The column oven was temperature programmed with a start-

ing temperature of 80°C for 1 minute and then ramped at 12°C/min to
205°C.

The final temperature, 205°C was held isotherraally until after

the analyte eluted.

The column was interfaced to the source of the

Kratos MS-50 mass spectrometer using an open split interface and deactivated fused silica transfer line.

The interface was maintained at

approx. 280°C.
Data were acquired from the Kratos MS-50 high resolution mass spectrometer operated in electron impact mode (70eV) at approx. 10,OOORP
(source teraerature was 250°C) and stored by the Kratos DS-55 data system
using a program called HRMPM (high resolution multiple peak monitoring).
During the chromatographic run the m/e 303.9016, 305.8987, and 311.8898
masses corresponding to the native tetrachlorodibenzofuran
lar ion peaks and the tetra

37

(TCDF) molecu-

Cl-labelled internal standard molecular

ion peak (m/e 311.8898) were monitored.

For the analysis of TCDD,

samples were placed into the source of the mass spectrometer by direct
introduction probe in order to obtain greater sensitivity.

The probe tip

was heated ballistically to approx. 200°C and held isothermally until
the sample evaporated.
TCDD ion and

In this case m/e 321.8936 and 333.9338, (native

C labelled TCDD internal standard ion) were monitored.

The area under the mass peak profile for each of the three ions monitored was summed over the time period in which the TCDF eluted.

The

area of the internal standard peak was ratioed to the area of the native
peak to compute the concentration of the native material.

The ratio of

the ra/e 303.9016 to 305.8987 intensities (M*, M+2*) along with the
coincidence of retention time on the gas chromatograpli provided
-6-

�additional data used in the verification of native TCDF.

Data acquired

for the.analysis for TCDD were processed in the same manner, summing the
mass peaks profiles over the time period in which the sample evaporated
from the probe capillary.

Calculations
For increased accuracy, the concentration and detection limits of
TCDDs and TCDFs in air were calculated using an isotope dilution internal
standard method as shown below.

The percent recovery ,of internal

standard (versus external standard) does not enter into these calculations and is provided in table 1 for information purposes only.
Cj = XC2 Aj/A2
Where

(eq. 1)

C, = the calculated concentration of native TCDF (or
TCDD) in pg/M3
X = a theoretical mass spectral response factor that
corrects for differences in isotope abundances (1
for

3

C TCDD, 2.5 for

Cl TCDF).

C. = the known concentration of added, isotopically
labeled TCDF (or TCDD) in pg/M3
A. = the measured area under the mass profile due to
native TCDF at ra/e 305.8987 (or TCDD at 322) in
arbitrary counts.
A- = the measured area under the mass profile due to
isotopically labeled TCDF at ra/e 311.8898 (or TCDD
at 334) in arbitrary counts
-7-

�We have used the above .calculation and made the assumption that the
labeled standard, added to the silica gel adsorbent prior to sampling, is
recovered through trapping and clean up identically to the TCDF or TCDD
in air.

Strictly however, one would expect to observe a slightly lower

recovery of internal standard if the trapping efficiency is &lt; 100%
3
(experimentally 78%/74M ) because internal standard is applied at the
beggining of the sampling period while trapped compounds are continuously
accumulating over a 48 hr period.

NSA 2 and NSA 3 samples fortified with

native TCDF and TCDD at the end of the trapping period were corrected for
this effect.
Detection limits were similarly calculated using equation 1,
substituting for A, the average MS noise (30 millimass units each side
of m/e 305.8987 for TCDFs) in arbitrary counts and incorporating a
standard detection limit factor of 2.5.
The recovery of

37

Cl labeled TCDF or

13

C labeled TCDD was

calculated as follows:
A7r
R - 100 -~

where

(eq. 2)

R = percent recovery
A

= the measured area at m/e 311.8898 due to

Cl

TCDF internal standard added prior to sampling.
r = the measured mass spectral response at m/e 311.8898
for an external

37

Cl TCDF standard in pg/area

f = the fraction sample injected
t = the total amount of

Cl TCOF internal standard

added prior to sampling in pg.

-8-

�RESULTS AND CONCLUSIONS
All 5 air samples taken from the 16th floor of the BSOB were found
to contain small amounts of a complex mixture of TCDFs as shown by the
typical high resolution ion chromatograms and mass profiles for sample A2
in figures 4-7.

The total concentration of observed TCDF isomers (obtain-

ed by summing scans containing the proper response at both 303.9013 and
3
305.8986 TCDF masses) ranged from 52 to 102 pg/tn of air. (See Table 1
which is a summary of results, giving TCDF and TCDD concentrations, detection limits, ion ratios, GC retention times, recoveries, and results of
blanks and fortified samples.)

Near the detection limit of the instrumen-

tation and using a highly selective SP2330 capillary GC column as the
only means of TCDF isomer separation, (2 other TCDF isoraers have been
shown to have nearly the same GC retention time on this column ( ) , the
3)
"2378" TCDF isomer was found to be a major TCDF component.

12-20% of

"2378" TCDF was found in all samples. These "2378" TCDF concentrations
3
ranged from 7.0 to 16 pg/m of air. For quality control, 2 air samples
taken from the Albany area and fortified to 6.6 and 5.5 pg/ni 2378 TCDF
3
were found to have concentrations of 8.1 and 5.4 pg/m (+23% and -2%
errors).

Although particulate and/or gaseous compounds were trapped

separately, they were combined prior to extraction and analysis.

There-

fore, all results represent a total of particulate + gaseous compounds.
3
Penta-CDF was detected at a concentration of 22 pg/m (total) only
in sample A2 as shown by the mass profiles in figure 8.

Other samples

3

had no d e t e c t a b l e penta-CDF at a d e t e c t i o n limit of c_a 5 pg/m .

It

is i m p o r t a n t to n o t e that q u a n t i t a t i o n for these h e a v i e r compounds was
s e v e r e l y l i m i t e d due. to the

lack of .3 Libeled p e n t a - C D F i n t u r n a l s t a n d a r d
-9-

�and native standards from which to obtain experimental response factors
and provide fortified quality control samples.
The TCDD analysis was accomplished using the direct insertion probe
HRMS rather than capillary GC/HRMS because of the greater sensitivity
that could be obtained.

No TCDD was detected in any air sample at detec-

3

tion limits of &lt; 1.3 pg/m . The MS signal due to internal

13

C 2378

2
TCDD standard in the samples (2.8 pg/m spiking level) was clearly evi- •
dent. Because of apparent chemical noise at these low levels, a slight
response of signal at ra/e 321.8935 was noted. However it did not meet
the normal analytical criteria for TCDD.

3
An Albany air sample fortified to 6.4 pg/m TCDD was similarly
3
analyzed and found ,to have a concentration of 5.4 pg/m (-16% error).
Future efforts will be directed towards improving our detecton
limits for TCDD.

-10-

�Table 1.

HRMS Results for BSOB 16th Floor Air Samples
Total Penta-CDF

Total TCDF

"2378" TCDF1
37

Concentration of
2,3,7,8-TCDF (pg/M3)

SAMPLE

detection
limit

3436
0/0

relative
retention
time

Cl TCDF
Recovery
()
%

concentration
(pg/M3)

304/306

2378/Total
()
%

concentration
(pg/M3)

i f.
lo
12
13
9.2
7.0

6.1

.76

1.0

86

93

.83

17

-6
_ _o

5.7
4.2
7.2
3.5

.90
.75
.76
.88

1.0

1.0
1.0

50
55
69
50

102
78
55
52

.0
8
.8
6
.75
.74

12
17
20
16

22^
ND(&lt;5)
ND(&lt;5)
ND(&lt;5)

Solv. Blank3
NSA 1** (background)

ND
ND

7.3
5.1

NA
NA

NA
NA

57
41

)
NSA 2-S (TCDF=6.6, TCDD-7.7)
»
NSA 3-S (TCDF=5.5, TCDD=6-4)

8.1 (+23%)
%
5.4 (- 2 )

3.1
28
.

.79
.9
7

1.0

35
61

A2 (2nd)

ND

8.8

NA

NA

Al
A2
B
C2
D

(NE
(NE
(SE
(NW
(SW

corner)
corner)
corner)
corner)
corner)

i.o-••

1.0

1

Analyzed by capillary GC/HRMS

2

At least 2 isomers were detected. Detection limits were approximately 5 pg/M3.

3

Cal-culated for a theoretical 60 M3 volume of air.

ti NSA 1-3: New Scotland Avenue Samples - considered quality control.
5

Analyzed by direct probe HRMS to obtain extra sensitivity.

6

Entire sample used for PCDFs.

Ratio of 342/340 was .53 and .76.

»

�REFERENCES

1.

Determination of Polychlorinated Dibenzofurans in Soot Samples
from a Contaminated Office Building, R.M. Smith, D.R. Hilker,
P.W. O'Keefe, S. Kumar, and K.M. Aldous.
Toxicology

2.

NYS Health Department,

Institute Report, March, 1982.

Comparisons of Chemical and Biological Data on Soot Samples from
the Binghamton State Office Building, G. Eadon, K. Aldous, G.
Frenkel, J. Gierthy, D. Hilker, L. Karainsky, P. O'Keefe, J.
Silkworth and R. Smith.

NYS Health Department, Toxicology

Institute Report, March, 1982.

3.

Synthesis of the 38 Tetrachlorodibenzofuran Isoraers and
Identification by Capillary Column Gas Chroraatography/Mass
Spectroraetry, T. Mazer, F. Hileraan, R. Noble and J. Brooks.
Anal. Chem. 55 (1983) 104-110.

4.

Modification and Evaluation of a High-Volume Air Sampler for
Pesticides and•Semi Volatile Industrial Organic Chemicals, R.
Lewis and M. Jackson, Anal. Chem. 54 (1982) 592-594.

-11-

�Table 1 Continued
TCDD5
TCDD

detection
limit

13

C TCDD
recovery

—6
&lt;1.2
&lt;1.3
&lt;1.3
ND

1.1
0.55
0.62
1.0

52
64
66
32

Solv. Blank

ND

0.53

57

NSA 1

ND

0.72

64

~6
5.4 (-16%) 0.27

58

Al
A2
B
C2
D

(NE corner)
(NE corner)
(SE corner)
(NW corner)
(SW corner)
(background)

NSA 2-S (TCDF=6.6, TCDD=7.7)
NSA 3-S (TCDF=5.5, TCDD=6-4)

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TIME 17: 3
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SCONS
42-201 100* INTENSITY 139105
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303.9470

RUHHfiME MDHM5
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RREfl ID:1
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PEfiK SUMMfiTION REPORT
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TIME 17:

3

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SCflH WIDTH
306 PPM
SCflN TIME
0.3 SECS
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                  <text>&lt;p style="margin-top: -1em; line-height: 1.2em;"&gt;The Alvin L. Young Collection on Agent Orange comprises 120 linear feet and spans the late 1800s to 2005; however, the bulk of the coverage is from the 1960s to the 1980s and there are many undated items. The collection was donated to Special Collections of the National Agricultural Library in 1985 by Dr. Alvin L. Young (1942- ). Dr. Young developed the collection as he conducted extensive research on the military defoliant Agent Orange. The collection is in good condition and includes letters, memoranda, books, reports, press releases, journal and newspaper clippings, field logs and notebooks, newsletters, maps, booklets and pamphlets, photographs, memorabilia, and audiotapes of an interview with Dr. Young.&lt;/p&gt;&#13;
&lt;p&gt;For more about this collection, &lt;a href="/exhibits/speccoll/exhibits/show/alvin-l--young-collection-on-a"&gt;view the Agent Orange Exhibit.&lt;/a&gt;&lt;/p&gt;</text>
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                <text>Typescript: Determination of TCDFs and TCDDs in Air Samples from the Sixteenth Floor of the Binghamton State Office Building, March 16, 1983</text>
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                <text>ambient air sampling</text>
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                <text>dioxin</text>
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                    <text>RBDID Number

°2193

Author

Eadon G

&gt; -

Center for Laboratories and Research, New York State

Report/Article TltlB Comparisons of Chemical and Biological Data on Soot
Samples From the Binghamton State Office Building

Journal/Book Title
Year

1982

Month/Day

March

Color
Number of Images

D

24

Dascrlpton Notes

Thursday, September 20, 2001

Page 2193 of 2293

�Comparisons Of Chemical and Biological Data
on Soot Samples From the Binghamton State
Office Building

G. Eadon, K. Aldous, G. Frenkel, J. Gierthy, D. Hilkerr L.
Kaminsky, P. O'Keefe, J. Silkworth and R. Smith

Center for Laboratories and Research
(
New York\State Department of Health
Albany, N^ 12201

March, 1982

�Soot samples from two separate samplings of the Binghamton
State Office Building (BSOB) have been the objects of a
coordinated interdisciplinary study at the New York State Health
Department. On May 26, 1981, replicate soot samples were
collected from above the ceiling panels of 16 of the 17 floors of
the BSOB.

Each sample was subjected to exhaustive soxhlet

extraction (benzene).

One portion of each extract was analyzed

for polychlorinated biphenyls (PCBs), another for polychlorinated
dibenzofurans (PCDFs) and related compounds.

A third portion of

all extracts not spiked with PCDDs and PCDFs as part of the
chemical analysis procedure was examined using the cell
keratinization assay.
Another set of experiments utilized a much larger soot
sample collected by a vacuum cleaner on the 3rd and 4th floors of
the BSOB shortly after the fire occurred.

The bulk of this

sample has been used in animal toxicology studies.

However/

portions of this soot were extracted and analyzed for PCBs,
PCDFs, 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) and
2,3,7,8-tetrachlorodibenzofuran (2,3,7,8-TCDF).

The cell

keratinization assay was also applied to an extract of this
sample.
The results of each of these studies have been described in
detail in separate reports (Smith et al. , 1981a, 1981b, 1982;
Silkworth et al., 1982; Gierthy et al., 1982).

This

paper will seek comparisons among the various chemical and
biological data sets generated with these samples, and will
attempt to determine whether the results are mutually consistent.

�Chemical Data
The number of samples which could be analyzed for PCDFs and
related trace contaminants is severely limited by the difficulty
of the analytical procedure.

In contrast, the quantitation of

the much more abundant PCBs is a fairly straightforward process;
more than 800 PCB analyses have already been reported on
BSOB-related samples.

If the ratios of PCB to PCDF are

approximately constant then the results of the PCB analyses can
be used to estimate PCDF levels, with a considerable savings in
time and manpower.

Table I contains analytical data relevant to

the PCB and PCDF (tetra through octa chlorinated)

concentrations

on soot samples collected from 16 of 17 floors of the BSOB, and
on the soot sample used in animal toxicology experiments.

The

PCB concentrations vary by nearly 3 orders of magnitude, while
total PCDF levels vary from not detected
approximately 1200 ppm.

«1.0 ppm) to

For the 11 samples in which the ratio of

total PCDFs to total PCBs has been determined, the total PCDFs
measured ranges from 51 ppm to 1200 ppm, and the ratio of PCDF to
PCB averages .066 * .024 (error limits represent one standard
deviation). t Thus, the total PCDF levels correlate with PCB
levels.
More detailed consideration of the data in Table I indicates
that the total concentrations of tetra CDFs, penta CDFs and hexa
CDFs (groupings which include the isomers predicted (see later)
to be most active with respect to acute oral toxicity and
keratinization) relative to the total PCDF concentration is
relatively constant (Table II).

In the 11 samples for which

these ratios have been determined, tetra CDFs constitute 33 + 5%

�of the total PCDF mixture, while penta CDFs constitute 40 + 3%,
and the hexa CDFs constitute 18 ± 7% of the total mixture.

Thus,

the PCB concentration can be used to predict approximate
concentrations of each family of chlorinated dibenzofurans in
these samples.

For illustrative purposes, Table III contains the

measured and predicted concentrations.
Further studies will be required to rigorously validate the
use of PCB analysis as a surrogate for the more elaborate
analytical procedures.

Since concentrations of dibenzodioxins

and biphenylenes (Stalling, 1981) have not yet been determined in
these samples, it cannot be demonstrated that the concentrations
of these compounds correlate with PCB concentrations.

Further,

the samples analyzed to date have all been collected before May,
1981 and have been predominantly obtained from the same location
on the 17 floors.

The validity of the observed correlation must

be tested with more recent samples and with samples taken at
other locations; the similarity of the ceiling panel samples and
vacuum cleaner sample is encouraging in the latter regard.
Finally, the validity of the observed correlation in the very
slightly contaminated samples likely to be generated during the
!

final phases of the clean-up should also be tested.

�Biological Data
Evaluation of the consistency of the chemical data and the
biological data requires knowledge of the concentrations and
toxicities of particular congeners believed to be especially
active.

Because of the very few reference standards available,

the laboratories of the Health Department have produced little
congener-by-congener

analytical data.

Therefore, in the

following discussions it will be necessary to assume that within
a particular isomeric series the relative concentration of a
given isomer is comparable to its concentration in a sample
earlier subjected to congener by congener analysis (Stalling,
1981; Rappe, 1981).
Among the tetra CDFs, the isomer believed to be most toxic
is 2,3,7,8-Tetra CDF (Poland et al., 1977).

Stalling and

Rappe report that this isomer constitutes 68% and 41% of the
tetra CDFs.

Based on these results it will be assummed that

2,3,7,8-TCDF constitutes 50% of the total tetra CDF concentration
in these samples.
Given the greater toxicity of 2,3,7,8-chlorinated isomers
(Poland et al., 1977) the most toxic penta CDF isomers are
predicted to be 1,2,3,7,8- and 2,3,4,7,8-penta CDF.

Stalling and

Rappe report that these congeners comprise together 47% and 53%
of the penta CDF mixture.

A value of 50% will be assumed in

subsequent discussions.
Given the greater toxicity of 2,3,7,8-chlorinated isomers
(Poland et al., 1977), the most toxic hexa CDF isomers are
predicted to be 1,2,3,4,7,8-, 1,2,3,6,7,8-, 1,2,3,7,8,9- and
2,3,4,6,7,8-hexa CDF.

Rappe reports that the total concentration

�of three of these isomers in a BSOB sample was 49% of the total
hexa CDF concentration.

A value of 50% will be assumed here for

the four isomers.
Knowledge of the relative concentrations of dibenzodioxins
and dibenzofurans will also be required for these discussions.
In the soot sample used in animal toxicology experiments, the
2,3,7,8-TCDD/2,3,7,8-TCDF ratio was determined to be .025 (Smith
et al., 1981b).
this sample.

This ratio will be used in connection with

However, since analytical data on the dioxin levels

in the remaining samples is not yet available, an estimate of
these concentrations must be made.

In a sample analyzed by Rappe

and Stalling, Rappe concluded that the tetra through octa
PCDD/PCDF ratio was about .01, and Stalling concluded that it was
less than .02.

In a heavily contaminated soot sample, Smith et

al (1981a) concluded that the 2,3,7,8-TCDD/2,3,7,8-TCDF ratio
averaged .015.

The average ratio observed in the three samples

was .017; this value will be assumed for the ceiling panel
derived soot samples.
Based on Stalling's report (1981), the biphenylene/dibenzofuran ratio in a sample was less than .067.

This value will of

i

necessity be used in subsequent discussions.

Efforts are

presently underway to obtain experimental data on the soot
samples currently under discussion to place these estimates on a
firmer basis.
a.

Animal Toxicology Experiments
It is difficult to rigorously demonstrate consistency

between results obtained via chemical analysis and acute toxicity
data for a number of reasons.

The chemical data is incomplete;

�7
not all classes of toxicants have been quantified,and the
concentrations of individual congeners have not been established.
More important, however, very limited data is available on the
acute oral toxicities of individual PCDFs, PCDDs or
Polychlorinated Biphenylenes.

Nevertheless, despite these and

other difficulties, crude comparison of this data will be
attempted.
A useful first step is to express the observed acute oral
toxicity of the soot in terms of "2,3,7,8-TCDD equivalents",
i.e., the concentrations of 2,3,7,8-TCDD, that, in an inert
matrix, would produce the observed LDgQ. An extract of soot
when administered to guinea pigs in aqueous suspension exhibited
an LD5Q equivalent to 327 mg soot/kg.

When 2,3,7,8-TCDD was

administered under identical conditions, it exhibited an LD50
of 19 ug/kg.

If the soot in fact had contained only 2,3,7,8-TCDD

at 58 ug/g, its extract would be predicted to exhibit an LD,-n
of 327 mg soot equivalents/kg.

Therefore, the "2,3,7,8-TCDD

equivalent" contamination of the soot is 58 ug/g.
The chemical data can then be used to "predict" the
"2,3,7,8-TCDD equivalent" concentration of the soot, based on
known toxicities of the components.

This is a complicated task,

since no data is available on the LDcris of dibenzofurans in
bu
guinea pigs other than 2,3,7,8-tetra CDF, and since very limited
data is available on the PCDDs.

The following assumptions will

therefore be made about the I&lt;DCQS of these compounds:

(1)

The

ratio of the LDcQs of a particular PCDF congener and
2,3,7,8-tetra CDF will be the same as the ratio of the LD5Qs oE
the correspondingly substituted PCDD congener and 2,3,7,8-TCDD.

�8
There is no direct experimental data to support this assumption.
(2)

The LD50s of PCDFs and PCDDs lacking chlorines on all four

lateral positions will be sufficiently high that their influence
can be ignored in this calculation.

This assumption is based on

the LD5Qs in guinea pigs of 2,8-diCDD, 2,3,7-triCDD, and
1,2,4,7,8-penta-CDD.

All have LE&gt;

s more than 450 times

higher than that of 2,3,7,8-Tetra CDD itself (Table IV).

(3)

Introduction of a single additional chlorine substituent on a
2,3,1,8-substituted congener has essentially no effect on the
congener's guinea pig LD

. This assumption is based on

comparison of the LD5Qs of 2,3,7,8-TCDD and 1,2,3,7,8~tetra-CDD
(Table IV).

(4)

Introduction of two additional chlorine

substituents on a 2,3,7,8-chlorinated congener raises its LD,-0
by a factor of at least 29. The assumption is based on comparison
of the LD5Qs of 1,2,3,4,7,8-, 1,2,3,6,7,8-, and
1,2,3,7,8,9-hexa CDD and 2,3,7,8-tetra CDD (Table IV).

(5)

The

LDf-QS of compounds with more than 6 chlorines will be
sufficiently large that their influence can be ignored in this
calculation.

This assumption is based on comparison of the

LD5Qs of 1,2,3,4,6,7,8-hepta CDD and 2,3,7,8-tetra CDD (Table

IV).
These assumptions require that attention be focussed only on
the tetra, penta, and hexasubstituted PCDDs and PCDFs.

The

concentration of 2,3,7,8-TCDF in the sample used in animal
toxicology experiments was measured at 48 ppm; since the data in
Table IV indicates that the LD5Q of 2,3,7,8-tetraCDF is about
three times that of 2,3,7,8-TCDD, this is equivalent in terms of
acute toxicity to a 2,3,7,8-TCDD concentration of ca. 16 ug/g.

�Based on assumption (2), other tetra CDFs can be neglected in
this calculation.

The penta CDFs were measured at 120 ug/g.

If

1,2,3,7,8- and 2,3,4,7,8-penta CDF together constitute 50% of the
penta CDFs, and if their LDcQS are equal to that of
2,3,7,8-TCDF, this is equivalent in terms of acute toxicity to a
2,3,7,8-TCDD concentration of ca. 20 ug/g.

Based on assumption

(2), other penta CDFs can be neglected in this calculation.
hexa CDFs have been measured at 70 ug/g.

The

The isomers believed to

have the lowest LD5Qs (1,2,3,4,7,8-, 1,2,3,6,7,8-, and
2,3,4,6,7,8-hexa CDF) are expected to comprise 50% of the total
hexa CDF mixture.

Since, based on assumption (4), their LD^s

are 29 times higher than that of 2,3,7,8-TCDF, this is equivalent
to a 2,3,7,8-TCDD concentration of 0.4 ug/g.
calculated

Thus, the PCDFs are

to constitute a "2,3,7,8-TCDD equivalent"

concentration of 36 ug/g.
The concentration of 2,3,7,8-TCDD itself has been measured
at 1.2 ppm in this sample.

Other tetrachlorinated dibenzodioxins

are predicted to have much higher LD,-QS and can be ignored.
The concentration of other PCDDs in this sample are unknown, but
are likely to be comparable to the TCDDs.

Thus, the dioxins as a

whole probably have a negligible influence on the soot's
"2,3,7,8-TCDD equivalent" concentration.
Stalling (1981) has reported on the presence of
polychlorinated biphenylenes in a soot sample from BSOB; he cites
unpublished results by Dr. Alan Poland that suggests that the
toxicity of the 2,3,6,7 congener is comparable to that of
2,3,7,8-tetra CDD.

If Stalling's ratio of biphenylene to

dibenzofuran is (.067) is assummed to hold for all of these

�10

compounds, and if it is assummed that the biphenylenes have
acute oral toxicities three times that of the corresponding
dibenzofurans, it can be calculated that the biphenylenes will
contribute about 0.2 times as much "2,3,7,8-TCDD equivalent"
activity as the dibenzofurans. Thus, to a very crude
approximation, the polychlorinated biphenylenes account for a
"2,3,7,8-TCDD equivalent" concentration of 7 ppm.
In summary, the dibenzofurans and the tetra CDDs are
estimated to constitute a "2,3,7,8-TCDD equivalent" activity of
37 ug/g.

Together, the remaining dibenzodioxins and the

biphenylenes probably provide a significant but smaller
"2,3,7,8-TCDD equivalent" activity.

This calculation is in good,

probably somewhat fortuitous agreement with the observed activity
in the soot-equivalent to a 2,3,7,8-TCDD concentration of 58

ug/g.
Since considerable effort has been devoted to animal
toxicology experiments on a single large sample of soot, it is
important to assess whether this sample is reasonably typical.
The data in Table I indicates that the average PCB concentration
in 16 samples collected above the ceiling panels at the BSOB is
(

7200; the PCB concentration in this sample is 5,000 ppm. " The
average total PCDF concentration on 14 such samples was ppm; the
total PCDF concentration in this sample is 320 ppm.

The average

ratio of total PCDF to PCB in the 12 samples for which this is
well defined is .066; the ratio for this sample was .063.

The

proportions of tetra- penta-, and hexa CDFs in this sample are
similar to those in the ceiling panel samples (Table II).
the sample used in animal toxicology experiments appears

Thus,

�11
comparable to the samples collected from above the ceiling
panels, based on presently available data.
b.

Cell Keratinization Assay
Development of the cell keratinization assay based on an in

vitro keratinization model (Knutson et al., 1981) has been
pursued because of its potential use as an alternative or
supplement to chemical analysis.

Both applications demand that

the biological and chemical methods generate mutually consistent
results.

One question can be answered fairly readily.

Do the

two methodologies agree which samples fall into particular broad
categories of contamination?

The samples and blanks run as part

of this program exhibit four broad categories of contamination.
Blanks did not exhibit positive responses in this assay.

A

single sample (floor 1) exhibited activity equivalent to 0.01 0.10 ppm 2,3,7,8-TCDD; chemical analysis detected only 0.2 ppm
Tetra-CDF.

Three samples (floors 4,6, and 14) exhibited

activities near 0.10 - 1.0 ppm; chemical analysis confirmed low
levels of PCDFs in these samples (total PCDFs of 51, 76, and 87
ppm).

The remaining samples in which PCDFs were detected

chemically exhibited activities ranging from 1.1 - 11 ppm to 5.3
!

- 53 ppm.

Chemical analysis confirmed that these samples were

more heavily contaminated (total PCDFs of 410 , 200, 320, 1200,
400, 750, and 670 ppm).
Table V.

These results are collected together in

They suggest that the keratinization assay results

correlate with chemical data.
It is markedly more difficult to determine whether the
activity observed in the cell keratinization assay is
quantitatively consistent with chemical analysis.

Little

�12

published information exists to relate the keratiniation
activities of the various compounds present in the soot to one
another.

However, the following assumptions will be made to

permit a crude calculation:

(1)

The ratios of the activity of a

particular dibenzofuran congener to 2,3,7,8-TCDF is equal to that
of the ratio of the activity of the corresponding dibenzodioxin
congener to 2,3,1,8-TCDD.
assumption.

(2)

There is no direct support for this

2,3,7,8-Tetra CDF is 1/20 as active as

2,3,7,8-TCDD (Knutson et al., 1980).

(3)

Congeners not

substituted at all four lateral positions are sufficiently
inactive to be neglected.

This assumption is based on comparison

of the activities of 2,3-, 2,7-, 1,6-, 1,3,6,8-, 1,3,7,8-, and
2,3,7- chlorodibenzodioxins to 2,3,7,8-tetra CDD.
al., 1980) (Table VI).

(4)

(Knutson et

Introduction of a single

additional chlorine on a 2,3,7,8 chlorinated nucleus decreases
activity by a factor of 2.

This assumption is based on a

comparison of the activities of 1,2,3,7,8-Penta CDD and
2,3,7,8-tetra CDD (Knutson et al., 1980) (Table VI).

(5)

Introduction of two or more chlorines depresses activity
sufficiently to make the activity of such compounds negligible.
This assumption is based on comparison of the activities of
1,2,3,7,8,9-hexa CDD and 2,3,7,8-tetra CDD (Knutson et al.,
1980) (Table VI).

(6)

Polychlorinated biphenylenes are 1/2 as

active as the corresponding dibenzodioxin.

This generalization

is based on comparison of the activities of 2,3,6,7-tetra CB and
2,3,7,8-tetra CDD (Knutson et al., 1980) (Table VI).
As a direct result of assumptions (3) and (5), the bulk of
keratinization activity will reside in tetra- and penta-

�13

chlorinated compounds.

As already discussed, 2,3,7,8-tetra CDF

is predicted to be by far the most active tetra CDF, and expected
to constitute 50% of the tetra CDF mixture.

Since 2,3,7,8-tetra

CDF is 1/20 as active as 2,3,7,8-TCDD, the "2,3,7,8-TCDD
equivalent" activity due to this compound can be obtained by
dividing the total tetra CDF concentration by 40.

Similarly, the

"TCDD equivalent" activity of the two most active penta CDFs can
be estimated by dividing the total penta CDF concentration by 80.
The calculated

"2,3,7,8-TCDD equivalent" activity due to PCDFs is

compared to the experimentally observed value for a number of
samples in Table VII.
The PCDDs will make a significant contribution to the cell
keratinizing activity of these samples; although they are
estimated to be 1/50 to 1/100 as abundant as the PCDFs, they may
be 20 times as potent in the assay.

The polychlorinated

biphenylenes may be even more important factors in this analysis.
Stalling's data suggests that they may be 1/10 to 1/20 as
abundant as the PCDFs.
as active.

However, they are reported to be 10 times

Thus, the calculated values in Table VII are likely

to be below the values that would be calculated if more complete
t

analytical data were available.

However, in view of the large

uncertainties present in these calculations and the data upon
which they are based, the calculated and experimental data are in
fair agreement.
It should be noted that the soot sample used in the animal
toxicology experiments exhibited a cell keratinizing activity of
2-20 ppm "2,3,7,8-TCDD Equivalents", and a calculated activity of
4 ppm due to PCDFs.

This differs from the "2,3,7,8-TCDD

�14

equivalents" calculated and observed in the animal toxicology
experiments

This does not represent a discrepancy in the data.

Rather, it is due primarily to the large difference between the
ratios of the guinea pig LD5Qs for 2,3,7,8-TCDF and
2,3,7,8-TCDD, and the corresponding ratios of cell keratinization
activity.
Conclusions
(1) Available chemical data indicate that the relative
concentrations of PCBs, tetra-, penta-, and hexa-CDFs, and total
PCDF are similar in soot samples taken from above the ceiling
panels of the BSOB, and in a sample collected by vacuum cleaner
during the early stages of the clean-up.

If this relationshiip

is valid for samples collected at other times and from other
locations, the PCB analysis can serve as a useful surrogate for
the more difficult analytical procedures.

(2)

A soot sample

exhibited an LDcQ in guinea pigs equivalent to 58 ppm
2,3,7,8-Tetra CDD.

If certain assumptions are made about the

chemical composition of this sample and the LD

s of the

compounds therein, it can be calculated that the PCDFs, tetra
CDDs, and the biphenylenes should account for ca. 45 ppm
"2,3,7,8-TCDD equivalent" activity.

Since this calculation

ignores other chlorinated dioxins, it is in good (probably
fortuitous) agreement with the observed value.

Based on these

results, there appears to be no basis for proposing unusual
synergistic or antagonistic effects among the components in this
mixture.

(3)

The cell keratinization assay can reliably

distinguish among samples containing widely differing
concentrations of PCDFs.

If certain assumptions are made about

�15

the chemical composition of compounds therein, it can be
calculated that the observed keratinizing activity in these
extracts is generally plausible.

(4)

Chemical analysis and the

cell keratinization assay suggest that the soot used in animal
toxicology studies is fairly typical of the soot samples
collected from above the ceiling pannels of the BSOB.

�TABLE I
Concentrations (ppm) of Polychlorinated Biphenyls and Polychlorinated Dibenzofurans in. Soot Samples Taken From the Binghamton State Office Building
Floor #
PCBsa
PCDFsb
Tetra CDF

2

28

3

4

1300

1

6

5

840

7

8

9

2800

6600

1800

23000

10

11

12

9600 21000 11000

13

3400

14

15

930 10000

16

9200

17

Ave

3-4*

6500 7200

5000

0.2

&lt;8g

16

220

23

190

70

320

140

250

d

d

32

300

h

220

145

100

Penta CDF

&lt;0.2g

&lt;9g

21

280

36

180

79

440

170

360

d

d

31

310

150h

260

165

120

Hexa CDF

&lt;0.3g

&lt;llg

13

180

14

35

32

290

84

260

d

d

e

56

89h

140

86

70

Hepta CDF

&lt;0.3g

&lt;12g

1.2

62

3

3.7

14

100

6.5

97

d

d

5.8

71

33h

32

31

20

Octa CDF

&lt;0.3g

&lt;14g

1.2

21

0.5

--

3

35

2

31

d

d

2.8

17

llh

15

11

4

51

760

76

410

200

1200

400

1000

—

87

750

670

438

310

.027

.062

.11

.052

.042

.048

.094

.075

.103

.066

.062

Total PCDF
Ratio Total PCDF cone.
PCB c
o
n
e

.

.

0

6

1

(a) quantitated as Arochlor 1254; data uncorrected for recovery
(b) correction for recovery incorporated
( ) not sampled because of dissimilar ceiling construction
c
(d) data not used because of poor recovery of internal

37

C1-Tetra CDF standard (&lt;10%)

(e) data lost because of instrumental malfunction; for purposes of calculation of total PCDF, it is assummed that hexa CDF is % the concentration of penta
( f Table 2)
c.
(f) soot collected by vacuum cleaner and used in animal toxicology studies
(g) detection limits are per congener, not per chlorination number
data not corrected for recovery.

Instrument malfunction caused loss of data on 37C1-Tetra CDF recovery

�Table II

Relative Proportions of Tetra-, Penta-, Hexa-, Hepta- and Octachlorodihenzofurans in Soot Samples
Taken from the Binghamton State Office Buildinga
Floor #

4

5

6

7

8

9

10

11

14

15

17

Aveb

Tetra CDF

31

29

30

46

35

27

35

25

37

39

33

33 ± 5

32

Penta CDF

41

37

47

44

40

37

41

36

36

41

39

40 ± 3

38

Hexa CDF

25

24

18

9

16

24

21

26

--

7

21

18 ± 7

22

2

8

4

1

7

8

2

10

7

10

5

6 ± 3

6

Hepta CDF

3-4°

_

Octa CDF

&lt;1

3

1

&lt;1

1

3

&lt;!

3

(a) Expressed as percent of total PCDF in sample.'
(b) Error limits represent one standard deviation.
(c)

Soot sample used in animal toxicology studies.

3

2

2

_-—

1

�CO

Table III
Comparison of Predicted3 (and Observed) Concentrations (ppm) of PCDFs in BSOB Soot Samples
Floor #

1

3

4

9

6

10

11

14

15

17

3-4

Jetra CDF

0.6(0.2) 26( 8)

17(16)

56(23)

133(190)

39(70)

60(320)

190(140)

420(250)

19(32)

200(300) 130(220) 100(100)

Penta CDF

0.9(&lt;.2) 30(&lt;9)

19(21)

64(36)

151(180)

45(79)

130(440)

220(170)

480(360)

21(31)

230(310) 150(260) 115(120)

Hexa CDF

0.3(&lt;.3) 16(&lt;11)

10(13)

33(14)

79(35)

23(32)

70(290)

115(84)

250(260)

11C")

120(56)

78(140)

60(70)

Hepta CDF

0.1(&lt;.3) 5.6(&lt;12)

3.6(1.2)
.6(1.2)

12(3)

28(3.7) 8.4(14)

99(100)

41(6.5)

90(97)

5(5.8)

43(71)

28(32)

22(20)

Octa CDF

.04(&lt;.3)

1.3(&lt;1.2) 4.2(0.5)

10(--)

35(35)

15(2)

32(31)

1.4(2.8

15(17)

10(15)

84
()

Total PCDF

1.9

2(&lt;13)
80

51(51)

3(3)

.400(1200)

(a) Prediction based on PCB levels and average ratio calculated in Table I and II

580(400)

1300(1000)

57(87)

610(754) 400(670) 300(310)

�19

Table IV
Influence of Structure and Chlorination Pattern on Guinea Pig
Oral LD5Qs (Male, Hartley, 200-250g)
Compound

LD3 U • &lt;f «—
cn(ug/kg)

2,3,7,8-Tetra CDD

2.5a

2,3,7,8-Penta CDF

5-10b

1,2,3,7,8-Penta CDD

3.1°

1,2,3 ,4,7,8-Hexa CDD

73C

1,2,3,7,8,9-Hexa CDD

60-100°

1,2,3,6,7,8-Hexa CDD

70-100°

1,2,3,4,6,7,8-Hepta CDD

&gt;600°

1,2,4,7,8-Penta CDD

1,125°

2,3,7-Tri CDD

29,444°

2,8-Di CDD

730,000°

a

J.B. Silkworth, D. McMartin, A.P. DeCaprio, R. Rej, S. Kumar
and L. Kaminsky (1981). Acute toxicity in guinea pigs and
rabbits of soot from a polychlorinated biphenyl-containing
transformer fire, N.Y. State Dept. of Health Report, January 6,
1982.
J.A. Moore, E.E. McConnell, D.W. Dalgard, and M.W. Harris
(1979). Comparative toxicity of three halogenated dibenzofurans
in guinea pigs, mice and thesus monkeys. NY Acad. Sci. 320,
151-163.
°E.E. McConnell, J.A. Moore, J.K. Baseman, and M.W. Harris
(1978). The comparative toxicity of chlorinated
dibenzo-p-dioxins in mice and guinea pigs. Toxi co 1.
Pharmacol. 44, 335-356.
0

�Table V
o
CSl

Comparison of the Observed Keratinization Activities with Total PCDF Concentrations
Observed
Floor I

"2,3,7,8-TCDD Equivalents(ppm)

Total
PCDF Concentrations

1

. 1 1
0 -

6

0.1-1.0

76

4

.11-1.1

51

14

.12-1.2

87

3

1.2-12

b

9

1.1-11

1200

8

1.6-16

200

3-4a

2-20

310

10

3.2-32

400

15

4.0-40

750

17

4.0-40

670

7

5.3-53

410

a

Soot used in animal toxicology experiments

•L^

Total concentration not defined, (cf. Table I)

b

(ppm)

�21

Table VI
Influence of Structure and Chlorination Pattern on Relative
Activity in the Cell Keratinization Assay3.
Compound

Relative Activity

2,3,7,8-Tetra CDD

1

2,3,7,8-Tetra CDF

0.05

2,3/6,7-Tetrachlorobiphenylene

0.5

1,2,3,7,8-Penta CDD

0.5

2,3,7-Tri CDD

0.01

1,3,7,8-Tetra CDD

0.01

1,2,3,7,8,9-Hexa CDD

0.005

1,3,6,8-Tetra CDD

&lt; .003

1,6,-DiCDD

&lt; .001
i

2.7-DiCDD

&lt; .001

2.3-DiCDD

&lt; .001

(a) Data adapted from J.C. Knutson and A. Poland (1980).
Keratinization of mouse teratoma cell line XB produced by
2,3,7,8-tetrachlorodibenzo-p-dioxin: an in vitro model of
toxicity, Cell 22, 27-36.

�Table VII
Comparison of the Observed Keratinization Activity in BSOB Soot Samples with Value
Predicted based on PCDF Concentrations

« Floor #

Observed
"2,3,7,8-TCDD equi

Lents" (ppm)

Calculated
"2,3,7,8-TCDD equivalents" (ppm)
PCDFs only

1

.Ol-.l

(b)

6

0.1-1.0

1

4

.11-1.1

1

14

.12-1.2

1

3

1.2-12

(b)

9

1.1-11

10

8

1.6-16

3

3-4a

2-20

4

10

3.2-32

6

15

4.0-40

10

17

4.0-40

9

7

5.3-53

7

(a)
-(b)

Sample used for animal toxicology studies,
PCDFs not detected in chemical analysis.

�;

23
REFERENCES

Gierthy, J.P. and Prenkel, G.D. (1982).

A preliminary report on

the c.,-aluation of an In Vitro assay for the detection of
"dioxin-like" activity using extracts of soot from the Binghamton
State Office Building.

New York State Department of Health

Report, January, 1982.

Knutson, J.C. and Poland, A. (1980).

Keratinization of mouse

cell line XB produced by 2,3,7,8-tetrachlorodibenzodioxin:

an in

vitro model of toxicity. Cell, 22, 27-36.

Poland, A., and Glover, E. (1977).

Chlorinated biphenyl

induction of aryl hydrocarbon hyudroxylase activity:
the structure-activity relationship.

a study of

Mol. Pharmacol., 13,

924-38.

Rappe, C. (1981) Report on the analysis of Binghamton soot.
Report, University of Umea, Sweden, 1981.

Silkworth, J. , McMartin, D., DeCaprio, A., Re j, R. , O'Keefe, P.,
and Kaminsky, L. (1982).

Acute toxicity in guinea pigs and

rabbits of soot from a polychlorinated biphenyl-containing
transformer fire.
January 6, 1982.

New York State Department of Health Report,

�'&gt; •

I

A

'i

24

i

Smith, R.M., O'Keefe, P.W. , Hilker, D.L., Jelus-Tyror, B.L., and
Aldous, K. (1981a).

Analysis of 2,3,7,8-tetrachlorodibenzofuran

and 2,3,7,8-tetrachlorodibenzo-p-dioxin in a soot sample from a
transformer explosion in Binghamton, New York.

New York State

Department of Health Report, February 20, 1981.

Smith, R.M., Hilker, D.L., O'Keefe, P.W., Kumar, S., O'Brien, J.,
Jelus-Tyror, B.L., and Aldous, K. (1981b)

Analysis of a

Binghamton soot sample for tetrachlorodibenzofurans and
tetrachlorodibenzo-p-dioxins.

New York State Department of

Health Report, October 1, 1981.

Smith, R.M., Hilker, D., O'Keefe, P.W., Kumar, S., Aldous, K.,
and Jelus-Tyror, B. (1982).

Determination of polychlorinated

dibenzofurans and polychlorinated dibenzodioxins in soot samples
from a contaminated office building.

New York State Department

of Health Report, March, 1982.

Stalling, D.L., (1981) Chlorinated dibenzofurans and related
compounds in soot formed in a transformer fire in Binghamton,
(

N.Y., Preliminary Report, Columbia National Fisheries REsearch
Laboratory, U.S. Fish and Wildlife Service.

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