ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF ENFORCEMENT
EPA-33O/2-79-O21
Pollutant Analyses
Hooker Chemicals and Plastics Corporation
Waste Disposal Sites
Niagara Falls, New York
(JULY 12 SEPTEMBER 7, 1979)
NATIONAL ENFORCEMENT INVESTIGATIONS CENTER
DENVER. COLORADO
DECEMBER 1979
-------
Environmental Protection Agency
Office of Enforcement
EPA/330/2-79-021
POLLUTANT ANALYSES
HOOKER CHEMICALS AND PLASTICS CORPORATION
WASTE DISPOSAL SITES
Niagara Falls, New York
[July 12-September 7, 1979]
William J. Stang
December 1979
National Enforcement Investigations Center
Denver, Colorado
-------
ACKNOWLEDGMENTS
The authors wish to thank the staff members of the NEIC,
Region II and EPA headquarters for their cooperation and
assistance in planning and conducting the Hooker Chemicals and
Plastics Corporation Waste Disposal Sites study, and preparing
this report.
-------
CONTENTS
I INTRODUCTION 1
II SUMMARY OF FINDINGS 3
WATER SAMPLE ANALYSES 3
AMBIENT AIR SAMPLE ANALYSES 5
MUTAGEN TESTING 5
TOXICITY EVALUATION 6
III SURVEY METHODS 7
WATER SAMPLING 7
AMBIENT AIR SAMPLING 10
IV SURVEY FINDINGS 12
WATER SAMPLE ANALYSES 12
AMBIENT AIR SAMPLE ANALYSES 21
MUTAGEN TESTING 21
V TOXICITY EVALUATION 23
REFERENCES 39
APPENDICES
A PRIORITY POLLUTANTS LISTING
B METHODS, ANALYTICAL PROCEDURES AND QUALITY CONTROL
C NON-PRIORITY POLLUTANTS, QUALITATIVE DATA SUMMARY
TABLES
1 STATION LOCATIONS FOR WATER SAMPLES 8
2 AIR SAMPLING LOCATIONS-HYDE PARK LANDFILL 11-
3 VOLATILE ORGANICS SAMPLING DATA 14
4 BASE-NEUTRAL EXTRACTABLE ORGANICS SAMPLING DATA .... 15
5 ACID-EXTRACTABLE PHENOLIC COMPOUNDS SAMPLING DATA ... 16
6 PESTICIDES AND PCB SAMPLING DATA 17
7 TOXICITY OF COMPOUNDS HOOKER CHEMICALS AND
PLASTICS CORPORATION WASTE DISPOSAL SITES 26
FIGURES
1 Hyde Park Landfill Area and Bloody Run Creek 13
2 S-Area Landfill and Water Treatment Plant Monitoring
Wells Sampled 19
3 102nd Street Landfill Area 20
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I. INTRODUCTION
The EPA and the Department of Justice (DOJ) are investigating
the operations at the Hooker Chemicals and Plastics Corporation in
regard to its hazardous waste disposal practices at Niagara Falls,
New York. The purpose of this investigation is to determine com-
pliance with applicable laws and regulations. Four waste disposal
sites are being investigated by EPA: Love Canal, Hyde Park Landfill,
S-Area Landfill, and 102nd Street Landfill. Extensive sampling of
groundwater, and/or surface waters and sediments have been conducted
at these sites by EPA Region II and State agencies. To supplement
these data, the National Enforcement Investigations Center (NEIC) was
requested to collect additional groundwater and surface water samples
from and adjacent to the Hyde Park, S-Area and 102nd Street Landfill
sites for mutagenicity and chemical analyses.
Sampling was conducted on July 12, 1979. In addition to the
analyses for mutagenic substances,* analyses were performed for or-
ganic priority pollutants.** Air sampling was conducted at the Hyde
Park Landfill site to determine if airborne pollutants from Hooker
operations were present. The potential source of these pollutants is
emission of volatile materials from the holding ponds into which the
leachate collected from the landfill is pumped. These ponds are
presently covered with a 22 mil plastic sheet to prevent emissions.
* Mutagenicity analyses were by the Salmonella/mammalian microsome
mutagenicity procedure (Ames test).
** Priority pollutants are derived from the June 7, 1976 Natural
Resources Council (NRDC) vs. Russell Train (USEPA) Settlement
Agreement. For a listing of the 129 pollutants see Appendix A.
-------
All samples collected were shipped to the NEIC laboratories
Denver, Colorado, for analyses. Document control, Chain-of-Custody,
and quality control/quality assurance procedures of the NEIC were
followed during this study.
-------
II. SUMMARY OF FINDINGS
To supplement information collected from previous EPA investiga-
tions, the NEIC, on July 12, 1979, conducted sampling adjacent to or
within three waste disposal sites: Hyde Park Landfill, S-area Land-
fill, and 102nd Street Landfill of the Hooker Chemicals and Plastics
Corporation, Niagara Falls, New York. These samples were analyzed
for mutagenic substances and organic pollutants during the period
July 16 to September 7. The conclusions and pertinent findings from
this investigation are discussed below for each disposal area.
WATER SAMPLE ANALYSES
Hyde Park Landfill
1. Analyses of the sample from the Hyde Park Landfill leachate
pond identified 25 organic compounds; 22 of these are prior-
ity pollutants.
2. Of the 25 compounds found in the Hyde Park leachate pond,
10 were also identified in a groundwater sample collected
near the Hyde Park Landfill. This site contained 18 or-
ganic compounds, 10 of which were priority pollutants.
3. Of the 25 compounds found in the Hyde Park leachate pond, 5
were also identified in the surface water sample collected
from Bloody Run Creek at University Street. A total of 10
compounds were identified at this station; 6 were priority
pollutants.
-------
4. Concentrations of organic compounds identified at or ad-
jacent to the Hyde Park Landfill ranged from low-level
detection of less than 1 [jg/1 to a high of 8,200 jjg/1.
5. None of the 129 priority pollutant compounds were detected
at the Armagost residential well.
S-Area Landfill
1. Organic characterization of groundwater samples collected
from the S-Area Landfill identified compounds from two
Hooker monitoring wells (No. 17 & 17a). Twenty-three of
the compounds were priority pollutants of which several
appeared at high concentrations (range 3 to 15,000 ug/1).
2. Twenty-three organic compounds were also identified in
samples collected from two stations (wells CW 2a and 6a) at
the Niagara Falls Water Treatment Plant (adjacent to the
S-Area Landfill). Twenty of the compounds were priority
pollutants. Concentrations ranged from 0.02 to 1,200 jjg/1.
Two compounds identified in Hooker well samples from the
landfill sites were also identified in groundwater collec-
ted from the water treatment plant property.
102nd Street Landfill
Groundwater collected from the 102nd Street Landfill contained
several priority pollutants. Only 3 compounds were identified
at low levels from the well located on 01 in Chemical Company
property. However, 15 priority pollutants were identified in the
groundwater sample collected from Hooker well No. 1. Concentra-
tions ranged from 3 to 1,200 pg/1.
-------
AMBIENT AIR SAMPLE ANALYSES
Air samples were collected using Tenax columns at five" locations
£p_ and on the Hyde Park Landfill site. A blank column was
carried to the field and returned to Denver for a quality control
reference.
The analyses identified benzene,, trichloroethylene, hexane, tetra-
chloroethylene, toluene, and chlorobenzene present in all columns at
concentrations greater than the detection limit of 5 [ig/m3. These
substances were also identified in two volatile organic s samples col-
lected from the leachate pond. The reference column was later deter-
mined to be contaminated and, therefore, failed to meet quality con-
trol requirements. No quantitative evaluation was possible. However,
the samples collected gff-si'tP and on top of the landfill showed no
significant amounts of the above substances greater than the blank.
The sample collected at the edge of the leachate pond, which was the
most likely station to determine high concentrations of these sub-
stances, showed that only tetrachloroethylene and toluene were slightly
higher than the reference column. No other chemicals were identified
in any columns at or above the detection limit of 5 ug/m3.
MUTAGEN TESTING
The Ames test for mutagenesis did not demonstrate mutagenic activ-
ity in any of the samples collected from stations adjacent to and on
the three landfill sites. Mutagenic activity was not apparent in
either the concentrated sample extracts or the filtered aliquots of
any of the samples.
-------
Inability to detect mutagem'c activity in the samples does not
necessarily mean that these substances are absent but that the muta-
gem'c effect may be below the detection level of the test system used;
additionally, the test system will not detect volatile mutagenic com-
pounds.
TOXICITY EVALUATION
The chemical analyses identified 49 organic compounds. A liter-
ature search was done to assess toxicity and health effects of all
these compounds. References used were the Registry of Toxic Effects
of Chemical Substances (RTECS), the Toxline data base, and other data
bases. Health effects and toxicity information was located for 36 of
the 49 compounds.
Of the 36 compounds, 18 have demonstrated human health effects
including systemic, pulmonary, gastrointestinal, central nervous system,
blood and psychotropic effects. Benzene and vinyl chloride are reported
to cause cancer in humans. Of the 49 compounds, 5 are reported to
produce an irritant effect on the skin, eye, and mucuous membranes.
Of the 36 compounds, 27 have produced animal health effects,
including neoplastic, carcinogenic, teratogenic, mutagenic or sen-
sory-organ irritant effect on laboratory animals.
-------
III. SURVEY METHODS
WATER SAMPLING
Ten locations were sampled within or adjacent to the Hyde Park,
102nd Street and S-Area Landfills [Table 1]. All NEIC samples were
collected in glass containers of the following volumes:
No. of Sample
Analysis Containers Volume
Mutagenicity 2 1 gallon3
Extractable Organics, 1 1 gallon
PCBs and Pesticides 2 40 ml
a Only 1 gallon was collected at Station
61801, Hyde Park Well, OW-6.
At all locations, duplicate samples were collected for analyses
by the Company. The Company formally requested and received a copy
of the NEIC procedure for the mutagenicity analysis. This was pro-
vided directly to their consultant, Dr. David Brusick of Litton
Bionetics.
The NEIC generally followed the same procedure used by EPA
Region II during their well sampling surveys conducted in April and
June 1979. This required that certain wells, specifically well OW6
(Station 01) and wells w-17, W-17a, CW-6a, and CW-2a (Stations 07-
10, respectively), be pumped prior to sampling. The volume pumped
was to be ten times the casing volume at static conditions. No pump-
ing was scheduled at Stations 04, 05, and. 06. N Field conditions caused
some variation from the originally planned procedure.
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Table 1
STATION LOCATIONS FOR WATER SAMPLES
HOOKER CHEMICALS AND PLASTICS CORPORATION
Niagara Falls, New York
July 12, 1979a
Station
No.
618 01
02
03
04
05
06
07
08
09
10
Time (hr) of Sample
Collection
1020
1157
1235
1325
1455
1530
1745
1745
1645
1645
Description
Monitor Well OW 6 near the Hyde Park Landfill
Leachate from ponds on the Hyde Park Landfill
Bloody Run Creek at University Street
Domestic well at Armagost residence on
Penrose Street
01 in Well B-2 at 102nd Street Site
Hooker Well #1 at 102nd Street Site
Monitor Well W-17 at S-Area
Monitor Well W-17a at S-Area
Monitor Well CW-6a at Niagara Falls Water
Treatment Plant
Monitor Well CW-2a at Niagara Falls Water
Treatment Plant
a Figures 1, 2 and 3 show Station locations.
-------
At Station 01 (OW-6), the pumps became clogged with a black-oily
substance within the water column. Company officials were notified
that drawdown would have to be done to the extent possible with a 2
cm (3/4 in) I.D. stainless steel bailer* 76 cm (30 in) long. The
stated depth in the well prior to bailing was about 2.4 e4n (8 ft);
the casing volume at this depth was approximately 5 liters (1.25 gal).
Twenty-three liters (6 gal) were removed from the well in dropping
the surface to the minimum level possible [that is, 76 cm (30-in)
water depth]. The well recovered to its static head in about 10
minutes, after which sampling commenced. Sample aliquots (ca. 300 ml)
were alternately poured into the NEIC and Company containers.
The wells at Stations 07 through 10 were not pumped before
sampling. Company officials reported that these wells had been drawn
down the previous day to accommodate sample collection by State
Health Department personnel and, in their opinion, no additional
pumping was necessary. It was mutually agreed that samples could be
bailed directly. Samples were also bailed, without prior pumping,
from the 102nd Street Landfill wells (Stations 05 and 06).
•
The Armagost residential well (Station 04) was pumped by the
owner for about 10 minutes prior to bailing samples. The static
water depth in this 15 cm (6-in) well was 9.5 m (31 ft) [total well
depth is 12.5 m (41 ft)]. The actual volume removed during this
period was not determined.
To collect leachate pond samples at the Hyde Park Landfill
(Station 02), wastewater was pumped into a clean 208 liter (55-gal)
drum from which the required sample volumes were taken using a
* A separate bailer was used for sampling at each well. The bailers
had been pre-washed 4 times with methylene chloride, dried and
wrapped in aluminum foil before leaving Denver.
-------
10
stainless steel beaker*. The Bloody Run Creek sample (Station 03)
was collected using a stainless steel beaker*.
AMBIENT AIR SAMPLING
Air samples were collected at five stations adjacent to, and on,
the Hyde Park Landfill site [Table 2]. Air, at the rate of 260 ml/min
was drawn through a 190 mm Tenax column using personnel samplers**
(MSA and Bendix-brand names). Two samples were collected at each
station. One was provided to the Company, which had requested a split.
Information on the type and flow rates of the personnel samplers was
also provided. Approximately 2,600 ml of air were drawn through the
columns during the 10-minute sampling period. The columns were then
recapped, wrapped in tissue paper and, along with a blank Tenax column
which was carried to the field and remained capped throughout, were
returned to Denver for volatile organics analyses.
* The beaker had been pre-washed four times with methylene chloride
and covered with aluminum foil before leaving Denver. A separate
beaker was used for each Station.
** The personnel samplers were calibrated on July 11 at Niagara Falls
using a 100 ml bubble meter as the calibration device. The flow
rate for both instruments was established at approximately 260 ml/min.
-------
11
Table 2
AIR SAMPLING LOCATIONS - HYDE PARK LANDFILL AREA
HOOKER CHEMICALS AND PLASTICS CORPORATION
Niagara Falls, N.Y.
July 12. 1979a
Station
No.
61802
12
13
Description
East edge of leachate
Park Landfill
Well OW-3, Northwest
Landf i 1 1
Located off Hyde Park
ponds, Hyde
of Hyde Park
Site about
Wind
Conditions
Slight Breeze
W - NW
Slight Breeze
W
Slight Breeze
Time (hr)
Collection
1228
1107
1130
midway along north property fence,
south of Power Authority Road
14 Top of Hyde Park Landfill - midway
west to east length
15 Top of Hyde Park Landfill at extreme
east end
Varying
W-NW
Slight Breeze
W-NW
Slight Breeze
W-NW
1200
1217
a Figure 1 shows Station locations.
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IV. SURVEY FINDINGS
WATER SAMPLE ANALYSES
Hyde Park Landfill
Characterization of the sample collected from the Hyde Park Land-
fill leachate pond [Station 02, Figure 1] identified 25 compounds
[Tables 3 through 6 and Appendix C]. Twenty-two of these are priority
pollutants; the remaining three non-priority pollutants were 2,4-dichlo-
rotoluene and isomers of chlorobenzaldehyde and chlorobenzoic acid.
Ten of the 25 compounds identified in the leachate pond were also
identified in the groundwater sample at Station 01. The latter sample
contained 18 organic compounds; 10 were priority pollutants. Five of
the 25 compounds were identified in the surface water sample collected
from Bloody Run Creek at University Street (Station 03). A total of
10 compounds were identified at Station 03; 6 were priority pollutants.
Station 03 contained 3 compounds (Di-n-butylphthalate, Diethylphthalate
and an isomer of tetrachlorobenzene) uncommon to Stations 01 and 02.
No priority pollutants were detected at the Armagost residential well
on Penrose Street (Station 04). Concentrations of organics identified
at Stations 01, 02, and 03 ranged from low-level detection of less
than 1 ug/1 to a high of 8,200 ug/1. Compounds in concentrations of
1,000 ug/1 or greater include two at Station 02 (methylchloride and
phenol) and four at Station 01 (carbon tetrachloride, chloroform,
1,2,4-trichlorobenzene and hexachloroethane) at Station 01.
-------
13
\
\ Uniersity
Niagara University
STA, 61803
-o\
o> \
> V ^
/
. 61804
-\
- *v~
\
\
\
Power . Ai
\
\
Niagara Steel
Furnishing Co
----,
Lafayette Ave.
f /-CD |~
/ Sherman V /
IP
OW4
ithority Road
nun /f»\
UWJ. f 1
OW2^^^7
OW3 'cftA.
cQ Home
. N cn Oil
^\ a Co.
v~7^~l
i
1 Rroif P^
/ Corp.
/
^|x-X^)w^ OW 6 STA. 61801
Jv±jk^ OW5 ^
/—X — —X — X — X— it— •*. j* _ CTA
'( — - — • — - —I X _ W^ O 1 /\ .
1 STA. U"- ^*^
-T61812 1 ^-^^
! i *"
Hyde Park Landfill ^.^
! ®-*@.STT."d61802 **\ STA.
| 61814
\ __ •
\ i i n
\ ' — , i 11 i • i
* i 1— ,1— i- Nalioridl
\ 1 r^
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~"8lT 0^
^^ V!^^^ 0W7
^ x
^3«^_
^^
ar^T 61815
i
Lead Industries
CD a
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Figure 1
Hyde Park Landfill Area and Bloody Run Creek
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14
Table 3
VOLATILE ORGANICS SAMPLING DATA3
HOOKER CHEMICALS AND PLASTICS CORPORATION
WASTE DISPOSAL SITES/NIAGARA FALLS, NEW YORK
July 12-September 7, 1979
Concentration (ppb or ug/1)
Chemical Name Station No.
Acrolein
Acrylonitrile
Benzene
Carbon tetrachloride
Chlorobenzene
1,2-Dichloroethane
1,1,1-Trichloroethane
1,1-Dichloroethane
1,1,2-Trichloroethane
1,1,2 , 2-Tetrachl oroethane
Chloroethane
Chloroform (Trichloromethane)
1,1-Dichloroethylene
1,2-trans-Dichloroethylene
1,2-Dichloropropane
1,3-Dichloropropylene
(1,3-Dichloropropene)
Ethyl benzene
Methylene chloride (Dichloromethane)
Methyl chloride (Chloromethane)
Methyl bromide (Bromomethane)
Bromoform (Tribromomethane)
Dichlorobromomethane
Trichlorofluoromethane
Dichlorodifluoromethane
Chlorodibromomethane
Tetrachloroethylene
Toluene
Trichloroethylene
Vinyl chloride
01
NDb
ND
ND
8,200
ND
ND
ND
ND
ND
ND
ND
1,500
ND
790
ND
ND
ND
270
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
02
ND
ND
370
270
ND
100
ND
ND
24
210
ND
940
ND
340
ND
ND
ND
150
1,000
ND
ND
ND
790
ND
ND
690
960
550
ND
06
ND
ND
24
ND
92
ND
ND
ND
ND
ND
ND
4
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
4
14
ND
ND
08
ND
ND
590
3,100
740
ND
ND
ND
75
ND
ND
900
7,800
15,000
ND
ND
ND
52
ND
ND
ND
ND
ND
ND
ND
ND
3
1,800
190
09 Detection
Limit
ND
ND
25
ND
510
ND
ND
ND
ND
ND
ND
ND
ND
41
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
3
ND
3
ND
_c
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
ld
7
10
10
1
1
10
10
1
1
1
1
i /\
10
a Single grab samples, collected July 12, 1979.
b ND means not detected at or above the detection limit.
c Acrolein cannot satisfactorily be determined by the method used.
d Methylene chloride is detected in blank samples at 4 + 3 ug/1.
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Table 4
BASE-NEUTRAL EXTRACTABLE ORGANICS SAMPLING DATA9
HOOKER CHEMICALS AND PLASTICS CORPORATION
WASTE DISPOSAL SITES/NIAGARA FALLS, NEW YORK
July 12-September 7, 1979
15
Chemical Name stati(jn NQ
Isophorone
Napthalene
Nitrobenzene
N-Ni trosodimethy 1 ami ne
N-Nitrosodiphenylamine
N-Ni trosodi - n-propy 1 ami ne
Bis (2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Diethyl phthalate
Dimethyl phthalate
Benzo (a) anthracene (1,2-Benzarthracene)
Benzo (a) pyrene (3,4-Benzopyrene)
3,4-Benzofluoranthene (Benzo(b)fluoranthene)
Benzo (k)fluoranthene
Chrysene
Acenaphthylene
Anthracene
Benzo(g,h,i)perylene (1,12-Benzoperylene)
Fluorene
Phenanthrene
Dibenzo(a,h)anthracene
Indeno (l,2,3-cd)Pyrene
Pyrene
2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD)
Benzidine
Acenaphthene
1,2 ,4-Trichlorobenzene
Hexachlorobenzene
Hexachloroethane
Bis(chloromethyl) ether
Bis (2-chloroethyl) ether
2-Chloroethyl vinyl ether
2-Chloronaphthalene
1,2-Oichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
3,3-Dichlorobenzidine
2,4-Dinitrotoluene
2, 6-Dimtro toluene
1,2-Diphenylhydrazine
Fluoranthene
4-Chlorophenyl phenyl ether
4-Bromophenyl phenyl ether
Bis (2-chloroisopropyl) ether
Bis (2-chloroethoxy) methane
Hexachlorobutadiene
Hexachlorocyclopentadiene
Concentration (ppb or gq/1)
01
NDb
ND
ND
NAC
NA
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
ND
ND
ND
ND
NA
ND
ND
NA
NA
ND
NA
ND
ND
3000
ND
1600
NA
ND
NA
ND
210
ND
380
ND
ND
ND
ND
ND
NA
ND
NA
NA
700
ND
02
ND
ND
ND
NA
NA
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
ND
ND
ND
ND
NA
ND
ND
NA
NA
ND
NA
ND
ND
180
ND
ND
NA
ND
NA
ND
51
ND
72
ND
ND
ND
NO
ND
NA
ND
NA
NA
ND
ND
03
ND
NO
ND
NA
NA
ND
ND
N0d
MS°
ND
MS
ND
ND
ND
NA
ND
ND
ND
ND
NA
ND
ND
NA
NA
ND
NA
ND
ND
MS
ND
ND
NA
ND
NA
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
ND
NA
NA
ND
ND
04
ND
ND
ND
NA
NA
ND
ND
ND
ND
ND
ND'
ND
ND
ND
NA
ND
ND
ND
ND
NA
NO
ND
NA
NA
ND
NA
ND
ND
ND
ND
ND
NA
ND
NA
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
ND
NA
NA
ND
ND
05
NO
ND
ND
NA
NA
ND
32
ND
MS
ND
ND
ND
ND
ND
NA
ND
ND
ND
ND
NA
ND
ND
NA
NA
ND
NA
ND
ND
ND
ND
ND
NA
ND
NA
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
ND
NA
NA
ND
ND
06
ND
ND
ND
NA
NA
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
ND
ND
ND
ND
NA
ND
ND
NA
NA
ND
NA
ND
ND
40
ND
ND
NA
ND
NA
ND
160
ND
710
ND
ND
ND
ND
ND
NA
ND
NA
NA
ND
ND
07
ND
ND
ND
NA
NA
ND
ND
ND
38
ND
ND
ND
ND
ND
NA
ND
ND
ND
ND
NA
ND
ND
NA
NA
ND
NA
ND
ND
13
ND
ND
NA
ND
NA
ND
ND
ND
ND
ND
ND
NO
ND
ND
NA
ND
NA
NA
ND
ND
08
NO
ND
ND
NA
NA
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
ND
ND
ND
ND
NA
ND
ND
NA
NA
ND
NA
ND
ND
2900
ND
ND
NA
ND
NA
ND
440
ND
600
ND
ND
ND
NO
ND
NA
ND
NA
NA
14
ND
09
ND
ND
ND
NA
NA
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
ND
ND
MS
MS
NA
ND
ND
NA
NA
ND
NA
ND
MS
170
ND
ND
NA
ND
NA
ND
ND
ND
990
ND
ND
ND
ND
ND
NA
ND
NA
NA
ND
ND
10 Detection
Limit
ND
ND
ND
NA
NA
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
ND
ND
ND
ND
NA
NO
ND
NA
NA
ND
NA
ND
ND
1100
NO
ND
NA
ND
NA
ND
140
ND
190
ND
ND
ND
ND
ND
NA
ND
NA
NA
42
ND
5
5
5
NA
NA
5
5
20
5
20
5
5
20
20
NA
20
20
5
5
NA
5
5
NA
NA
5
NA
20
5
5
5
5
NA
5
NA
5
5
5
5
20
20
5
5
5
NA
5
NA
NA
5
20
a Grab samples, collected July 12, 1979.
b NO means not detected at or above the detection limit
c NA means not analyzed for.
d MS means the compound was identified by mass spectrometry but was below the quantitative detection limit.
-------
Table 5
ACID-EXTRACTABLE PHENOLIC COMPOUNDS SAMPLING DATA3
HOOKER CHEMICALS AND PLASTICS CORPORATION
WASTE DISPOSAL SITES/NIAGARA FALLS, NEW YORK
July 12-September 7, 1979
Concentration (ppb
Chemical Name Station
2,4,6-Trichlorophenol
para-Chl oro-meta-cresol
2-Chlorophenol
2,4-Dichlorophenol
2,4-Dimethylphenol
2-Nitrophenol
4-Nitrophenol
2,4-Dinitrophenol
4 , 6-Di ni tro-o-cresol
Pentachlorophenol
Phenol
a Grab samples, collected
b ND means not detected at
No. 01
NDb
ND
ND
ND
ND
ND
ND
ND
ND
ND
840
July 12,
or above
02
ND
ND
ND
240
ND
ND
ND
ND
ND
ND
3200
1979.
the
03
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
54
detection
04
ND
ND
ND
ND
ND
ND
ND
ND -
ND
ND
ND
limit.
05
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
06
ND
15
7
57
3
ND
ND
ND
ND
ND
ND
07
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
8
or |jg/l)
08
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
3500
09
ND
ND
2
11
ND
ND
ND
ND
ND
ND
ND
10
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1200
Detection
Limit
5
5
5
5
5
5
5
10
10
10
5
CTl
-------
Table 6
PESTICIDES AND PCS SAMPLING DATA3
HOOKER CHEMICALS AND PLASTICS CORPORATION
WASTE DISPOSAL SITES/NIAGARA FALLS, NEW YORK
July 12-September 7, 1979
Chemical Name
b ta
Aldrin
Dieldrin
Chlordane
4,4' -DDT
4,4' -DDE(p.p'-DDX)
4,4' -DDD(p.p'-TDE)
or Endosul fan- Alpha
p-Endosul fan-Beta
Endosul fan sulfate
Endrin
Endn'n aldehyde
Heptachlor
Heptachlor epoxide
a-BHC-Alpha
p-BHC-Beta
Y-BHC(lindane)-Gamma
6-BHC-Delta
PCB-1242 (Arochlor 1242)
PCB-1254 (Arochlor 1254)
PCB-1221 (Arochlor 1221)
PCB-1232 (Arochlor 1232)
PCB-1248 (Arochlor 1248)
PCB-1260 (Arochlor 1260)
PCB-1016 (Arochlor 1016)
Toxaphene
Concentration
tion No. 01
NDb
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
02
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
90
40
400
ND
ND
ND
ND
ND
ND
ND
ND
ND
03
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
2.3
ND
0.17
ND
ND
ND
ND
ND
ND
ND
ND
ND
04
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
05
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.15
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
06
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1200
8
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
(ppb or uq/1)
07
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
58
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
08
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
180
ND
58
ND
ND
ND
ND
ND
ND
ND
ND
ND
09
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1.9
ND
ND
1.3
ND
ND
ND
ND
ND
ND
ND
ND
10 Detection
Limit
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
14
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.1
0.2
1.0
0.5
0.1
0.4
0.2
0.2
1.0
0.2
0.4
0.1
0.1
0.02
0.1
0.02
0.02
1.0
1.0
1.0
1.0
1.0
2.0
1.0
5.0
a Grab samples, collected July 12, 1979.
b ND means not detected at or above the detection limit.
-------
18
S-Area Landfill
Volatile orgam'cs were not determined at Station 07 (Monitor
Well W-17, Figure 2). A total of five organic compounds were identi-
fied from the sample collected at this site; 4 were priority pollutants
[Tables 3 through 6]. Concentrations were low, ranging from 8 ug/1
to 58 ug/1.
Twenty-two organic compounds were detected from Station 08 (Well
W-17a); 19 were priority pollutants, of which several appeared at
high concentrations (range 3 ug/1 to 15,000 ug/1).
Analyses of groundwater samples collected at Stations 09 and 10
[Wells CW-6a and CW-2a, respectively, Figure 2] identified 15 organic
compounds at Station 09; 14 were priority pollutants ranging in con-
centration from 0.02 ug/1 to 990 ug/1. Eight organic compounds were
detected at Station 10, 6 were identified as priority pollutants
[Tables 3 through 6 and Appendix C]. Concentrations of organic com-
pounds at Station 10 ranged from 14 to 1,200 ug/1. Only two compounds
(1,2,4-trichlorobenzene and phenol) were present at concentrations of
1,000 ug/1 or greater, both identified at Station 10.
102nd Street Landfill
Groundwater collected from the 102nd Street Landfill [Stations
05 and 06, Figure 3] contained several priority pollutants [Tables 3
through 6]. Only 3 compounds were identified from Station 05. However,
15 priority pollutant compounds were identified from the groundwater
sample collected at Station 06 (Hooker Well No. 1). Concentrations
ranged from less than 1 to 32 ug/1 at Station 05, and from 3 to 1,200
ug/1 at Station 06.
-------
CITY
WATER
WORKS
RESERVOIR
FILTER ROOM
CW6a
STA. 61809
Existing Pump Station
>ii!
i ii i
Intake is
/ One Mile vAway
/ I '' I
Old
Pump
House
CW2a O-«-STA.
\
53rd Street _ I J I _
~~ K~A ~~ \ *~ n T
LEGEND
• Bedrock
O Overburden
I I
I I
I I
I I
I I
I I
I I
I I
I I
I 1
I I
11!
| re1
•oi
W17"
STA. 61R08
x W17
STA. 61807
I
S-AREA
Landfill
I
Lagoon
vil
•a
£ \
'!'
I
Lagoon
I I -^
I '
Figure 2
S-Area Landfill and Water Treatment Plant Monitoring Mel Is Sampled
QJ
s_
o
jz
on
s_
(O
L.
(O
CD
-------
LUVC
CANAL
AREA
Buffalo Ave.
QJ
i-
C
evj
o
-N-
GRIFFON
PARK
X
X
HOOKER CHEMICALS AND -o
PLASTICS CORPORATION
i
Wetlands
Area
Approximate locations of
sampling stations
FLOW
01.
Outfall
Pipe
Figure 3
102nd Street Landfill Area
-------
21
AMBIENT AIR SAMPLE ANALYSES
Analysis of the Tenax columns was performed on a Finnigan 1015
GC/MS.* The chemicals were separated on a 2.4 m x 0.3 cm (8 ft x
1/8 in) stainless steel column packed with 0.2% Carbowax 1500 on 60/80
mesh Carbopack C. The results were checked against Tenax trap blanks
and traps loaded from permeation tube standards. The permeation
rates were determined by weight loss.
The Tenax column blank and the other columns showed that ben-
zene, trichloroethylene, hexane, tetrachloroethylene, toluene, and
chlorobenzene were present at concentrations greater than the de-
tection limit of 5 ug/m3. These substances were also identified in
the volatile organics samples collected from the leachate pond
(Station 02). The reference column was later determined to be con-
taminated and failed to meet quality control requirements. No quan-
titative evaluation of the results was possible. However, the Tenax
column samples collected at Stations 12, 13, 14, and 15 showed no
significant amounts of the above substances greater than the blank.
Moreover, significant amounts of benzene, trichloroethylene, hexane,
and chlorobenzene were not present in the air sample collected on the
edge of the leachate pond (Station 02), which would have been the
most likely location for these substances. Tetrachloroethylene and
toluene were higher at this station than in the blank. No other
chemicals were detected in any of the columns at or above the detection
limit of 5 ug/m3.
MUTAGEN TESTING
The standard bacterial assay for mutagenicity was performed on
liquid sample concentrates using the plate incorporation method, as
* Gas Chromatograph/Mass Spectrometer.
-------
22
described by Ames, et al.1 This test consists of specially de-
veloped strains of Salmonella typhimurium that are auxotrophic for
the amino acid, histidine (i.e., unable to grow without histidine
supplemented to their media). The organisms have been genetically
altered so when they are subjected to certain mutagenic and carci-
nogenic substances they will mutate and regain the natural ability to
synthesize histidine. Thus, only mutant colonies can grow on media
which does not contain histidine and their growth indicates presence
of a mutagenic substance. Mutagenic activity based upon use of bac-
teria as indicator organisms correlates closely (>90% probability)
with inducement of cancer in laboratory animals by organic com-
pounds. 2»3»4.5.6.7
Acidic and basic sample extracts and undiluted, filtered samples
were prescreened for mutagenic activity using five standard Salmonella
tester strains: TA 98, TA 100, TA 1535, TA 1537 and TA 1538. Samples
were first tested individually. If they showed negative mutagenicity,
they were then subjected to metabolic activation by adding rat li-ver
homogenate (S-9 mix) [Appendix B].
The mutagencity test did not demonstrate mutagenic activity in
any of the ten samples.* Concentrated extracts of the sample collected
from Station 01 (Monitor Well OW6), adjacent to the Hyde Park Landfill,
were toxic to the Salmonella tester strains; therefore, bacterial
mutagenicity could not be determined for this material. Mutagenic
activity was not apparent in either the concentrated sample extracts
or the filtered aliquots of any of the remaining samples.
* Inability to detect mutagenic activity in the samples does not ne-
cessarily mean that these substances are absent but that the muta-
genic effect may be below the detection limit of the test system
used. The Salmonella test does not detect some of the important
chlorinated carcinogens such as chloroform, carbon tetrachloride
and hexachlorobenzene. The concentration technique employed eli-
minates the volatile alkyl halides.
-------
V. TOXICITY EVALUATION
The chemical analyses identified 49 organic compounds. To as-
sess toxicity and health effects, these compounds were searched in
the Registry of Toxic Effects of Chemical Substances (RTECS), which
is an annual compilation prepared by the National Institute for
Occupational Safety and Health. The Registry contains toxicity data
for approximately 36,900 substances, but does not presently include
all chemicals for which toxic effects have been found. Chemical
substances in RTECS have been selected primarily for the toxic effect
produced by a single dose, some lethal and some non-lethal. Substan-
ces whose principal toxic effects result from exposure over long pe-
riods are not included. Toxic information on a chemical substance is
determined by examining and evaluating the published medical, biologi-
cal, engineering, chemical and trade information documents.
The 49 compounds were also searched in the Toxline data base,
which is a computerized bibliographic retrieval system for toxicology
containing more than 618,000 records taken from material published in
primary journals. It is part of the MEDLINE file from the National
Library of Medicine and is composed of ten subfiles:
(1) Chemical-Biological Activities 1965 (taken from Chemical
Abstracts, Biochemistry Sections)
(2) Toxicity Bibliography 1968 (a subset of Index Medicus)
(3) Abstracts on Health Effects of Environmental Pollutants
1971 (published by Biological Abstracts)
-------
24
(4) International Pharmaceutical Abstracts 1970 (published by
the American Society of Hospital Pharmacists)
(5) Pesticides Abstracts 1967 (compiled by EPA)
(6) Environmental Mutagen Information Center 1969 (Dept. of
Energy, Oak Ridge National Lab)
(7) Environmental Teratology Information Center 1950 (Dept. of
Energy, Oak Ridge National Lab)
(8) Toxic Materials Information Center (Dept. of Energy, Oak
Ridge National Lab)
(9) Teratology file 1971-1974 (a collection of citations on
teratology complied by the National Library of Medicine)
(10) The Hayes File on Pesticides (a collection of more than
10,000 citations on the Health aspects of pesticides compiled
by Dr. W. J. Hayes, Jr., EPA)
Additional data bases searched to locate or support toxic informa-
tion on all 49 compounds were: (1) Toxicology Data Bank (TDB), from
the National Library of Medicine, which currently contains information
on about 2,500 substances; (2) Oil and Hazardous Materials Technical
Assistance Data System (OHMTADS), an EPA file, containing toxic data
for about 1,000 compounds; (3) Excerpta Medica, a medical file with
a section on toxicology and environmental pollution; and (4) Chemical
Abstracts.
The RTECS search yielded information on 36 of the 49 compounds.
The Toxline search yielded 883 citations to human health effects from
the 36 compounds, providing support to the toxic information from
RTECS.
-------
25
Of the 36 compounds, 18 have demonstrated human health effects,
including systemic, pulmonary, gastrointestinal, central nervous system,
blood and psychotropic effects. Benzene and vinyl chloride are reported
to cause cancer in humans. Of the 49 compounds, 5 produce an irritant
effect on the skin, eye and mucous membranes [Table 7].
Of the 36 compounds, 27 have produced animal health effects,
including neoplastic, carcinogenic, teratogenic, mutagenic or irri-
tation to the skin, eye and mucous membranes of laboratory animals.
— -\
The,three-compounds which were not located in the RTECS were:
acenapthene, acenaphthylene, and 2,4-dinitrotoluene. These were
searched in Toxline as well. No information was discovered on toxic
and health effects to humans. The 11 isomers of non-priority pollu-
tants identified (NEIC Qualitative Data Summary, Appendix C) cannot
be searched without more information.
-------
TABLE 7
TOXICITY OF COMPOUNDS
HOOKER CHEMICALS AND PLASTICS CORPORATION WASTE DISPOSAL SITES
NIAGARA FALLS. NEW YORK
Chemical Other Toxicity Data
Compound Name Molecular Abstracts Aquatic Toxicity Route of enari~, Type.of
Formula Service No. Entry " sPecies Dose"
Anthracene C14H10 120-12-7f Oral-rat
Subcutaneous-rat
Benzene C6H6 71-43-2f TLm 96: Skin-rabbit
100-10 ppm
Eye- rabbit
Oral -human
Oral -human
Inhalation-human
Inhalation- human
Inhalation-man
Oral-rat
Inhalation- rat
Intraperitoneal-rat
Oral -mouse
Oral-mouse
I ntravenous-rabbi t
Inhalation-mouse
Skin-mouse
Intraperi toneal -mouse
Subcutaneous-mouse
Oral-dog
Inhalation-dog
Inhalation- cat
I ntraper i toneal -gui nea
pig
Subcutaneous-frog
Inhalation-mammal
Benzene, Chloro- C6H5C1 108-90-7f TLm 96: 100-1 ppm Oral-rat
Subcutaneous-rat
Oral-rabbit
I ntraper i toneal - rat
Intraperi toneal -gui nea
pig
Inhalation-mouse
TDLo:
TDLo:
TDLo:
LDLo:
LCLo:
TCLo:
TCLo.
LD50:
LC50:
LDLo:
LD50:
TDLo:
LDLo:
LC50:
TDLo:
L050:
TDLo:
LDLo:
LCLo:
LCLo:
LDLo:
LDLo:
LCLo:
LD50:
LDLo:
LD50:
LDLo:
LDLo:
LCLo:
Dose
18 gm/kg
3,300 mg/kg
15 mg
88 mg
130 mg/kg
50 mg/kg
20,000 ppm
210 ppm
2,100 mg/m3
3,800 mg/kg
10,000 ppm
1,150 mg/kg
4,700 mg/kg
1 mg/kg
88 mg/kg
9,980 ppm
1,200 gm/kg
468 mg/kg
2,700 mg/kg
2,000 mg/kg
146,000 mg/m3
170,000 mg/m3
527 mg/kg
1,400 mg/kg
20,000 ppm
2.910 mg/kg
7,000 mg/kg
2,830 mg/kg
7,400 mg/kg
4.100 mg/kg
15 gm/m3
Duration*"
78WI
33WI
24H
open
5M
4YI
7H
49WI
13D
(Preg.)
5M
Effectsd
Carcinogenic
Neoplastic
Mild
Irritation
Moderate
Irritation
Central
Nervous
System
Blood
Carcino-
genic
Mutagenic
Neoplastic
Teratogenic
Exposure
Limits6
TLV (air):
Cl 25 ppm
OSHA std (air):
TWA 10 ppm;
Cl 25 ppm;
Pk 50ppm/10M/8H
NIOSH recm std
(air): Cl 1 ppm/60M
TLV (air): 75 ppm
OSHA std (air):
TWA 75 ppm
INS
cn
-------
TABLE 7 (Continued)
TOXICITY OF COMPOUNDS
HOOKER CHEMICALS AND PLASTICS CORPORATION WASTE DISPOSAL SITES
NIAGARA FALLS. NEW YORK
Chemical
Compound Name Molecular Abstracts Aquatic Toxicity
Formula Service No.
Benzene. C6H4C12 95-50-lf
1,2-dichloro-
Benzene. C6H4C12 106-46-7f
1,4-dichloro-
Benzene. Ethyl- C8H10 100-41-4f TLm 96:100-10
ppm
Benzene, C6H3C13 120-82-lf TLm 96: 10-1 ppm
1,2,4-trichloro-
1,3-Butadiene, C4C16 87-68-3f
Hexachloro-
Other Toxicitv Data
REnJry°f ' S"ec1eS
Oral -human
Oral-rat
Inhalation-rat
Intraperitoneal-rat
Intravenous-mouse
Oral -rabbit
Intravenous- rabbit
Oral-guinea pig
Inhalation-guinea pig
Eye-rabbit
Oral -human
Oral -human
Eye- human
Oral-rat
Intraperitoneal-rat
Oral-mouse
Subcutaneous-mouse
Oral-guinea pig
Inhalation- human
Oral-rat
Inhalation-rat
Skin-rabbit
Inhalation-guinea pig
Skin-rabbit
Eye- rabbit
Oral-rat
Oral-mouse
Intraperitoneal -mouse
Oral-rat
Oral-rat
Intraperitoneal-rat
Oral-mouse
Inhalation-mouse
Intraperitoneal-mouse
Oral-guinea pig
Typebof
Dose
LDLo:
LD50:
LCLo:
LD50:
LDLo:
LD50:
LDLo:
LDLo:
LCLo:
LDLo:
TDLo:
LD50:
LD50:
LD50:
LD50:
LDLo:
TCLo:
LD50:
LCLo:
LD50:
LCLo:
LD50:
LD50:
LDLo:
LD50:
TDLo:
LD50:
LD50:
LCLo:
LD50:
LD50:
Dose Duration
500 mg/kg
500 mg/kg
821 ppm 7H
840 mg/kg
400 mg/kg
500 mg/kg
250 mg/kg
2,000 mg/kg
800 ppm 24H
100 mg 30 sec.
500 mg/kg
300 mg/kg
80 ppm
500 mg/kg
2,562 mg/kg
2,950 mg/kg
5,145 mg/kg
2,800 mg/kg
100 ppm 8H
3,500 mg/kg
4,000 ppm 4H
5,000 mg/kg
10,000 ppm
15 mg 24H
open
100 mg
756 mg/kg
766 mg/kg
500 mg/kg
90 mg/kg
15 gm/kg 2YC
175 mg/kg
110 mg/kg
235 ppm 4H
76 mg/kg
90 mg/kg
. Exposure
Effects0 Limits6
TLV (air): 50 ppm
OSHA std (air):
Cl 50 ppm
Mild
Irritation
TLV (air): 75 ppm
Systemic
OSHA std. (air):
Irritation TWA 75 ppm
Irritant TLV (air): 100 ppm
OSHA std (air):
TWA 100 ppm (skin)
Mild
Irritation
Irritation
TLV (air):
5 ppm
Carcinogenic
Unreported-mammal LD50: 200 mg/kg
ro
-si
-------
TABLE 7 (Continued)
TOXICITY OF COMPOUNDS
HOOKER CHEMICALS AND PLASTICS CORPORATION WASTE DISPOSAL SITES
NIAGARA FALLS, NEW YORK
Chemical Other Toxicity Data
Compound Name Molecular Abstracts Aquatic Toxicity Route of , . Typehof
Formula Service No. Entry " sPecles Dose"
Carbon CC14 56-23-5f TLM 96: Skin-rabbit
Tetrachloride 100-10 ppm
Eye-rabbit
Eye- rabbit
Skin-Guinea
pig
Oral-human
Oral -woman
Inhalation-human
Oral -woman
Oral -man
Inhalation- human
Inhalation-human
Oral-rat
Inhalation-rat
Inhalation-rat
Skin-rat
Intraperi toneal -rat
Subcutaneous-rat
Oral-mouse
Oral-mouse
Inhalation-mouse
Intraperi toneal -mouse
Subcutaneous-mouse
Oral-dog
Intraperi toneal -dog
Intravenous-dog
Inhalation-cat
LDLo:
TCLo:
TDLO:
TDLO:
LCLo:
TCLO:
LD50:
LCLo:
TCLO:
LD50:
LDSO:
TDLo:
LDSO:
TOLo:
LC50:
LDSO:
LDLo:
LDLo:
LDSO:
LDLo:
LCLo:
Dose
4 mg
2,200 ug
500 mg
800 mg
43 mg/kg
1,800 mg/kg
20 ppm
1,800 mg/kg
1,700 mg/kg
1,000 ppm
317 ppm
2,800 mg/kg
4,000 ppm
300 ppm
5,070 mg/kg
1,500 mg/kg
133 gin/kg
12,800 mg/kg
4,800 mg/kg
9,526 ppm
4,675 mg/kg
12 gm/kg
1,000 mg/kg
1,500 mg/kg
125 mg/kg
38,110 ppm
Duration0 Effectsd
Mild
Irritation
30 sec Mild
Irritation
24H Severe
Irritation
24H Moderate
Irritation
Systemic
Central
Nervous
System
Pulmonary
System
Central
Nervous
System
Exposure
Limits6
TLV (air):
10 ppm (skin)
OSHA std (air):
TWA 10 ppm;
Cl 25; pk 200/5M/4H
NIOSH recm std
(air): Cl 2ppm/60M
30M Gastrointestinal
Tract
4H
6-150 Teratogenic
(Preg)
25WI Neoplastic
88DI Carcinogenic
8H
2H
ro
CO
-------
TABLE 7 (Continued)
TOXICITY OF COMPOUNDS
HOOKER CHEMICALS AND PLASTICS CORPORATION WASTE DISPOSAL SITES
NIAGARA FALLS, NEW YORK
Chemical
Compound Name Molecular Abstracts Aquatic Toxicity
Formula Service No.
Carbon
Tetrachloride (cont'd)
Chloroform CHC13 67-66-3f TLm 96: 100-10
(Trichloromethane) ppm
Other Toxicity Data
"Entry0' -SPec1es
Subcutaneous-cat
Oral-rabbit
Intraperitoneal -rabbit
Subcutaneous-rabbit
Intravenous-rabbit
Inhalation- guinea-pig
Oral-hamster
Inhalation- frog
Inhalation-mammal
Oral -human
Inhalation-human
Inhalation-human
Oral-rat
Oral-rat
Inhalation-rat
Inhalation-rat
Oral -mouse
Oral -mouse
Inhalation-mouse
Intraperitoneal -mouse
Subcutaneous-mouse
Oral-dog
Inhalation-dog
Intraperitoneal-dog
Intravenous-dog
Inhalation-cat
Oral-rabbit
I nhal at ion- rabbit
Subcutaneous-rabbit
Inhalation-guinea pig
Inhalation-frog
Inhalation-mammal
Skin- rabbit
Type.of
Dose
LDLo:
LD50:
LDLo:
LDLo:
LD50:
LCLo:
TDLo:
LCLo:
LCLo:
LDLo:
TCLo:
TCLo:
LD50:
TDLo:
LCLo:
TCLo:
LD50:
TDLo:
LC50:
LD50:
LD50:
LDLo:
LC50:
LD50:
LDLo:
LCLo:
LDLo:
LC50:
LDLo:
LCLo:
LCLo:
LCLo:
Dose
300 mg/kg
6,380 mg/kg
478 mg/kg
3,000 mg/kg
5,840 mg/kg
20,000 ppm
3,680 mg/kg
58,000 mg/m3
50,000 ppm
140 mg/kg
1,000 mg/m3
5,000 mg/m3
800 mg/kg
70 gm/kg
8,000 ppm
100 ppm
1,120 mg/kg
18 gm/kg
28 gm/m3
1,671 mg/kg
704 mg/kg
1,000 mg/kg
100 gm/m3
1,000 mg/kg
75 mg/kg
35,000 mg/m3
500 mg/kg
59 gm/m3
3,000 mg/kg
20,000 ppm
6,000 mg/m3
25,000 ppm
10 mg
Duration*"
2H
30WI
5M
1Y
7M
78WI
4H
7H/6-15D
(Preg)
120DI
4H
2H
5M
24H
open
d Exposure
Effects0 Limits6
Carcinogenic
TLV (air): 25 ppm
Systemic
Central OSHA std (air):
Nervous TWA 50 ppm
System
Neoplas- NIOSH recm std
tic (air): Cl 2 ppm/60M
Teratogenic
Carcinogenic
Mild
Irritation
Eye-rabbit
148 mg
Irritation
ro
vo
-------
TABLE 7 (Continued)
TOXICITY OF COMPOUNDS
HOOKER CHEMICALS AND PLASTICS CORPORATION WASTE DISPOSAL SITES
NIAGARA FALLS. NEW YORK
Compound Name
m-Cresol ,
4-Chloro
Cyclohexane,
1,2,3,4,5,6-Hex
alpha- isomer
Molecular
Formula
C7H7C10
C6H6C16
achloro-,
Cyclohexane. C6H6C16
1,2,3,4,5,6-Hexachloro-,
Chemical
Abstracts Aquatic Toxicity
Service No.
59-50-7f
319-84-6f
319-85-7f
Other Toxicity Data
*££/' ' SPec1es
Oral-rat
Subcutaneous-rat
Intraperitoneal -mouse
Subcutaneous-mouse
Oral-rat
Oral -rat
Oral-mouse
Oral -mouse
Oral-rat
Oral-mouse
Type.of
Dose
LDLo:
LD50:
LDLo:
LDLo:
LD50:
TDLo:
TDLo:
TDLo:
LD50:
TDLo:
Dose
500 mg/kg
400 mg/kg
30 mg/kg
200 mg/kg
177 mg/kg
17 gm/kg
8,350 mg/kg
10 gm/kg
6,000 mg/kg
29 gm/kg
Durationc
48WC
24WC
24WC
2YC
. Exposure
Effects0 Limits6
Carcinogenic
Carcinogenic
Carcinogenic
Carcinogenic
beta-isomer
Cyclohexane, C6H6C16
1,2,3,4,5, 6-Hexachloro-,
delta-isomer
Cyclohexane, C6H6C16
1,2,3,4,5,6-Hexachloro-,
gamma-isomer
(Lindane)
319-86-8'
58-89-9'
TLm 96:
under 1 ppm
Ethane, C2H4C12
1,2-Dichloro-
(Ethylene Dichloride)
107-06-2'
TLm 96:
1,000-100 ppm
Oral-rat
Oral-child
Oral-child
Oral-rat
Skin-rat
Intraperitoneal-rat
Oral-mouse
Oral-mouse
Intraperitoneal-mouse
Oral-dog
Intravenous-dog
Oral-rabbit
Skin-rabbit
Intravenous-rabbit
Oral-guinea pig
Oral-hamster
Oral-bird, wild
Intramuscular-bird,
wild
Inhalation-human
Oral-human
Oral-man
Oral-human
Oral-rat
LD50: 1,000 mg/kg
LDLo:
TDLo:
LD50:
LD50:
LDLo:
LD50:
TDLo:
LDLo:
LD50:
LDLo:
LD50:
LD50:
LDLo:
LD50:
LD50:
LDLo:
LDLo:
TCLo:
TDLo:
LDLo:
LDLo:
LD50:
180 mg/kg
111 mg/kg
76 mg/kg
500 mg/kg
35 mg/kg
86 mg/kg
29 gm/kg
75 mg/kg
40 mg/kg
8 mg/kg
60 mg/kg
50 mg/kg
4,500 ug/kg
127 mg/kg
360 mg/kg
100 mg/kg
26 mg/kg
4,000 ppm
428 mg/kg
810 mg/kg
500 mg/kg
12 M9/kg
52WC
Systemic
Carcinogenic
TLV (air):
0.5 mg/m3
OSHA std (air):
TWA 500 ug/m3
(skin)
Central
Nervous
System
Gastro-
intestinal
tract
TLV (air): 50 ppm
OSHA std (air):
TWA 50 ppm;
Cl 100;
PK 200/5M/3H
-------
TABLE 7 (Continued)
TOXICITY OF COMPOUNDS
HOOKER CHEMICALS AND PLASTICS CORPORATION WASTE DISPOSAL SITES
NIAGARA FALLS, NEW YORK
Chemical Other Toxicity Data
Comp, .md Name Molecular Abstracts Aquatic Toxicity Route of , . Type, of
Formula Service No. Entry " sPecies Dose0
Etha j,
1,2 .Hchloro- (cont'd) Inhalation-rat
Intraperitoneal-rat
Subcutaneous- rat
Oral -mouse
Inhalation-mouse
Intraperitoneal-mouse
Subcutaneous-mouse
Oral-dog
Intravenous-dog
Oral -rabbit
I nhal at ion- rabbit
Subcutaneous- rabbit
Inhalation-pig
Inhalation-guinea pig
Intraperi toneal -gui nea
pig
Skin-rabbit
Eye- rabbit
Oral-rat
Oral-mouse
Eth .ie, Hexachloro- C2C16 m 67-72-lf Oral-human
Oral-rat
I ntraper i toneal -mouse
Intravenous-dog
Subcutaneous-rabbit
LCLo:
LD50:
LDLo:
LDLo:
LCLo:
LD50:
LDLo:
LDLo:
LDLo:
LD50:
LCLo:
LDLo:
LCLo:
LCLo:
LDLo:
TDLo:
TDLo:
LDLo:
LD50:
LDSO:
LDLo:
LOLo:
d Exposure
Dose Duration Effects Limits
1,000 ppm 4H
74 M9/kg
500 mg/kg
600 mg/kg NIOSH recm std (air)
5,000 mg/m3 2H TWA 1 ppm;
40 |jg/kg Cl 2 ppm/15M
380 mg/kg
2,000 mg/kg
175 mg/kg
860 mg/kg
3,000 ppm 7H
1,200 mg/kg
3,000 ppm 7H
1,500 ppm 7H
600 mg/kg
625 mg open Mild
Irritation
63 mg Severe
Irritation
26 gm/kg 78WI Carcinogenic
81 gm/kg 78WI Carcinogenic
50 mg/kg TLV (air): 1 ppm
6,000 mg/kg (skin)
4,500 mg/kg
325 mg/kg OSHA std (air):
4,000 mg/kg 1 ppm (skin)
Eth ne,
1, i ,2,2-tetrachloro-
C2H2C14
79-34-5'
Oral-human
Oral-human
Inhalation-human
Inhalation-rat
Oral-mouse
Inhalation-mouse
Intraperitoneal-mouse
Oral-dog
Intravenous-dog
Inhalation-cat
Subcutaneous-rabbi t
TLDO:
30 mg/kg
LDLo:
TCLo:
LCLo:
TDLo:
LCLo:
LDLo:
LDLo:
LDLo:
LCLo:
LDLo:
50 mg/kg
1,000 mg/m3
1,000 ppm
58 gin/kg
9.000 mg/m3
30 mg/kg
300 mg/kg
50 mg/kg
19.000 mg/m3
500 mg/kg
30M
4H
58WC
40M
45M
Central
Nervous
System
Central
Nervous
System
Carcinogenic
OSHA std (air):
TWA 5 ppm (skin)
NIOSH recm std
(air): TWA 1 ppm
-------
TABLE 7 (Continued)
TOXICITY OF COMPOUNDS
HOOKER CHEMICALS AND PLASTICS CORPORATION WASTE DISPOSAL SITES
NIAGARA FALLS, NEW YORK
Chemical
Compound Name Molecular Abstracts Aquatic Toxicity
Formula Service No.
Ethane, 1,1,2- C2H3C13 79-00-5f TLm: 96:
Trichloro- 100-10 ppm
thene. 1,1- C2H2C12 75-35-4f TLm 96:
dichloro- 1,000-100 ppm
(1,1-Pichloro-
ethyli-ne)
Ethylene, Chloro- C2H3C1 75-01-4f TLm 96:
(Vinyl Chloride) over 1,000 ppm
Other Toxicity Data
REniry°f ' S"ecies
Oral -human
Oral-rat
Inhalation-rat
Intraperitoneal-mouse
Subcutaneous-mouse
Oral-dog
Intraperitoneal-dog
Intraveneous-dog
Subcutaneous-rabbi t
Skin-rabbit
Skin-guinea pig
Inhalation-cat
Inhalation-human
Oral-rat
Inhalation-rat
Inhalation-rat
Inhalation-rat
Oral -dog
Intravenous-dog
Subcutaneous-rabbi t
Inhalation-mouse
Inhalation-mouse
Inhalation-man
Oral -rat
Oral -rat
Inhalation-rat
Inhalation-rat
Inhalation-mouse
Inhalation- hamster
Inhalation-rat
Inhalation-rat
Inhalation-mouse
Oral-rat
Typebof
Dose
LDLo:
LD50:
LCLo:
LD50:
LD50:
LDLo:
LDLo:
LDLo:
LDLo:
LCLo:
TCLo:
LD50:
LCLo:
TCLo:
TCLo:
LDLo:
LDLo:
LDLo:
LC50:
TCLo:
TCLo:
LD50:
TDLo:
TCLo:
TCLo:
TCLo:
TCLo:
TCLo:
TCLo:
TCLo:
TDLo:
Dose
50 mg/kg
1,140 mg/kg
500 ppm
994 mg/kg
227 mg/kg
500 mg/kg
450 mg/kg
95 mg/kg
500 mg/kg
500 mg
1,440 mg
13,100 mg/m3
25 ppm
200 mg/kg
10,000 ppm
55 ppm
55 ppm
5.750 mg/kg
225 mg/kg
3,700 mg/kg
98 ppm
55 ppm
500 ppm
500 mg/kg
11 gm/kg
250 ppm
6,000 ppm
250 ppm
500 ppm
6,000 ppm
250 ppm
50 ppm
34 gm/kg
Duration0
Effectsd
Exposure
Limits6
OSHA std (air):
TWA 10 ppm (skin)
8H
TLV (air): 10 ppm
open
15M
4.5H
24H
6H/52WI
6H/1YI
22H
6H/1YI
4YI
136WI
4H/130WI
4H/12-18D
(Preg)
35 WI
4H/30W-I
4H/12-180
(Preg)
39WI
6H/12WI
136WI
Mild
Irritation
Irritation
Systemic
Neoplastic
Equivocal
Tumor i genie
Agent
Equivocal
Tumorigenic
Agent
Carcinogenic
Carcinogenic
Carcinogenic
Carcinogenic
Carcinogenic
Carcinogenic
Neoplastic
Carcinogenic
Carcinogenic
Carcinogenic
(skin)
TLV (air):
10 ppm
NIOSH recm std
TWA 1 ppm;
Cl 5ppm/15M
TLV (air): 200
OSHA std (air):
TWA 1 ppm; Cl
5 ppm/15M
NIOSH recm std
TWA 1 ppm;
Cl 5 ppm/15M
(air):
ppm
(air):
t^i
-------
TABLE 7 (Continued)
TOXIC1TY OF COMPOUNDS
HOOKER CHEMICALS AND PLASTICS CORPORATION WASTE DISPOSAL SITES
NIAGARA FALLS, NEW YORK
Chemical
Compound Name Molecular Abstracts Aquatic Toxicity3
Formula Service No.
Ethylene, C2H2C12 156-60-5f
1.2-Dichloro-(E)-
•
Ethylene, Tetra- C2C1, 127-18-4f TLm 96:
chloro- (Tetra- 100-10 ppm
chloroethene)
Ethylene, C2HC13 79-01-6f TLm 96:
Trichloro- 1,000-100 ppm
(Trichloroethene)
Other Toxicitv Data
Route of . s .
Entry species
Inhalation-human
Inhalation-mouse
Inhalation- cat
Inhalation- human
Oral -human
Inhalation-man
Inhalation-man
Inhalation-rat
Oral mouse
Inhalation-mouse
Intraperitoneal-mouse
Oral -dog
Intraperitoneal-dog
Intravenous-dog
Oral -cat
Oral -rabbit
Subcutaneous-rabbi t
Oral -mouse
Oral -human
Inhalation-human
Inhalation-human
Inhalation-man
Oral -rat
Inhalation-rat
Oral -mouse
Inhalation-mouse
Intravenous-mouse
Oral -dog
Intraper i toneal -dog
Intravenous-dog
Subcutaneous- rabbi t
Oral-cat
Inhalation-cat
Inhalation-guinea pig
Eye- human
Type.of
Dose
TCLo:
LCLo:
LCLo:
TCLo:
LDLo:
TCLo:
TCLo:
LCLo:
LD50:
LCLo:
LD50:
LDLo:
LD50:
LDLo:
LOLo:
LDLo:
LDLo:
TDLo:
LDLo:
TCLo:
TCLo:
TCLo:
LD50:
LCLo:
TDLo:
LCLO:
LD50:
LDLo:
LD50:
LDLo:
LDLo:
LDLo:
LCLo:
LCLo:
Dose
4
75
43
4
8
23
5
4
2
4
5
2
6
4
8
3
5
1
1
5
32
37
,800
,000
,000
200
500
280
600
,000
,850
,000
,671
,000
,100
85
,000
,000
,200
86
50
,900
160
110
,920
,000
135
,000
34
,860
,900
150
,800
,864
,500
,200
5
mg/m3
mg/m3
mg/m3
ppm
nig/ kg
ppm
ppm
ppm
nig/ kg
mg/m3
mg/kg
ing/ kg
rag/kg
mg/kg
mg/kg
mg/kg
mg/kg
gm/kg
mg/kg
mg/m3
ppm
ppm
mg/kg
ppm
gm/kg
ppm
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/m3
Ppm
ppm
Duration
10M
2H
6H
2H
10M
4H
2H
41WC
10M
83M
8H
4H
27WI
2H
2H
40M
Effects'1
Central
Nervous
System
Systemic
Eye
Central
Nervous
System
Carcinogenic
Central
Nervous
System
Central
Nervous
System
Irritant
Exposure
Limits6
OSHA std (air):
TWA 100 ppm;
Cl 200;
PK 300/5M/3H
_
NIOSH recm std
TWA 50 ppm;
Cl 100 ppm/15M
TLV (air): 100
OSHA std (air):
TWA 100 ppm;
Cl 200;
PK 300/5M/2H
NIOSH recm std
TWA 100 ppm;
•
(air)
ppm
(air)
Cl 150 ppm/lOM
Carcinogenic
Irritation
CO
CO
-------
TABLE 7 (Continued)
TOXICITY OF COMPOUNDS
HOOKER CHEMICALS AND PLASTICS CORPORATION WASTE DISPOSAL SITES
NIAGARA FALLS, NEW YORK
Chemical . Other Toxicity Data
Compound Name Molecular
Formula
Ethyl ene,
Trichloro-
(Tnchloroethene) (cont'd)
Methane, Chloro- CH3C1
(Methyl Chloride)
Abstracts Aquatic Toxicity Route of e-....s-.
Service No. Entry " bPecies
Skin-rabbit
Eye- rabbit
Oral -human
Inhalation- human
Inhalation-man
Intraperitoneal -mouse
Subcutaneous-dog
Oral -rabbit
74-87-3f TLm 96: over Inhalation-rat
1,000 ppm Inhalation-mouse
Inhalation-dog
Inhalation-cat
Inhalation-guinea pig
Type, of
Dose Dose
LDLo:
TDLo:
LCLo:
LD50:
LDLo:
LDLo:
LC50:
LC50:
LCLo:
LCLo:
LCLo:
500 mg
20 mg
7 gm/kg
812 rag/kg
2,900 ppm
3,000 mg/kg
150 mg/kg
7,330 mg/kg
152,000 mg/ra3
3,146 ppm
15,000 ppm
128,700 mg/m3
20,000 ppm
. Exposure
Durationc Effects0 Limits6
24H Severe Irritation
24H Severe Irritation
Systemic
30M
7H
7H
4H
2H
TLV (air):
100 ppm
OSHA std (air):
TWA 100 ppm
Cl 200; PK 300/
5M/3H
Methane, CH2C12
Dichloro-
(Methylene Chloride)
75-09-2'
TLm 96:
1,000-100 ppm
Methane, CC13F
Trichlorofluoro-
75-69-4'
Inhalation-human
Oral-human
Inhalation-human
Oral-rat
Inhalation-rat
Inhalation-mouse
Intraperi toneal-mouse
Subcutaneous-mouse
Oral-dog
Inhalation-dog
Intraperitoneal-dog
Subcutaneous-dog
Intravenous-dog
Inhalation-cat
Oral-rabbit
Subcutaneous-rabbit
Inhalation-guinea pig
Inhalation-rat
Intraperitoneal-mouse
TCLo:
500 ppm
1YI
LDLo:
TCLo:
LD50:
LC50:
LC50:
LD50:
LD50:
LDLo:
LCLo:
LDLo:
LDLo:
LDLo:
LCLo:
LDLo:
LDLo:
LCLo:
LCLo:
LD50:
500 mg/kg
500 ppm
167 mg/kg
88,000 mg/m3
14,400 ppm
1,500 mg/kg
6,460 mg/kg
3,000 mg/kg
20,000 ppm
950 mg/kg
2,700 mg/kg
200 mg/kg
43,400 mg/m3
1,900 mg/kg
2,700 mg/kg
5,000 ppm
10 ppm
1,743 mg/kg
8H
30M
7H
7H
4.5H
2H
20M
Central
Nervous
System
Blood
TLV (air): 200 ppm
OSHA std (air):
TWA 500 ppm; Cl
1,000; PK 2.000/
5M/2H
NIOSH recm std (air):
TWA 75 ppm;
PK 500 ppm/15M
TLV (air):
1000 ppm
OSHA std (air):
TWA 1,000 ppm
CO
-------
TABLE 7 (Continued)
TOXICITY OF COMPOUNDS
HOOKER CHEMICALS AND PLASTICS CORPORATION WASTE DISPOSAL SITES
NIAGARA FALLS, NEW YORK
Chemical Other Toxicity
Compound Name Molecular Abstracts Aquatic Toxicity Route of . . Type^of
Formula Service No. Entry " sPecies Doseb
Phenol C6H60 108-95-2f TLm 96: Skin-rabbit
100-10 ppm
Skin-rabbit
Eye- rabbit
Oral -human LDLo:
Oral -rat LD50:
Skin-rat LD50:
Intraperitoneal-rat LD50:
Subcutaneous- rat LDLo:
Oral -mouse LD50:
Skin-mouse TDLo: 4
Intraperitoneal-mouse LD50:
Subcutaneous-mouse LD50:
Intravenous-mouse LD50:
Oral -dog LDLo:
Parenteral-dog LDLo: 2
Oral -cat LDLo:
Subcutaneous-cat LDLo:
Parenteral-cat LDLo:
Oral -rabbit LDLo:
Skin-rabbit LD50:
Intraperitoneal-rabbit LDLo:
Subcutaneous-rabbit LDLo:
Intravenous-rabbit LDLo:
Parenteral- rabbit LDLo:
Intraperitoneal-guinea LDLo:
pig
Subcutaneous-guinea pig LDLo:
Subcutaneous- frog LDLo:
Parenteral -frog LDLo:
Subcutaneous- frog LDLo:
Phenol, o-Chloro- C6HSC10 95-57-8f Oral-rat LD50:
Intraperitoneal-rat LD50:
Subcutaneous- rat LD50:
Oral -mouse LD50:
Skin-mouse TDLo: 4
Subcutaneous- rabbit LDLo:
Intravenous- rabbit LDLo:
Subcutaneous- guinea pig LDLo:
Subcutaneous- frog LDLo:
Oral -mammal LD50:
Data
Dose Duration0
500 mg 24H
535 mg open
5 mg
140 ing/kg
414 mg/kg
669 mg/kg
250 mg/kg
650 mg/kg
300 mg/kg
,000 mg/kg 20WI
360 mg/kg
344 mg/kg
112 mg/kg
500 mg/kg
,000 mg/kg
80 mg/kg
80 mg/kg
500 mg/kg
420 mg/kg
850 mg/kg
620 mg/kg
620 mg/kg
180 mg/kg
300 mg/kg
300 mg/kg
450 mg/kg
75 mg/kg
290 mg/kg
290 mg/kg
670 mg/kg
230 mg/kg
950 mg/kg
670 mg/kg
,800 mg/kg 12WI
950 mg/kg
120 mg/kg
800 mg/kg
400 mg/kg
440 mg/kg
Effects'1
Severe
Irritation
Severe
Irritation
Severe
Irritation
Carcinogenic
Neoplastic
Exposure
Limits6
TLV (air):
5 ppm (skin)
OSHA std (air):
TWA 5 ppm
(skin)
NIOSH recm
std (air):
TWA 20 mg/m3;
Cl 60 mg/m3/15M
oo
en
-------
TABLE 7 (Continued)
TOXICITY OF COMPOUNDS
HOOKER CHEMICALS AND PLASTICS CORPORATION WASTE DISPOSAL SITES
NIAGARA FALLS, NEW YORK
Chemical
Compound Name Molecular Abstracts Aquatic Toxicity3
Formula Service No.
Phenol, C6H4C120 120-83-2f
2-,4-Dichloro-
•
Phenol, C6HC1S0 87-86-5f
Pentachloro-
Phthalic Acid, C24H3804 117-81-7f
Bis (2-Ethylhexyl)
Ester
Other Toxicity Data
"ffiV - *»«"
Oral-rat
Intraperitoneal-rat
Subcutaneous-rat
Oral-mouse
Skin-mouse
Skin-rabbit
Oral -human
Oral -man
Oral -rat
Oral-rat
Inhalation-rat
Skin-rat
Intraperitoneal-rat
Subcutaneous-rat
Subcutaneous-mouse
Subcutaneous-dog
Oral -rabbit
Skin-rabbit
Intraperitoneal -rabbit
Subcutaneous-rabbi t
Eye-rabbit
Oral-man
Oral-rat
Intraperitoneal-rat
Intraper i toneal - rat
Intravenous-rat
Oral -mouse
Oral-mouse
Intraperitoneal -mouse
Oral -rabbit
Skin- rabbit
Skin-guinea pig
Type.of
Dose
LDLo:
LD50:
LD50:
LD50:
TDLo:
LDLo:
TDLo:
TDLo:
LD50:
LD50:
LD50:
LD50:
LD50:
TDLo:
LDLo:
LDLo:
LDLo:
LDLo:
LDLo:
TDLo:
LD50:
LD50:
TDLo:
LDLo:
LD50:
TDLo:
LD50:
LD50:
LD50:
LD50:
Dose
580 mg/kg
430 mg/kg
1,730 mg/kg
1,600 mg/kg
312 mg/kg
10 mg
29 mg/kg
196 mg/kg
60 mg/kg
50 mg/kg
11,700 ug/kg
105 mg/kg
56 mg/kg
100 mg/kg
46 mg/kg
135 mg/kg
70 mg/kg
40 mg/kg
135 mg/kg
70 mg/kg
500 mg
143 mg/kg
31 gm/kg
30,700 mg/kg
30 gm/kg
300 mg/kg
30 gm/kg
7,500 mg/kg
14 gm/kg
34 gm/kg
25 gm/kg
10 gm/kg
d Exposure
Duration0 Effects0 Limits6
39WI Carcinogenic
24H Mild TLV (air):
open Irritation 0.5mg/m3 (skin)
Central OSHA std (air):
Nervous TWA 500 \ig/m3
System
9D Teratogenic
(Preg)
Neoplastic
Irritation OSHA std (air):
Gastro- TWA 5 mg/m3
intestinal
Tract
5-15D Tetratogenic
(Preg)
80 Teratogenic
(Preg)
oo
-------
TABLE 7 (Continued)
TOXICITY OF COMPOUNDS
HOOKER CHEMICALS AND PLASTICS CORPORATION WASTE DISPOSAL SITES
NIAGARA FALLS. NEW YORK
Chemical Other Toxicity Data
Compound Name Molecular Abstracts Aquatic Toxicity3 Route of _ cnecies Typebof
Formula Service No. Entry 3pet Dose
Phthalic Acid, Cj6H220« 84-74-2f TLM 96: Oral-human
Dibutyl Ester 1000-100 ppm Oral-human
Oral -mouse
Intraperitoneal-rat
Intraperitoneal-rat
Phthalic Acid, C1ZH1404 84-66-2f Eye-rabbit
Di ethyl Ester Oral -human
Inhalation- human
Intraperitonal-rat
I ntraper i toneal -rat
I ntraperi toneal -mouse
Oral -rabbit
I ntravenous- rabb i t
Subcutaneous-guinea pig
Toluene C7H8 108-88-3f TLm 96: Eye-human
100-10 ppm Oral -human
Inhalation-human
Inhalation-man
Oral-rat
Inhalation-rat
Intraperitoneal-rat
Inhalation-mouse
Skin-rabbit
Skin-rabbit
Eye- rabb it
Subcutaneous- frog
2,4-Xylenol C8H100 105-67-9f Oral-rat
(2,4-Dimethylphenol) Skin-rat
Oral-mouse
Skin-mouse
LDLo:
TDLo:
LD50:
LD50:
TDLo:
LDLo:
TCLo:
LDSO:
TDLo:
LDSO:
LDLo:
LDLo:
LDLo:
LDLo:
TCLo:
TCLo:
LD50:
LCLo:
LDLo:
LC50:
LD50:
LDLo:
LDSO:
LD50:
LDSO:
TDLo:
Dose Duration0
5,000 mg/kg
140 mg/kg
12,000 mg/kg
3,050 mg/kg
874 mg/kg 5-15D
(Preg)
112 mg
500 mg/kg
1,000 mg/m3
5,058 mg/kg
1,232 mg/kg 5-150
(Preg)
2,749 ing/kg
1,000 mg/kg
100 mg/kg
3,000 mg/kg
300 ppm
50 mg/kg
200 ppm
100 ppm
5,000 mg/kg
4,000 ppm 4H
800 mg/kg
5,320 ppm 8H
14 gin/kg
435 mg
870 ug
920 mg/kg
3,200 mg/kg
1,040 mg/kg
809 mg/kg
5,600 mg/kg 28WI
Effectsd
Eye
Teratogenic
Irritation
Irritant
Teratogenic
Irritation
Central
Nervous
System
Psychotropic
Mild
Irritation
Mild
Irritation
Carcinogenic
Exposure
Limits6
TLV (air): 5 mg/m3
OSHA std (air):
TWA 5 mg/m3
TLV (air):
5 mg/m3
-
TLV (air): 100 ppm
(skin)
OSHA std (air):
TWA 200 ppm
Cl 300; PK 500/10M
NIOSH recm std
TWA 100 ppm;
Cl 200 ppm/lOM
(air)
.
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TABLE 7 (Continued)
TOXICITY OF COMPOUNDS
HOOKER CHEMICALS AND PLASTICS CORPORATION WASTE DISPOSAL SITES
a Aquatic Toxicity:
b Other Toxicity Data:
c Duration:
d Exposure Limits:
TLm 96:
LD50 -
LCLo -
LC50 -
LDLo -
TDLo -
TCLo -
TD
M
H
D
W
Y
C
I
NR
NIOSH -
OSHA -
TWA -
TLV -
Cl
Pk
96-hour static or continuous flow standard protocol, in parts per million (ppm)
lethal dose 50% kill
lowest published lethal concentration
lethal concentration 50% kill
lowest published lethal dose
lowest published toxic dose
lowest published toxic concentration
toxic dose
minute;
hour
day
week
year
continuous
intermittent
not reported
National Institute for Occupational Safety and Health
Occupational Safety and Health Act of 1970
time-weighted average concentration
threshold limit value
ceiling
peak concentration
Blood - Blood effects; effect on all blood elements, electrolytes, pH, protein, oxygen carrying or releasing capacity.
Carcinogenic - Carcinogenic effects; producing cancer, a cellular tumor the nature of which is fatal, or is associated with the formation
of secondary tumors (metastasis)
Central Nervous System - Includes effects such as headaches, tremor, drowsiness, convulsions, hypnosis, anesthesia.
Eye - Irritation, diplopia, cataracts, eye ground, blindness by affecting the eye or the optic nerve.
Gastrointestinal - diarrhea, constipation, ulceration.
Irritant - Any Irritant effect on the skin, eye or mucous membrane.
Mutagenic - Transmissible changes produced in the offspring.
Neoplastic - The production of tumors not clearly defined as carcinogenic.
Psychotropic - Exerting an effect upon the mind.
Pulmonary - Effects on respiration and respiratory pathology.
Systemic - Effects on the metabolic and excretory function of the liver or kidneys.
Teratogenic - Nontransmissible changes produced in the offspring.
This chemical has been selected for priority attention as point source water effluent discharge toxic pollutant (NRDC vs Train consent decree)
co
oo
-------
39
REFERENCES
1. Ames, B.N., McCann, J., and Yamansaki, E., Methods for Detecting
Carcinogens and Mutagens with the Salmonella/Mammalian - Microsome
Mutagenicity Test. Mutation Research. 31 (1975) 347-364.
2. Commoner, B., Chemical Carcinogens in the Environment, Presentation
at the First Chemical Congress of the North American Continent,
Mexico City, Mexico, Dec. 1975.
3. Commoner, B., Development of Methodology, Based on Bacterial
Mutagenesis and Hyperfine Labelling, For the Rapid Detection and
Identification of Synthetic Organic Carcinogens in Environmental
Samples, Research Proposal Submitted to national Science Foundation,
February, 1976.
4. Commoner, B., Henry, J.I., Gold, J.C. , Reading, M.J., Vithayathil,
A.J., "Reliability of Bacterial Mutagenesis Techniques to Distinguish
Carcinogenic and Noncarcinogenic Chemicals," EPA-600/1-76-011,
Government Printing Office, Washington, D.C. (April 1976).
5. McCann, J., Ames, B.N., Detection of Carcinogens as Mutagens,
in the Salmonella/Microsome Test: Assay of 300 Chemicals, Proc.
Nat. Acad. Sci., 73 (1976) 950-954.
6. Purchase, I.F.H., et. al., An Evaluation of 6 Short-Term Tests
for Detecting Organic Chemical Carcinogens. British Journal of
Cancer. 37, (1978) 873-902.
7. Sugimura, T., et. al., Overlapping of Carcinogens and Mutagens,
In Magee P.N., S. Takayama, T. Sugimura, and T. Matsushima, eds.,
Fundamentals in Cancer Prevention, Univ. Park Press, Baltimore, Md.,
pp. 191-215, 1976.
-------
APPENDIX A
PRIORITY POLLUTANTS LISTING
-------
A-l
RECOMMENDED LIST OF PRIORITY
POLLUTANTS
Compound flame
1. *acenaphthene
2. *acrolein
3. *acrylom'trile
4. *benzene
5. *benzidine
6. *carbon tetrachloride (tetrachloromethane)
*Chlorinated benezenes (other than dichlorobenzenes)
7. chlorobenezene
8. 1 ,2,4-trichlorobenzene
9. hexachlorobenzene
*Ch1orinated ethanes (including 1 ,2-dichloroethane,
1 ,1 ,1-trichloroethane and hexachloroethane)
10. 1 ,2-dichloroethane
11. 1,1 ,1-trichloroethane
12. hexachloroethane
13. 1,1-dichloroethane
14 1,1,2-trichloroethane
15. 1 ,1 ,2,2-tetrachloroethane
16 chloroethane
*Chloroa1kyl ethers (chloromethyl , chloroethyl and mixed ethers)
17. bis(chlororr,ethyl) ether
*Specific compounds and chemical classes as listed in ^e consent
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A-2
18. bis(2-chloroethyl) ether
19 2-chloroethyl vinyl ether (mixed)
*Ch1orinated naphtalene
20. 2-chloronaphthalene
*Chlorinated phenols (other than those listed elsewhere;
. includes trichlorophenols and chlorinated cresols)
21. 2,4,6-trichlorophenol
22. parachlorometa cresol
23. *chloroform (trichloromethane)
24. *2-chlorophenol
*Dichlorobenzenes
25 1,2-dichlorobenzene
26. 1,3-dichlorobenzene
27. 1,4-dichlorobenzene
*Dichtorobenzidine
28. 3,3'-dichlorobenzidine
*Dichloroethylenes (1,1-dichloroethylene and 1,2-dichloroethylene)
29 1,1-dichloroethylene
30. 1,2-trans-dichloroethylene
31. *2,4-dichlorophenol
*Dichloropropane and dichloropropene
32. 1,2-dichloropropane
33. 1,2-dichloropropylene (1,3-dichloropropene)
34. *2,4-dimethylphenol
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A-3
*Dim'troto1uene
35. 2,4-dinitrotoluene
36. 2,6-dinitrotoluene
37. *1,2-diphenylhydrazine
38. *ethylbenzene
39. *fluoranthene
*Ha1oethers (other than those listed elsewhere)
40. 4-chlorophenyl phenyl ether
41. 4-bromophenyl phenyl ether
42. bis(2-chloroisopropyl) ether
43. bis(2-chloroethoxy) methane
*Ha1omethanes (other than those listed elsewhere)
44. methylene chloride (dichloromethane)
45. methyl chloride (chloromethane)
46. methyl bromide (bromomethane)
47. bromoform (tribromomethane)
48. dichlorobromomethane
49. trichlorofluoromethane
50. dichlorodifluoromethane
51. chlorodibromomethane
52. *hexachlorobutodiene
53. *hexachlorocyclopentadienc
54. *isophorone
55. *naphthalene
56. *nitrobenzeiici
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A-4
*Nitrophenols (including 2,4-dinitrophenol and dinitrocresol)
57. 2-nitrophenol
58. 4-nitrophenol
59. *2,4-dinitrophenol
60. 4,6-dinitro-o-cresol
*Nitrosamines
61. N-nitrosodimethylamine
62. N-nitrosodiphenylamine
63. N-nitrosodi-n-propylamine
64. *pentachlorophenol
65. *phenol
*Phtha1ate esters
66. bis(2-ethylhexyl) phthalate
67. butyl benzyl phthalate
68. di-n-butyl phthalate
69. di-n-octyl phthalate
70. diethyl phthalate
71. dimethyl phthalate
*Po1ynuclear aromatic hydracrarbons
72. benzo(a)anthracene (1,2-benzanthracene)
73. benzo (a) pyrene (3,4-benzopyrene)
74. 3,4-benzofluoranthene (benzo(b)fluoranthene)
75. benzo(k)fluoranthane (11,12-benzofluoranthene)
76. chrysene
77. accnaphthylene
78. anthracene
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A-5
79. benzo(ghi)perylene (1,12-benzoperylene)
80. fluroene
81. phenathrene
82. dibenzo (a,h)anthracene (1,2,5,6-dibenzanthracene)
83. indeno (1,2,3-cd)pyrene (2,3-o-phenylenepyrene)
84. pyrene
85. *tetrachloroethylene
86. *toluens
87. *trichloroethylene
88. *vinyl chloride
Pesticides and Metabolites
89. *aldrin
90. *dieldrin
91. *chlordane (technical mixture & metabolites)
*DDT and Metabolites
92. 4,4'-DDT
93. 4,4'-DDE (p,p'-DDX)
94. 4,4'-DDD (p.p'-TDE)
*endosu!fan and metabolites^
95. a-endosulfan-Alpha
96. b-endosulfan-Beta
97. endosulfan sulfate
*endrin and metabolites
98. endrin
99. endrin aldehyde
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A-6
*heptach1or and metabolites
100. heptachlor
101. heptachlor epoxide
*hexachlorocyc1ohexane (all isomers)
102. a-BHC-Alpha
103. b-BHC-Beta
104. r-SHC (lindane)-Gamma
105. g-BHC-Delta
*polychlorinat5d biphenvls (PCB's]
106. PCB-1242 (Arochlor 1242)
107. PCB-1254 (Arochlor 1254)
108. PCB-1221 (Arochlor 1221)
109. PCB-1232 (Arochlor 1232)
110. PCB-1248 (Arochlor 1248)
111. PCB-1260 (Arochlor 1260)
112. PCB-1016 (Arochlor 1016)
113. *Toxaphene
114. *Antirnony (Total)
115. *Arsenic (Total)
116. *Asbestos (Fibrous)
117. *Beryllium (Total)
118. *Cadmuim (Total)
119. *Chromium (Total)
120. *Copper (Total)
121. *Cyanide (Total)
12.2.- *LeJ
-------
A-7
123. *Mercury (Total)
124. *Mickel (Total)
125. *Selenium (Total)
126. *Silver (Total)
127. *Thallium (Total)
128. *Zinc (Total)
129. **2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)
*Specific compounds and chemical classes as listed in the consent decree
**This comoound was specifically listed in the consent decree. Because
of the extreme tuxicity (TCDD). We are recommending that laboratories
not acquire analytical standard for this compound.
-------
APPENDIX B
METHODS, ANALYTICAL PROCEDURES,
AND QUALITY CONTROL
-------
B-l
MUTAGEN ASSAY METHODS
Sample Extraction
Prior to extraction, samples were allowed to settle for one hour.
The aqueous portion of the samples were then decanted; the sediment
was discarded.
For basic-neutral extractions, one-liter portions of decanted
sample were adjusted above pH 12 with NaOH. Each one-liter aliquot
was extracted three times (5 minutes each) with 35 ml of dichloro-
methane. The solvent fraction was then separated, mixed with anhydrous
sodium sulfate to remove any emulsion and filtered (Whatman No. 1
filter paper) into a one-liter round bottom flask. The aqueous frac-
tions were retained for acidic extraction. These were adjusted below
pH 2 and the above procedure repeated.
The combined solvent fractions (approximately 420 ml) were evapor-
ated to dryness at 44° C in a rotoevaporator.* The residue was resus-
pended into 35 ml** sterile dimethylsulfoxide (DMSO), labeled and re-
frigerated at 4°C until assayed by the Ames procedure.
An alternate mehtod of preparing samples for the Ames Assay consis-
ted of filtering 50 ml aliquots of unconcentrated sample through a
0.22 micro-meter pore-size membrane filter. Filtered samples were
labeled and refrigerated at 4°C until assayed by the Ames procedure.
* Using this method the estimate of mutagenic activity from complex
mixtures is low, because: 1) the volatile alkyl halides are lost
in the dichloromethane/DMSO exchange, and 2) the Salmonella test
detects only about 90% of carcinogens as mutagens. Some of the
important chlorinated hydrocarbons are not detected, i.e., chloro-
form, hexachlorobenzene, etc.
** Sample No. 01 required 50 ml DMSO for complete solution. This
material was later found to be contaminated. The solution was
sterilized by filtration through a ultra-fine, fritted-glass
filter prior to the Ames Assay.
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B-2
Bacterial Mutagem'city Assay
The Standard Ames Salmonel1 a/mammal Ian microsome mutagenicity
assay was performed using the agar-plate incorporation procedure as
described by Ames, et aJL1 Sample extracts and filtered whole (uncon-
centrated) aliquots were screened with Salmonella typhimurium tester
strains TA 98, TA 100, TA 1535, TA 1537 and TA 1538, first indivi-
dually and then in the presence of rat liver homogenates (S-9 mix).
Mutagenesis Assay by Preincubation Method
Undiluted extracts of samples 01 and 02 contained large amounts
of organic materials. Additionally, Sample No. 01 was toxic to the
Salmonella tester strains. To allow the liver homogenate more time
to react with the organic mixture, and to possibly reduce the toxi-
city of Sample No. 01, the sample extracts were preincubated in the
presence of S-9 mix and the tester strains at 20°C for 20 minutes
prior to the agar-plate assay.
Quality Control
A four-liter volume of sterile distilled water was added to a
clean, 1-gallon amber glass bottle and treated as a sample. This
served as a quality reference for the sample bottles, distilled
water, extracting solvents, emulsion removal, and the. concentration
process. A DMSO sample was tested to ensure that this material
did not interfere with test results. These quality control pro-
cedures were repeated five times during the study.
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B-3
The tester strains TA 1535, TA 1537, TA 1538, TA 98 and TA 100
were exposed to diagnostic mutagens to confirm their natural reversion
characteristics. The strains were tested for ampicillin resistance,
crystal violet sensitivity, ultra-violet light sensitivity, and histi-
dine requirement. Spontaneous reversion rates were tested with each
sample series.
Rat liver homogenate was tested with 2-aminofluorene with strains
TA 1538, TA 98 and TA 100 to confirm the metabolic activation process.
Sterility checks were performed on solvents, extracts, liver
preparation, and all culture media.
-------
B-5
VOLATILE ORGANIC COMPOUNDS 8Y GC/MS
INVESTIGATIONS CENTER
1.0 Scope and Application
1.1 Water and wastewater sanples may be analyzed for purgeable
organic compounds, typically methylene chloride through ethyl
benzene by GCAlS. Both qualitative and quantitative data are
generated. This procedure includes data evaluation as defined
for screening of industrial wastes for "priority pollutants"
as well as data for complete organics characterization of any
purgeable components.
2.0 Summary of Method
2.1 Aliquots of aqueous samples are purged with an inert gas. low
molecular weight and slightly soluble components are stripped
from the solution and trapped on a porous polymer adsorbent
trap. Organic components are then desorbsd from the trap by
rapid heating onto an analytical gas chromatographic (GC) col-
umn. As separated components elute from the GC column, they are
detected by a quadrupole mass spectometer. Quantitation of
compounds identified from their spectra is effected either by
external or internal standard techniques.
3.0 Sample Handling and Preservation
3.1 Samples may be collected as duplicate grab samples. Duplicates
are useful for reanalysis of the sample if needed. If data
are to be correlated to other 24 hours composite samples, col-
lect multiple grab samples at regular intervals. They may be
composited at the lab prior to analysis.
3.2 Preserve the samples by maintaining at or below 4°C during
-------
3-6
shipment and storage. Samples containing residual chlorine
require the addition of O.lg Na2S203 par 100 ml of sample to
reduce the renvaining chlorine.
4.0 Definitions and Corrments
5.0 Interferences
5.1 Samples containing residual chlorine can produce halogenated
organics in excess of what was present at the time of collec-
tion. Therefore the addition of a reducing agent is necessary
if residual chlorine is .suspect.
5.2 No head space is allowed in a sample. Samples containing head
space may loose volatile species and produce erronous results.
5.3 Samples exposed to vapors of volatile organic compounds may
absorb those vapors and produce erronous data. Blanks must be
handled and transported concurrently with samples to identify
potential contamination.
6.0 Apparatus
6.1 Sample Bottles: 1 oz. glass bottles equipped with teflon-lined
silicone septa and screw caps (Pierce #13074 and #12722 or
equivalent). Before sampling, wash used bottles with soap
(Alconox or equivalent) and tap water, rinse with tap water.
New bottles require only washing with tap water. Bake bottles
at 200°C and septa at 80°C for 30 minutes. Allow to cool in a
desicator with charcoal adsorbant to maintain an organics-free
atmosphere. Then cap the bottles and hold for sampling.
6.2 Sample handling syringes: Samples arc transferred using 5.0 ml.
gas-tight syringes equipped with gas-tight valves and 6"- needles.
(Tekmar or equivalent)
-------
B-7
-6.3 Liquid sample concentrator: Tekmar LSC-1 or equivalent with
the following modifactions:
6.3-.1 Replace existing trap with a thin wall (0-020" stain-
less steel (SS) trap packed with 15 cm 60/80 mesh Tenax
GC (Applied Sciences). Wrap the trap with f iberglass
insulated heating wire (Briskheat, 7 ohm per foot Nichrcme
wire for direct contact with metal or equivalent). Wrap
the platinum resistance element between the SS tubing
and the heating wire. Attach the heater wire and resis-
tance element to the appropriate terminals.
6.3.2 Add a trap made of 12" of 3/8" copper tubing packed with
activated charcoal (190°C for 4 hours) immediately ahead
of the purging chamber.
6.3.3 Add a GC flow controller such that f low'going to the
GC column is regulated. The GC column then beccmes com-
pletely independent of the existing GC flow systems.
6.4 GC column: Separations are effected using an 8' by 1/8" SS
column packed with 0.2% Carbowax 1500 on 60/80 Mesh Carbopack C
(available from Supslco).
6.5 Gas chrorutograph: A Varian 1400 or equivalent equipped with
a linear temperature programmer.
6.6 Detector: Finnigan 1015 mass spectrometer with Systems Indus-
trios System 150 data system, or equivalent instrument capable
of collecting continuous repetative mass spectra (CRMS) over
'a range of 33 to 260 aim in 5 seconds or less. The data system
/on
must bo capable of generating multiple extracted *» current
profiles (CIPC).
-------
B-8
6.7 Glassware: All glassware is washed as described in section
6.1 and baked at 105°C (up to 200°C) for at least 30 minutes.
6.8 Analytical Balance: Capable of measuring O.OOOlg for standards
preparation.
7.0 Reagents
7.1 Organic-Free water: Pass tap water through a 2 x 40 cm column
of charcoal activated by heating to 190°C for four hours.
7.2.a Concentrated Standards (Liquid components): Stock solutions
are prepared at ca. 1 rag/ml in pesticide analysis grade meth-
anol. Due to the high volatility of some compounds, exact
concentrations are calculated from the volume of pure compound
used and its density. To 10.0 ml of methanol in a 14 ml vial
with a teflon-lined screw cap, add 10.0 ul of pure compound,
seal, mix and store in a freezer at -20°C. This stock standard
f — p'* „ 1
may be stable for two months" dependent upon the volatility of
the component. Calculate the concentration from the volume
of pure compound and its density as follows:
ng/ul = 10.0 x lO'^l x (density)g_ x 1 ng x _10"3 ml
"10.0 ml ml 10-i'g 1 ul
7.2.b Concentrated Standards (Gaseous components): Stock solutions
of gaseous components my be prepared similarly to liquid com-
ponents with the following change. Prepare a vial containing
10.0 ml of rethanol, weigh the capped bottle and record this
tare veight. Carefully bubble 'die pure gaseous component into
the ncciuinol. When enough gas ius been absorbed into the meth-
anol (estimated), reseal tha vial 3rd rewciejh. The increase
in weight represents the amount of pure component added. Calculate
-------
B-9
the concentration as follows:
ng/ul = (net weight)n>g x 1 ng x 10" J ml
1(T6 mg ul
7.3 Working concentrate: Ranove the stock standard from the freezer
and allow to equilibrate to ambient temperature. With a 250
microliter syringe, prepare a mixed Standard with each component
at 20 ng/ul in methanol.. Seal the solution in 2 ml crimp seal
vials with teflon-lined septa. These working standards may be
stable up to one month depending or. the volatility of the ccm-
pcnents.
7.4 Analytical standards for GC/MS: Using a microliter syringe,
add 1 to 50 ul of the working concentrate to a 5.0 ml aliquot
of organic-free water. Analyze iirmediately. Each ul of working
concentrate when added to 5.0 ml of water is equivalent to 4 ug/1
(ppb).
7.5 Internal standards: In the same manner as 7.2 and 7.3, prepare
a single working concentrate of bronochlormethane (CH2BrCl)
and 1,4 dichlorobutane (C4II8C12) at 100 ng/ul each.
8.0 Procedure
8.1 Instrument Preparation
8.1.1 Install the gas chromatographic (GC) column by directly
passing through the injection port. Attach the colunn
using tcClon ferrules only to allow subsequent disman-
tcling the system. Connect the other end of the tubing
'to the trap cxic of the Tetarar LSC-3. Attach a source
oC ultra-pure -helium to the inlet of the Teknvir. Adjust
the column flowrate to 3Cml/min. Carefully check the
svstcm for leaks.
-------
B-10
8.1.2 Periodically, replace the charcoal in the internal filter
of the LSC-1.
S.I.3 Set up the GC for 60°C initial and 170°C final temperatures,
an 8°C/min. program rate, and hold at the filial temper-
ature.
8.2 Mass spectrometer calibration
8.2.1 Adjust and calibrate the mass spectrometer according to
the iranufacturer' s specifications.
8.2.2 Analyze an organics-free-water blank to verify a clean
system.
8.2.3 Analyse a standard mix at a concentration near the mid-
point of the calibration curve. Check the response of
factors calculated for the multipoint calibration curve.
Check the response of each compound and verify if it is
v/ithin the range of response factors calculated for the
multi point calibration curve. If not, determine the
cause of the problem, make the necessary corrections
and reanalyze the standard.
8.3 Sample Analysis
8.3.1 Equilibrate sample bottles to ambient temperature and
pour an/ aliquot directly into a 5.0 ml syringe. Imme-
diately insert the plunger, invert die syringe, expel
any air and adjust the volume to 5.0 ml. Composite
samples may be prepared by adjusting the volume to the
desired amount for the individual aliquot and adding
thin to a second syringe. Continue preparing the individual
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B-11
aliquots until the composite is prepared. Dose the
sample with 10 ul (1 ug each standard) of the internal
standard solution to yeild a concentration of 200 ug/1.
8.3.2 Remove a glass purge device from the oven and cool in
the charcoal-filled desicator. Attach to the Tekmar
and introduce the sample.
8.3.3 Purge the sample for 12 minutes at 40 ml/min. onto the
Tenax trap. At the sa.TS time, cool the GC oven to ambi-
ent temperature by leaving the oven door open.
8.3.4 Set the trap desorb temperature to 180°C, switch to the
desorb mode and start a tiaer. After 3h minutes, begin
collection of CRMS using the following conditions:
Mass range: 20-27; 33-260
Integration time: 17 ms.
Or scan time up: 4 seconds
And scan time down: 0.1 seconds
After four minutes, switch back to purge mode, close JUe
and set the temperature to 60°C.
8.3.5 After eight minutes, begin the GC temperature program.
8.3.6 While the sample is running, remove the purge device
and join the purge inlet and outlet line with a short
piece of 1/4" tubing. Turn on the trap bake and adjust
the temperature to 200°C. Bake out the trap for at least
5 minutes. Wash the purge device with methanol and
place in an oven as describee! in section 6.1.
8.3.7 Collect data until the last components have elctod from
the GC column. Typically, 30 minutes.
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B-I;
8.4 Data Evaluation
8.4.1 After each analysis, plot the reconstructed ion chrcmato-
gram (RIC) and extracted ion current profiles (EIC?) for
each internal standard added. Integrate the areas of the
selected peaks and ccmpare to the limits calculated in
section 9.6. If the base peak areas are outside the
acceptable ranges, evaluate the problem and reanalyze
the sample. If the da^a are acceptable, process the
data as required for organics characterization or pri-
ority pollutants as described below.
8.4.2 Organics Characterization. Select a spectrum and sub-
tract the background for each peak of interest. Generate
a plot of the spectrum for analysis. In addition, per-
form a search of the current NBS spectra library and
print out the results. (ref. 2)
8.4.3 Priority Pollutant Evaluation. Using the protccal pro-
cedures (ref. 3), generate and evaluate each compound's
EICP for the selected ions. Compounds that are present
may be quantitated as described in the protccal and sum-
marized in section 8.4.4.
8.4.4 Quantitation. Compounds identified are quantitated by
the internal standard techniques. An ion of the compound!
is selected and integrated over the GC peak. The area
of an internal standard (typically 1,4-dichlorobutane,
m/c 55) ion is also determined. The concentration of
the component is then determined based on the amount of
internal standard (200 ppb here) and the relative response
-------
B-13
factor determined in section 8.4.5 by the following
equation:
Cc = Ac x Cs_
As Rf
Where: Cc = concentration of component (p?b)
Ac = area of component ion
As = area of internal standard ion
Cs = concentration of internal standard (ppb)
Rf = relative response facton (unitless)
8.4.5 Determination of Response factors: Prior to the analysis
of samples, response factors for the compounds of interest
relative to the internal standard must be determined and
verified over a concentration range. Analyze 200 ppb
(typical for VGA's) for each compound. Mixed standards
are acceptable. Measure the areas of the ions of interest
of the internal standard and the components in the stand-
ards. Calculate the response factors as follows:
Rf = Ac x Cj;
As Cc
Where: Rf = relative response factor
As = area of internal standard ion
Ac = area of component ion
Cs = concentration of internal standard (ppb)
Cc = concentration of component. (ppb)
9.0 Quality Control
9.1 Standard Curve - Prior to ths determination of any sample com-
ponents by GC/MS using internal standards, linearity for each
standard component must be established over a typical working
range of 20 to 200 ppb. This requires analysis of at least
four concentration levels: 0, 20, 100 and 200 ppb. Cal-
culate the response factors relative to one internal standard
-------
B-14
and determine the mean and percent relative standard deviation
(?,RSD). Acceptable data are indicated by a %RSD of less than
20. Values outside this range indicate problems with response
linearity and the linear range nust be carefully evaluated.
Table I shows typical data for 22 of the priority pollutants.
Daily, one standard mix at the midpoint of the linear range
must be analyzed and the response factors should fall within
the range indicated above. The SEED range should be updated
as more data are generated to reflect changes in the method's
performance.
9.2 Precision - To determine the percision of the method a regular
• o
program of analyses of replicate aliquots of environmental sam-
ples must be carried out. The precision criterion should be
developed from 15 sets of replicate results accumulated over a
period of time during the routine analysis program. At least
two replicate aliquots of a well mixed sample must be analyzed
with each set of 20 samples or less analyzed at a given time.
These replicate data must be obtained for each parameter of
interest.
Initially, samples selected for replicate analysis should
be those tliat are most representative of the interference poten-
tial of the sample type. As the program progresses, samples
representing the entire range of concentrations and interference
potential should be designed into the replicate analysis program.
After 15 replicate results hive been obtained, calculate
the range (R) of these results as fcllcvs:
-------
B-15
where R! is the difference between the results of the pair
(Xj. and Xl2) from '-ample i-1 through n. The concentration of
each sample is represented by the mean:
where X is the average of the results of the replicate pair.
A preliminary estdjaats of the critical difference (Ifc) between
k
replicate analysis for any specific concentration level (C)
can be calculated as: '
n n
R =3.27
From these data develop a table of such Ifc values for various
C values that span the concentration range of interest.
These preliminary critical difference values may be used
to judge the acceptability of the succeeding replicate results.
To do this, calculate the mean (X) and difference (R) between
the replicate results. Referring to the table of critical range
values developed above, find the C nearest to X and use its RC
to evaluate the acceptability of R. If the R is greater than
Rc, the system precision is out of control and the source of
this unusual variability should be identified and resolved be-
fore continuing with routine analysis and periodically (after
25 to 30 ucditioral pairs of replicate res-alts are obtained)
revxse, update, and improve the table of critical range values.
9.3 Recovery - Determine the recovery of the method for the analysis
-------
B-16
of environmental samples by adding a spike (T^, true value)
sufficient to approximately double the background concentration
i
level (X-) of the sample selected earlier for replicate anal-
ysis (Section Al). If the original concentration is higher
than the midpoint of the standard curve (range of the method),
then the concentration of the spike should be approximately
one-half the original concentration. If the concentration of
the original sample was not detectable, the concentration of
the spi-ke should be five to fifteen times the lower limit of
detection. The volume"of standard added in agueous solution
should not dilute the sample by more than ten percent. The
volume of standard added in an organic solvent solution should
be kept small (100 ul/1 or less), so that the solubility of
the standard in the water will not be affected.
Analyze the sample, calculate the observed value (0^),
and then calculate the recovery for the spike as follows:
P = 100 (Oi - XjJAi
where E^ is the percent recovery. If the sample was diluted
due to the addition of the spike, adjust X^ accordingly.
After determining P- for at least 15 spike results, cal-
culate the mean percent recovery (P) and standard deviation
(S ) of the recovery as follows:
n n „
P = (E P- - (Z PiP/n
i-13- i=2
n n ~
S = 1 Z P - (I P:,) /n
? n^I i-1 i=2
-------
B-17
where n = the number of percent recovery values available.
If the percent recovery of the spike is not within the
interval of P ± 3 S , the system accuracy is out of control
and the source of this systematic error should be identified
and resolved before continuing with routine analysis.
At least one spiked sample must be analyzed along with
each set of 20 samples or less that is analyzed at a given time.
This spiked data must be obtained for each parameter of interest.
Record the recovery data of all spiked analyses and periodically
(every 25 to 30 data points) revise, update, and improve the
accuracy criteria.
9.4 System Blank - An orgonics-free-water blank must be analyzed
daily showing no contamination of the analytical system. If
EICP methods are being used to located pollutants, the blank
must also be subjected to the same analysis procedure. Data
collected from blanks may also be used to determine detection
limits based upon the responses of any components present. Cal-
culate detection limits for each component as twice the noise
measured. Typical detection limits are 1 to 2 ppb.
9.5 Field Blanks - A field blank must be analyzed with each set
of samples fron a given source. This is particularly important
since volatile organics samples can potentially be contaminated
due to exposure of organic solvents. The blanks must be ana-
lyzed in the sonic manner as the sample. Field blanks for pur-
geablcs arc sent from the laboratory to the sampling site and
returned as a check on possible contamination of the sample by
permeation of volatilcs through the septum seal.
-------
B-18
When interferences occur, the analytical results must be
discarded unless sufficient data from these blanks is available
to permit correction of the results.
9.6 internal Standards - Measure the areas of the quantitation ions
selected for the internal standards. Record the'measured values
in the GC logbook. Since instrument variations are usually
small within operating day, let the internal standard response
from the calibration standard be X and reference any variation
to X. Check each subsequent measurement and if it is outside
the range of X ± 15%, consider the analysis out of control.
Resolve the problem and reanalyze the sample. As more data
are collected, update the limits periodically.
10.0 Calculations
10.1 If the concentration of standard solutions and internal
standards in aqueous solutions are reported in ppb (parts per
billion), no further calculations are necessary. Dilutions,
when necessary, may be calculated assuming a 10% solution is
one part sample diluted to 10 parts with organic-free water
by:
true cone. = measured cone, x 100
%sol.
11.0 Precision and Accuracy - This section suimnrizes the quality con-
trol for precision, accuracy, recoveries and detection limits.
Thssc data shew that: for the 16 pollutants evaluated:
a. The within^iay precision is ca. ± 107, (ccmpouid dependent).
b. The day-to-day precision is ca. ± 26°. (based on tha second
internal standard response).
-------
B-19
c. The mean average recovery below 50 ppb is 110%.
d. All 16 compounds are detectable at 1 ppb.
11.1 Precision - Insufficient data have been collected to determine
ranges described in section 9.2. However, the data fron 2
Replicate Analyses are reported here:
Name Avg. Diff.. Avg_-. Diff.
benzene 1 2 5-6 °
carbon tetrachlcride ND — ND
chlorobenzene ND — 1.85 0.1
1,2-dichloroethane ND — 1.45 0.1
1,1,1-trichloroethane ND — 4.65 0.7
1,1,2-trichloroethane 2.4 0.2 333 14
1,1,2,2-tetrachloroethane ND — ND
chloroform ND ~ 20 2
1,2-trans-dichloroethene ND — ND
1,2-dichloropropane ' ND — ND
ethyl benzene ND — ND
irethylene chloride (a) — 13-8 I-5
brcroform ND ~ ND
bromo dichlorcpropane ND — ND
toluene ND — 8.75 0.1
trichloroethene ND — 1-45 0.1
a-, R«=licate Analysis contaminated with mcthylene chloride
i i *• • .
Tnasa c^ca she.-/ the luethoJ to l:c reprccluosble to ca. 101
(ccmouna dependant) for analysis pcrfcrmad on tha sanvc day.
Another measure of precision is the analysis of samples collected
-------
B-20
in duplicate at the sampling site. One such sample was ana-
lyzed and the results shown below:
Name Avg. Diff.
benzene 1.4 0
carbontetrachloride ND
chlorobenzene 3.75 0.3
1,2-dichlorcethane 7.6 4.4
1,1,1-trichloroethane ND
1,1,2-trichloroethane 981, 29
1,1,2,2-tetrachloroethane ND
chloroform 1.35 2.7
1,2-trans-dichloroethene ND
1,2-dichloropropane ND
ethylbenzene ND
methylenechloride 3.87 6.06
bromoform ND —
bromochloromethane ND
toluene 1.25 2.5
trichloroethene 1.65 0.5
11.2 Accuracy - The accuracy of the inethcd may be estimated from
the recovery data in section 11.3. Another measure of the
overall inethcd accuracy may be obtained from evaluation of
the measured concentrations for the second internal standard
(brcmochlorancchane)• Since this standard is added to every
sa-Tple at a constant concentration, it provides a reasure of
the accuracy of the results in each sar.plc. Overall, for 90
-------
B-21
determinations, the measured concentration was 199/ ± 51 ppb
(199 ± 26's) for brorochloromathane at 200 ppb added concen-
tration.
11.3 Recovery - The accuracy of the method may be estimated based
on the recoveries obtained from spiking real samples with
known amounts of pollutants. For 5 samples spUced below 50
F?b, the average recoveries and standard deviations are shown
below:
Mare %Recovery
benzene 136 ± 37
carbontetrachloride HO ± 20
chlorobenzene 124 ± 32
1,2-dichloroethane 102 ± 15
1,1,1-trichloroethone 115 ± 19
1,1,2-trichloroethane 93 ± 28
1,1,2,2-tetrachloroethane 112 ±26
chloroform H3 ± 24
1,2-trans-dichloroethene HO ± 26
1,2-dichloropropar.G 104 ± 9.5
ethylbenzene 103 ± 14
methylcne chloride 96 ± 33
brcmoform 91 ± 22
brcrrodichlorcmethane 113 i 24
toluene 142 ± 31
trichlOL-oethcne 10G ± 19
One saiwle spiked at 200 ppb yielded the following recoveries:
-------
B-22
Name %Recovery
benzene3 2^
carbontetrachloride 76
chlorobenzene 107
1,2-dichloroethanea 7 5
1,1,1-trichloroethane 7 8
l,l,2-trichloroethanea 42
1,1,2,2-tetrachloroethane 9 6
chloroform3 H
1,2-trans-dichloroethene 7 9
1,2-dichloropropane 10
ethyl benzene 144
methylene chloride 24
broroform °0
bromodichloromethane 91
toluene ^
tr ichloroethene 8 6
Compounds noted "a" were present in the sample at high con-
centrations and the addition of 200 ppb exceeded the linear
response range.
11.4 Detection Limit - When using automatic data processing pro-
cedures, the detection limit is difficult to define. Since
the first step in data processing is identification of the
spectrum, the detection limit has been defined here as: The
miniitttrr. amount producing on identifiable mass spectrum. Once
the compound is identified, the amount present is measured.
-------
B-23
A reagent water blank was spiked at 1 ppb, analyzed and the
data automatically processed. The results are listed below:
Naire
benzene
carbontetrachlorids
chlorobenzene
1,2-dichloroethane
1, i,l-trichlorcethane
1,1,2-trichloroethane
1,1,2,2-tetrachloroethane
trichloroethane
1,2-trans-dichloroethene
1,2-dichloropropane
ethyl benzene
methylenechloride
brcmoform
bromodichlorcmethane
toluene
trichloroethane
%Recoverv
139
97
148
129
133
120
106
119
132
94
105
176
75
171
114
111
These data show detection of all the compounds spiked at 1 ppb.
During the reduction of sair.ple data, many compounds can be
identified at concentrations as lav as 0.2 ppb. In these
casas, the concentrations ore reported as "MS" indicating a
n-ass spectral identification but the concentration is below
the verified limit of 1 ppb. Cornpounds not detected arc
reported as "ND".
Mcthylene chloride generally shows large variability in
-------
B-24
quantitative results near the detection limit. This is due
to 2 factors, first is its volatility and second is the poten-
tial contamination of samples from the laboratory air. There-
fore the detection limit is defined as 3 times the standard
deviation of blank determinations (16 ppb). The mean back-
ground (2.9 ppb) is subtracted from each value followed by
application of the detection limit.
Toluene elutes coincident with the internal standard
1,4-dichlorobutane. The carbon isotope peak at m/e 91 there-
fore yields a constant toluene background (2.8 ± 1.2 ppb).
The detection limit is then defined as 3 standard deviations
of the background (3.6 ppb). Due to the consistency of the
background, 2.8 is subtracted from each value measured before
applying the 3.6 ppb detection limit.
12.0 References
(1) Memo from James Eichelberger and William Budde to EPA GC/MS
users titled "Perfluorobromobenzene Reference Compound for
use with Typical Purge and Trap Columns that do not Transmit
DFTPP Readily," March 10, 1978.
(2) National Bureau of Standards, EPA-NIH-MSDC Mass Spectral
Library.
(3) "Samples and Analysis Procedures for Screening of Industrial
Effluents for Priority Pollutants," U.S. EPA, Environmental
Monitoring and Support Laboratory - Cincinnati, Oliio, March,
1977 revised April, 1977.
-------
B-25
(4) "The Determination of Volatile Organic Compounds at the ug/1
Level in Water by Gas chroratography." Thoiras A. Bellar and
James J. Lichtcnbsrg, Jour. Am. Water. Warks Assoc., 66_ (12),
739, (1974).
-------
Comoound
TIICHLOKnFLUOROMETHWE OJ8° 35
1,1-DICIILnROETHYLEME 1'20 24
BRO'IOCHLOROMETHANE a °-783 14
1,1-DICHLOROETHANE ]-03 15
TRANS-1.2-DICHLOROETHYLEHE °-762 16
CHLOROFORM °'957 16
1,2-DICHLOROETHANE °'734 15
1,1,1-TRICHLOROETHANE: °'544 2l
CARBON TETRACHLORIDE °-593 1B
BRO'IODICHLOROMETHANE °'992 3'5
1,2-DICHLOROPROPANE °'735 13
TRANS-1.3-DICHLOROPROPENE °'314 15
TRICHLOROETHYLENE °'559 15
DIBRO'IOCHLOROMETHAHE °'464 36
CIS-1.3-DICHLOROPROPEME °-240 10
1,1,2-TRICHLOROETHANE °'429 6'3
BENZENE 1-4°
BRO'IOFORM °'2°°
TETRACHLOROETHYLEUE °'441 ]1
l,4-D!CHLOR03UTANEai) 1>0 N^
1,1,2,2-TETRACHLOROETHAME °'725 5>?
TOLUE..E '-38 '^
CHLOROEEilZENE °'866 7'5
a Internal standards ah/.v/s at 200 ppb.
^ Used as relative response of 1.0.
Sean of a ceter,n',raticns a- 20, 50. 100, and 2CO ppb
-------
B-27
Quality Control Data
Volatile Organics Analysis (Purgeables)
One sample, Station 6, was analyzed in replicate and also spiked. In
the replicate analyses, four components were detected each time (benzene,
chlorobenzene, tetrachloroethene and toluene) with an average deviation
of 8%, with a range of relative percent deviation from 2 to- 14 percent.
Chloroform was detected at 8 ug/1 in one analysis and was ND in the second.
In the spiked sample, all 25 components were detected, with an average
81% recovery.
Table 1
Purgeables-QC Results
Spiked Sample Component
Cone, ug/1 Recovered Percent
Benzene
Carbon tetrachloride
Chlorobenzene
1,2-Dichloroethane
1,1,1-Trichloroethane
1,1-Dichloroethane
1,1,2-Trichloroethane
1,1,2,2-Tetrachloroethane
Chloroethane
Chloroform
1,2-Dichloropropane
1,1-Dichloroethene
cis-1,3-Dichloropropene
Ethyl benzene
Methylene chloride
Methyl chloride
Methyl bromide
Bromoform
Bromodichloroethane
Trichlorof1uoromethane
Dibromochloromethane
Tetrachloroethene
Toluene
Trichloroethane
Vinyl chloride
64
100
192
40
40
100
100
40
300
100
100
100
40
40
100
300
300
40
40
40
100
100
40
100
300
61
73
180
28
15
69
94
50
310
64
69
110
26
2
64
64
220
44
30
100
97
84
28
75
140
95
73
94
70
38
69
94
125
103
64
69
110
65
5
64
21
73
110
75
250
97
84
70
75
47
Average
81%
-------
B-28
Table 1 (Cont.)
Replicate Component Analysis 1 Analysis 2
Benzene 23 ug/1 24
Chlorobenzene 100 84
Chloroform 8 NO
Tetrachloroethene 4 3
Toluene 13 15
-------
B-29
2.0
BASE/NEUTRAL PRIORITY POLLUTANT ANALYSIS BY GLASS CAPILLARY
GAS CHROMATOGRAPHY/MASS SPECTROMEW
NATIONAL ENFORCEMENT INVESTIGATIONS CENTER-JUNE 1979
1°?PVh?s me?ho"is°applicable to the extractable base/neutral priority
pollutant organic". The majority of the base/neutrals can be anal-
1 2 TheVimU o^detecS^for this method is from 5 to 20 ug/1 (ppb)
depending on the type of compound.
1.3 The nominal concentration range is from 5 to 100 ug/1 Jppb). Hign
er concentrations may be handled by dilution prior to analysis.
SnSnJ solvent extracts of aqueous, sediment, or solid samples
are injected into a glass capillary column gas chromatograph dir-
ctly ou fed to a qlladrupole electron-impact mass sped:rometer via
a small diameter heated glass lined stainless steel tube. A split-
ess Injection technique is used. The resultant ^ss spectra are
collected and stored by a computer controlled data system The
identifications are made by automatic computer etching of the
<;amnle soectra and relative retention times with those of standard
pectra from a special stored library of the base/neutral priority
oSllutants Quantitative results are obtained for each compound
uP?lng a response factor for each standard relative to an internal
standard.
3'° SJ^oncentrated solvent extracts can contribute interferences
Common solvent interferences are: diacetone alconol (4-methy -
4°hJdroxJ-2-Sentanone) from acetone and cyclohexene from dichlor-
3.2 (-^"interferences from sodium sulfate are the phthalates.
4'° ^''"several of the base/neutrals are difficult to identify by this
.nethod. Two-Chloroethylvinyl ether, bis(chlorornethy e, e and
3 3-dichlorobenzidine have never been identified using this col
4 2 iSpnorone inS^cScMorocyclopentadiene chromatograph fairly
well but cannot be identified by the computer search on most
occasions at 40 ug/1 (ppb) and obviously higher concentrations
4.3 B^lb'nzyWhal.te is often misulentified as J^utylphtholate
^E?»^^^^
data auditing readily solves this problem.
-------
B-30
4.4 Several of the PAH's are more difficult to identify at lower
levels, but with higher concentrations above 50 ug/1, they should
be readily identified.
5.0- Apparatus • . . ., ...
5.1 Finnigan Model 9500 gas chromatograph equipped with a glass capil-
lary column. - ...
5 1.1 Grob type glass lined injector for splitless injection.
sil'z Capillary glass column, 25 meters X 0.25 mm ID, OV-101.
5.2 Finniaan Model 3200 electron impact mass spectrometer.
5.2.T Glass lined stainless steel tubing direct coupling to GC.
5.3 Finnigan INCOS data system (1). . . .
5.3.1 MSDS software 3.1, 7/1/78, Revision B
6.0 Procedure
6.1 Gas Chromatography
6.1.1 Inject 1 to 2 ul of sample into the gas chromatograph.
with purge valve turned off for 1 min. after injection.
At precisely 1 min. open purge valve (Purge flow 50 ml/min)
6.1.2 The initial column oven temperature is equilibrated at
60°C and held for 1 min. after injection, then a temper-
ature program is initiated at 4°C/min to 22°C. The final
temperature is held until 70 minutes have elapsed. The
column flow is adjusted to give a nominal flow^of 1.5 ml/
min at 100°C. The injector temperature is 250°C.
6.2 Mass Spectrometry.
6.2.1 The following MS instrumental parameters are used:
Electron multiplier voltage - 1800 volts
Lens voltage - 50 volts
Collecter voltage - 35 volts
Extractor energy voltage - 6 volts
Ion Energy voltage . - JO volts
Electron energy voltage - 70 volts
Emission current •• - °-5 ma
6.2.2 The following data acquisition parameters are used:
Scan time - 2 seconds
Mass range - 35_? 350 AMU
Sensitivity - 10 amp.
6.2.3 The data acquisition is initiated immediately upon sample
injection in a suspended mode. At 4" minutes the ionizer is
turned on and at 5 minutes the data collection is begun.
The data acquisition contunues for a total of 70 minutes
from injection then stops. This data handling is automatic-
ally controlled by an in house procedure. (See Appendix I)
624 The quantitation and preservation of the scan number of an
added dln anthracene internal standard are hardcopied for
monitorlHg the integrity of the GC/MS system. Again this
is done utilizing an in house procedure. (See Appendix II)
6.2.5 The data is then processed using an automatic conputerized
search and quantitation procedure. The quantitation is ob-
tained based on the response factors relative to an internal
standard. This procedure is also an in house procedure
-------
B-31
(See Appendix III), utilizing standard operating methods. (1)
7.0 Precision and Accuracy
7.1 Data not available
8'° ' sl^Thf quantitation is done using the nanograms/microliter obtained
from the response factors derived from analysis of a standard mix
of Priority pollutants with an internal standard added. Response
factors Ire calculated based upon the integrated areas of selected
Ions for each component in a standard mix. Appendix IV lists the
ions selected to date. Response factors are calculated as
follows:
Resp. Fact = Areas * REF. AMNT/(REF. AREA * AMNT)
Area = area of component response
Ref Amnt = amount of internal reference standard
Ref Area = area of internal reference standard response
Amm:. = amount of component analyzed in standard.
n=. AREA*. Resp Fact)
8.2 The concentration of the sample component is calculated in ug/1
as follows: .
uq/1 = ng 100% cone, vol in ml „ IQtU
ul * extract vol in liters % soln.
9-° g^^The^ss^pectrometer is tuned and calibrated daily using a per-
fluorotributylamine (FC-43) calibration compound.
9 2 A standard mix containing eight compounds is analyzed on the GC/
MS These compounds give a representative cross section of types
of compounds. The compounds are:
1 1,2-Dichlorobenzene"
2 N-Rethyl aniline
3 2, 6-Dimethyl phenol
4 Napthalene
5 p-Nitrotoluene
6 1,2,4,5-Tetrachlorobenzene
7 Biphenyl
8 Tetradecane
10.0 Reference^ ^ ^^ ^ Operators Manual § Revision 3,» Finnigan
Instruments, March 1973.
-------
B-32
Attachment I
TRRCE QF PROCEDURE BNPPflO
* EROSE.-C PRIORITY POLLUTflNT BflSE-NEUTRRLS DRTfl flCOUISlTION SEUP3
* CT1HE (SEC) PROHPT PCTIQH 3
* C 0 NOME TURN DIvrJTES OFF 3
* C 3B BEEP; BEEP; 2EEP; INJECT Sfl.'PLE 3
* C 90 BEEP; BEEP TUSN DIVERTER OM; STSRT CC PROGRfin3
* C2SO BEEP TUSH OM IONIZER 3
* C3QO NONE RCOUI3TION STARTED 3
* :SCPP;C70 STRRT RUN PRESS C.TJRIRGE PETUSH.]
* COPTER PRESSING MRRIOGE FsTUWI YOU DILL HBVE3
* C30 SECONDS BEFORE YOU 1NJZCT2PRUSE;
* RCOU CI;rilC9;T2;S:G:55:00;E:):;ERnS£:
* C IHJECT SflrPLE IIVEDIflTCLV rtFTER THRD EEEP3
* IHIT-M5;CEEP;C=EP;CEEP;E3M;E;
* CSnKPLE SHOULD HPVE BEEN INJECTED fiT THIS TIKE]
JK CLHEM TJiE TERMIMAL OcEPS PWIN. 3
* CTURH DIVERTER OM PUD STfiRT GC PROCR1.13
» uaiT »45;BEEP;BEEP;ERflSE;
w U31TS47
* CDIVERTER SHOULD 3E OM RND THE GC PROG^RmiNG RT THIS
« CTU3N ON IONIZER fiT THE SOUND Or THE FRNrR3E3;
* SONG(GFF);EPnSE;
* L'aiTi»125;
* CIOMIZER SHOULD BE ON RT THIS TIPE3:
« LWITfl50.-r.COU CS;E);ra?xC CI;VlCEOaO;D15a. I650.530;EJ
IK
EPOSE
SCPP
:K SCnilCKtSS RSNGE LCU 35:hIGH 353;UP 1.35;DO'JN O.CO;HOLD TlrE TOP 0.ea:90TTOM O.CS)
SCBN (rflSS RflNGE LOU 35:H:GK 350:U? I.95.-DOLN O.CO.-HOLD TIME TOP O.BB.-BOTTOri O.CS)
PRU3E
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EPfiSE
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IHIT s47
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LMIT -12'J
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-------
B-33
Attachment II
TRflCE OF PKDCEDuRE BNDOKE
* PfiiJn(I;H;E3;rfiP(!;V2033E3:HI.22Ca.7BQ:E) .
* ;CHRO (I;R:SPP.i:M:tPP. I21:=P°. l2I;HI.2:fl5.3:G-15.15.-H-15. !5:E) ;
*
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TOP (I:V2EaCC0:HI.2009.70Q:E)
ChRO (I;R;5PP,I2l;lPP.12l;"PP.:2l;Nl,2;fl5.3:G-l5.I5;H-15.I5;E)
FEED
BEEP
-------
B-34
Attachment III
*".CPPl5MTY POLuiTflHT EWLUflTIOH PROGRfiM. SEE PRIPOL.DS FOP EXPLPINflTONJ
* ' LR TTEN flPRIL 24.1979 BY O.J.LOGSDON II US EPfi NEIC 303-231-15613
* icREVtSED RPRIL 24.1973 OY O.J.LOGSDON II US EPfl NEIC 303-234-46613
* -SETL 51;SETS S2
* ;EDSL YES (-;1;U;E);EDSL NO (-:U;E)
* ;SETN PR1POL
* :PRIP03
* .-FEED
* ;BEEP;3c£?:E=EP
*
SETL SI
SETS 5Z
EDSL YES (-:1:U:E)
EDSL HO (-:U:E)
SETM PR IPOL
PRIPOO
* GETH:PRIPCI;LOOP
K
GETN
PR IPO I
* jSETO SI.-EDGL C-;U:E):SETL «0;SET1 *1
* ;FILE CK PRIN.99'H;E>
* ;PfiRfl (I:H:E);CHPO (I;HI.20aB;400:E)
IK ;PRIP06;SETL oQjSETiO M4:PR1P02
* ;EDLL tB'l;E):PRIN (OP1):FILE CC PRIN.99.n:xN:E)
* ';FEED
* ;QUfiN CI:H;E)
* ;FEED;BEEP
*
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EDOL (-;U;E3
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FILE (K PRIN.99/N:E)
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CKRO (I:H1.2aQa:4Q3:E)
PR IPOS
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* ;SE«/V (I;S.t;V2t,e230:N2.1Q.5CO;D-2S.25;E)
* ;F3!?07
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* ;E=EP.G:EP.t.E=P:CEEP;E::EP:3EEP:BEEP;BEEP
* ;PETU P3IP01
*
I? P.G.C.E)
-------
B-35
* .-FRIF03
* ;LOOP
*
SET1 MB
SET 14
S!RR (i.s-s:V2SeaM-HI.IB.10;D-2B.20:E)/V
PRIM c-4.2:'14.6. ".5.G:'I6.6;C:E>1CX
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* FRIT04
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IF PRIP05':r.PSIP05
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PRIM <6PD
FILE
-------
B-37
Quality Control Data
Base-neutral Extractables
Two samples were spiked with nine priority pollutants at 133 ug/1,
extracted and analyzed. The same samples were analyzed in duplicate
as well. The average recovery was 78 percent. The low recovery reflects
the problems of water-solvent emulsions which required centrifugation
to separate.
Duplicates data were minimal, with only five compounds showing results
above the detection limits in the original samples.
Table 1
Base-neutral Extractables-QC Results
Spiked Samples
Sample 06 Sample 07
Component Cone, ug/1 Recovered Percent Cone. Recovery' Percent
p-Dichlorobenzene 840 180 21% 133 140 105%
Isophorone 133 210 160 133 100 75
1,2,4-Trichlorobenzene 173 160 92 146 84 58
2-Chloronaphthalene 133 99 74 133 97 73
Acenaphthalene 133 98 73 133 102 77
Dinitroluene 133 140 105 133 103 77
Anthracene 133 79 59 133 100 75
Di-n-butyl phthalate 133 67 50 133 95 72
Pyrene 133 125 94 133 83 62
Averages 81% 75%
Duplicate Samples
Sample 06
Component Analysis 1 Analysis 2
p-Dichlorobenzene 710 ug/1 1000
1,2,4-lrichlorobenzene 40 160
o-Dichlorobenzene 160 590
Sample 07
1,2,4-Trichlorobenzene 13 2
phthalrts 38 5
-------
B-38
ADJUSTED pH EXTRACTION TECHNIQUE
FOR ORGANICS ANALYSIS
NATIONAL ENFORCEMENT INVESTIGATIONS CENTER-JANUARY 1979
1.0 Scope and Application
1.1 This procedure is applicable to the analysis of water and
wastewater samples for a broad spectrum of organic pol-
lutants. The primary use is to extract Priority
Pollutants (1) for analysis by GC-MS.
2.0 Summary of Method
2.1 Water and wastewater samples are extracted with CH2C12
(dichloromethane) at a basic pH to extract neutrals and
bases and then at an acidic pH to extract phenols. The
extracts are dried and filtered by passing over anhydrous
N32S04 and concentrated to 5-10 ml in a Kuderna-Danish
(KD) apparatus, then finally concentrated to 1.0 ml in
a graduated centrifuge tube under a gentle stream of
purified air.
2.2 The concentrated extracts are sealed in 1 ml serum vials
and stored in a refrigerator until analysis.
3.0 Sample Handling and Preservation
3.1 Prior to extraction, samples are refrigerated and ex-
tracted as soon as possible, generally within 48 hours.
Samples may be held 5 days or more if necessary.
4.0 Interferences and Detection Limits
4.1 The detection limits must be 10 ug/1 or less. (2)
Concentration of a sample containing 10 ug/1 of a com-
ponent to 1.0 ml yields an extract concentration of
10 ng/ul.
4.2 In some samples, industrial wastes, in particular, the
concentration of some components may be so great that
dilution is necessary for analysis on glass capillary
GC.
In most cases, however, the extreme sensitivity of
glass capillary GC will allow dilution by a factor of
10 without lowering the detection limit below 10 ug/1.
-------
B-39
5.0 Apparatus
5 1 Separately funnels: 2 1 glass with teflon or glass stoppers
and stopcocks. No stopcock grease is used.
5.2 Drying column: .Ml glass 3 cm diameter by 50 cm with attached
250 ml reservoir.
5 3 Concentrator: 250 ml Kuderna-Danish (KD) evaporative
concentrator equipped with a 5 or 10 ml receiver amphu.e
and a 3 ball Snyder column.
5.4 Centrifuge tubes: 12 ml glass tubes graduated in 0.1 ml
marks.
5.5 Graduate: 1 1 glass graduated cylinder.
5.6 Vials: 1 ml with teflon-coated septum sealing caps.
6.0 Reagents
6 1 Extraction solvent: Pesticide analysis grade CH^Clo
(dichloromethane). Burdick and Jackson, distilled tn
glass, or equivalent.
6 2 Dilution solvent: Pesticide analysis grade acetone, Bur-
dick and Jackson, distilled in glass or equivalent.
6 3 Drying agent: Analytical reagent grade granular anhydrous
SS (sodium sulfate), rinsed with CH2C12 immediately
before use.
' 6.4 Glass wool that has been extracted with CH2Cl2-
6.5 6N MaOH for pH adjustment.
6.6 6N HC1 for pH adjustment.
6.7 pll paper for pH measurement.
6.8 Purified air: Compressed air filtered through activialed
charcoal.
7.0 Procedure
7.1 Thoroucjhly mix the sample and measure J"^,^ ""P1"
with a graduate. Transfer the sample to a 2 1 separato.y
funnel -
-------
B-40
7.2 Measure and record the initial sample pH.
7.3 Base-Neutral Fraction
7.3.1 Adjust the pH with 6N NaOH to 11 or greater and
record the value.
732 Serially extract with 3 successive portions of
100, 50 and 50 ml of CH2C12. Shake each extract
at least 2 minutes.
7.3.3 If emulsions form, use a wire or stirring rod to
break it up, pass the emulsion through glass wool,
or centrifuge if necessary.
734 Measure the volume of solvent recovered (graduations
on a beaker are adequate) and record. More than
85 percent recovery constitutes a satisfactory
extraction.
7 3.5 Place a glass wool plug in a drying column and add
ca 10 cm of Na?S04 with at least 50 ml of CH2C12-
Pour the combined extract through the column. Follow
with 100 ml of acetone. Collect the O^Clg and
acetone and transfer to a KD assembly.
736 Concentrate on a hot water bath at 80-90°C until
the extract almost stops boiling. Quantitatively
transfer the receiving tube contents to a graduated
centrifuge tube. Concentrate the extract to 1.0 ml
by blowing a gentle stream of purified air over the
surface of the solvent. Transfer the concentrate
to a 1 ml vial and cap. Mark the liquid level and
label with the sample number, fraction identifier
(B for base neutrals and A for acids), your initials
and the date.
7.4 Acids Fraction
7.4.1 Adjust the pH of the aqueous layer with 6N HC1 to
2 or less and record the result.
7.4.2 Proceed witn the extraction as in 7.3.2.
7.5 Analysis Preparation
751 If the sample is being analyzed by capillary GC,
typically dilute an aliquot 1:5 (2Q% solution) in
acetone.
-------
B-41
7.5.2 If CH2Cl2 solvent is a problem during the analysis,
exchanae the extract into acetone. Add 2 ml of
acetone to the extract in a centrifuge tube and
concentrate to 1.0 ml with a gentle stream of
purified air.
8.0 Quality Control
8.1 With each batch of samples, the following quality control
c^c'^s must be performed. Two of each type check is to
bt dL-.ie for the first 20 samples with one of each check
done on each additional 20 samples.
8.1.1 Reagent Blank: Extract 1 1 of organics free water
using the same procedure as for samples. These
should be done randomly with samples to check for
contamination of various reagents, etc.
8.1.2 Duplicate Extraction: Select a sample, split it
and extract both aliquots. Carry each extract
through the entire analytical scheme. Determine
the relative percent differences for each component.
8.1.3 Spike: If a number of pollutants are suspected,
prepare a spike by splitting the sample and adding
known amounts of the pollutants to one aliquot
and extract both aliquots. Carry each extract
through the entire analytical scheme and determine
the percent recoveries for each compound added.
If no specific pollutants are suspected, spike
with the standard mix described in Reference 3.
8.2 If reference samples (external audit samples) are avail-
able that are applicable to the project, analyze one sample
during the project.
9.0 Calculations
9.1 Solvent recovery:
% Recovery = volume recovered (ml)^'IOO
volume added (ml)
9.2 Pollutant recovery (spiked samples):
% recovery = (concentration measured - initial concentration) mu
concentration added
9.3 Relative percent difference (RPD):
RPD = HI - D? *100
'(Ui + U2)/2
Where D] = first sample value
D2 = second sample value (duplicate)
-------
B-42
Table I. Recovery Data Obtained from Analysis of Spiked Tap Water.
Mean3 Std. Dev. % Std.a
Phenol
Hexachl oroethane-Ni trobenzene
Isophorone
1,2,4-Trichlorobenzene
Naphthalene
Hexachlorobutadiene
Hexachl orocycl opentadi ene
2-Chloronaphthalene
Acenaphthalene
Dimethyl Phthalate
Acenaphthene
2.4-Dinitrotoluene
Fluorene
Di ethyl Phthalate .
n-Nitrosodiphenylamine (Diphenylamine)
4-Bromodiphenyl ether
Hexachl orobenzene
Phenanthrene
Anthracene
Di-N-Butyl Phthalate
Fluoranthene
Pyrene
Butyl benzyl Phthalate
A \i o v» a no
56 7b
+J\J 9 I
43.0
58.8
55.0
46.5.
11 -i"
31.7
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63.8
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76.2
75.8
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75.5
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9.4
a Based on 4 samples
b Based on 3 samples
-------
B-43
10.0 Precision and Accuracy
10 1 Precision and accuracy vary with the pollutants measured.
' Table I shows data obtained from the analysis of 4 tap
water samples spiked with the listec :ollutants at 100 ug/1.
11.0 References
(1) NRDC v. Train, 8, E.R.C. 2120 (1976).
(2) "Sampling and Analysis Procedures for Screening of
Industrial Effluents for Priority Pollutants", U.S. EPA,
EMSL-Cincinnati, March, 1977, revised April, 1977.
(3) Organics Analytical Quality Control Manual, EPA-NEIC,
February, 1979.
-------
B-44
Quality Control Data
Base-neutral Extractables
Two samples were spiked with nine priority pollutants at 133 ug/1,
extracted and analyzed. The same samples were analyzed in duplicate
as well. The average recovery was 78 percent. The low recovery reflects
the problems of water-solvent emulsions which required centrifugation
to separate.
Duplicates data were minimal, with only five compounds showing results
above the detection limits in the original samples.
Table 1
Base-neutral Extractables-QC Results
Spiked Samples
Sample 06 Sample 07
Component Cone, ug/1 Recovered Percent Cone. Recovery' Percent
p-Dichlorobenzene 840 180 21% 133 140 105%
Isophorone 133 210 160 133 100 75
1,2,4-Trichlorobenzene 173 160 92 146 84 58
2-Chloronaphthalene 133 99 74 133 97 73
Acenaphthalene 133 98 73 133 102 77
Dinitroluene 133 140 105 133 103 77
Anthracene 133 79 59 133 100 75
Di-n-butyl phthalate 133 67 50 133 95 72
Pyrene 133 125 94 133 83 62
Averages 81% 75%
Duplicate Samples
Sample 06
Component Analysis 1 Analysis 2
p-Dichlorobenzene 710 ug/1 1000
1,2,4-Trichlorobenzene 40 160
o-Dichlorobenzene 160 590
Sample 07
1,2,4-Trichlorobenzene 13 2
Di-n-butyl phthalate 38 5
-------
Quality Control Data
Acid Extractables
B-45
The same two samples spiked for base-neutrals weirr. also spiked and
analyzed in duplicate for phenolics. The ~p'ke concentrations were
between 21 and 79 ug/1 for the eleven componci.1.1:. The average recovery
was 73%.
Five components were detected in sample 06, and one component in sample
07. The average deviation was 25%.
Table 2
Acid Extractables-QC Results
Spiked Samples
Component
Sample 06
Cone, ug/1 Recovered Percent
2,4,6-Trichlorophenol 54
4-Chloro-3-methylphenol 71
2-Chlorophenol 69
2,4-Dichlorophenol 115
2,4-Dimethylphenol 43
2-Nitrophenol 70
4-Nitrophenol 21
2,4-Dinitrophenol 55
4,6-Dinitro-o-cresol 48
Pentachlorophenol 63
Phenol 71
Averages
31
19
29
5
13
26
15
43
30
17
22
43%
57%
27
47
4
30
37
72
78
63
27
31
Cone.
54
56
62
58
40
70
21
55
48
46
79
Sample 07
Recovered Percent
57
-51
57
50
26
51
28
86
79
51
46
103%
105
91
92
86
65
73
133
156
164
111
58
Duplicate Samples
Sample 06
Component
4-Chloro-3-methylphenol
2-Chlorophenol
2,4-Dichlorophenol
2,4-DiiW£tl>ibO phenol
Pentachlorophenol
Sample 07
Phenol
Analysis 1
14 ug/1
6
49
2
28
10
Analysis 2
16
7
65
3
5
-------
B-46
COMPUTER ASSISTED EVALUATION OF
ORGANIC PRIORITY POLLUTANT GC/MSTATA
NATIONAL ENFORCEMENT INVESTIGATIONS CENTER-JUNE 1979
1.0 Introduction
11 This procedure is applicable to GC/MS data collected under constant
analytical conditions for the organic priority pollutant defined
in "Sampling and Analysis Procedures for Screening of Industrial
Effluents for Priority Pollutants". (1) By developing appropriate
libraries, data for any groups of selected organic pollutants can
be evaluated.
2.0 Summary of Method
2 1 GC/MS data files are processed by location of an internal standard
that is used for response and retention time reference. Components
of interest are then located by reverse searching from library
spectra If a compound is located and the match is sufficient, it
is quantitated and its spectrum optionally printed. The concen-
trations are then calculated from each component found using a
relative response quantitation technique. Printed reports of both
quantitative and qualitative results are available.
3.0 Definitions and Comments
3 1 Unlike the 3 ion and retention time compound identification tech-
nique described for priority pollutant analysis in reference 1,
this procedure allows the user to audit each identification where
the spectra are printed. Thus, each identification is unambiquous
and marginal data may be eliminated.
4.0 Interferences
4 1 In some cases, a spectrum may match the library reference sufficently
to be passed. During quantitation, however, the ion of interest may
be too weak to locate and no entry will be made in the quantitation
list. In such a case, no entry at all (e.g. no "not found entry)
will appear in the quantitation report. The name and match results
will, however, appear in the qualitative data report.
4 2 Occasionally, multiple peaks will be detected during quantitation
due to background interferences and multiple entries will be made
in the quantitation list. Generally, the entry having the same
label as the correct spectrum is used for quantitation and the
others arc disregarded. In some instances, however, the correct
selection is not obvious and manual evaluation of the quantitation
results must be done.
-------
B-47
4 3 When isomers of a chemical elute too close to one another, the
system may misassign them. Manual evaluation then is usually
required to properly identify the isomers.
5.0 Apparatus
5.1 Finnigan INCOS data system software, Revision 3.1 or later. To
initially set up this procedure, the user must understand and be
proficient in the use of MSDS. (2)
6.0 Procedure
6.1 Procedure Set Up
6 1 1 Load the procedures listed in Appendix I into the system
disc or create the procedures from the trace of PRIPOL in
Appendix II.
6.2 Library Set Up
6.2.1 Build a user library containing spectra of interest. Each
entry should have relative retention time (RRT) data,
response factor (RF) data and a reference peak for RRT and
RF references. Appendix III is a typical library. The
library should include the internal standard (S).
622 Create library lists on the system disc with entries that
reference the desired library entries. The first entry of
the library list must be an internal standard. Appendix
IV shows three library lists used for selected priority
pollutants
6.2.3.1 If the RRT and RF data initially entered in the library
was about correct, evaluate data from a standard mix.
Edit the resulting quantisation list and manually add
any entries not identified.
6232 If no RRT and RF data were initially available, manually
locate and quantitate the components of interest including
the internal standard. Write each quantitation result
into a quanlist and edit the list to include the peak
references.
6.2.4 Using "QUAN", update the response factors (R), retention
times (T) and relative retention times (S). Using the QUAN
commands F3 and H, print out the updated list and response
factors, retention times and relative retention times.
6.3 Routine Use
6.3.1 Analyze samples, standards and quality control samples using
the same instrument conditions used to set up the libraries.
-------
B-48
632 Using the name!1st editor, create a name list "PRIPOL"
containing the names of the data files to be processed.
6.3.3 Execute the procedure as follows:
PRIPOL library list, yes (no)
Where: Library list is the appropriate user library list
name.
Yes (no) selects printout of the spectra at a peak
that was identified by the procedure.
634 Appendix V is an example of PRIPOL output using a library
list containing one internal standard and one component.
The "yes" option was selected.
7.0 Quality Control
7 1 Each identification can be manually audited if the "yes" option
was selected. Inaccurate qualitative results may then be checked
and manually corrected.
7 2 Quantitation data accuracy is monitored by use of standard quality
control techniques such as daily standardization, replicate analysis
and sp kes (3) Daily calibration of the method can be accommodatec
by analyzing the standard data first, updating the relative response
factors, obtaining hard copy of the new factors and then analyzing
sample data.
8.0 Precision and Accuracy
8.1 The overall precision and accuracy is limited to the quality of the
raw data being processed.
9.0 References
m "Sampling and Analysis Procedures for Screening of Industrial
Effluents for Priority Pollutants", U.S. EPA, Environmental Monitoring
and Support Laboratory, Cincinnati, Ohio, March 1977, Revised
April 1977.
(2) "INCOS Data System - MSDS Operators Manual - Revision 3", Finnigan
Instruments, March 1978.
(3) "Quality Assurance Program for the Analyses of Chemical Constituents
in Environmental Samples", U.S. EPA, Environmental Monitoring and
Support Laboratory, Cincinnati, Ohio, March 1978.
(4) "Organic Pollutant Analysis Quality Assurance and Document Control
Procedures", U.S. EPA, NEIC, Denver, Colorado, Revision 1, April 1979.
-------
B-49
Attachment I
PROCEDURES NEEDED TO RUN PRIPOL
PR IPOL
PR IPOS
PR IPO 1
PR IPO?
PRIP03
PRIFC4
PR IPOS
PR IPOS
FRIP07
METHODS NEEDED TO RUN PRIKJL
PRINP1
PRIHP2
-------
B-50
Attachment I la
TRflCE OF P°OCEDU'E PR I POL „„„„„„ t
HE.C 3.3-23^66.1
* Y I BY O.J.LOCSDOH II US EPft NEIC 3B3-234-4661 1
* ;SETL SI .-SETS S2.-SETQ TEM?
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* ;SETN PRIPOL
IK ;PR!P03
* ;FEED
* ;SEEP:S=£?:S=cP
*
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EDSL YES C-;1;U;E>
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SETM PRIPOL
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* GETH;PRIPOI:LOOP
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* ;EDOL SI (-jU.-E).-SETL s8:SETI
* .-FILE
BEEP
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srn.
SETHI '!•:
PRIP02
CCT1 'IU
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(1:5. ::v::OCOC.MI. 10. 10:0-10. \0ir.)
. i'4. '.". l.j '."3.6: ' lu.b.C C)
-------
B-51
Attachment lib
* JPR1P03
* ;LOOP
*
SET1 I IB
SET 14
SEflR CI;SJK:V2D03?P;NI.1B.18;D-!B.10:E)/V
PR IN <14.2jll4.6;MS.6sll6.6:C:E)/KX
PR IPOS
* PRIPG-1
* :EDOL SI (-;N;J>:fl:E>
*
PRIP04
* IF PHIPOJ M6.PRIP04 *50a
* ;SETl !14
w ;EDOL C-.-U.t)
* ;CHRO (l;R.S:0;N1.2:n>5.3;G-4.4:D-5.5:E)
* -fDQL TEI1P.S1 CU*20. 10B;fl,E)
* ;PRIPG5
* ,-RETU PPIP03
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IF PRIP04I I6.PRIPO<»*50B
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EDDL TEMP,SI (Dfc2a,100;fi:E)
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* IF PRIP35 I27.PRIP05
* ;LIER t!:C:DS;HS;E)
*
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PRIM (OP1)
FILE (C PRIN.99.M:'N:E)
FEED
OUmi 51 (I;F2:H;E)
FEED
BEEP
LOO?
FCCD
BCD'
BECP
DECP
-------
B-52
Attachment He
_„...„ .e -„ - PR1G
-------
Attachment III
B-S3
Nfitl HUM: Nflr=
trr FOSr,ULfl
RET TIME EftSE
flREfl U.P.«1 U.P.»2
PR 1: 01 flCENfiPHTHENE
154 C12.H10
0.706 154.808 43. OB
PP 2: 02 flCROLEIN
56 C3.K4.0
O.C30 0.333133.23
PP 3: 03 flCRYLONlTRILE
53 C3.H3.M
O.SE3 53.B3aiE3.Ca
PP 4: 04 BENZENE
78 CG.H6
B.65Q 78.C301S3.33
PP 5: 05 8EN2IDINE
184 C12.H1Z.N2
1.345 184.030 2Q.C0
PP 6: 06 CflRBONTETRfiCHLORIDE
152 C CL4
8.493 ii7.ooai3D.ea
PP 7: 07 CHLOROaENZEME
112 C6.H5.CL
1.103 ii2.oa0ieo.oa
PP 8: 08 l^^-TRICHLOROBD'ZENE
100 C6.H3.CL3
0.385 74.003 40.03
PP 9: 09 HEXflCHLOROEEHZCHE
282 C6.CL6
0.924 284.000 ^3.03
pp 10: 10 1.2-DIOILOROETHAIIE
98 C2.H4.CL2
0.414
62.000130.00
PP 11: 11 1.1.1-IRlCHLOPOETUflllE
132 C2.H3 CL3
U.'t73
97.C30i33.00
PP 12: 12 IIEXnCMLOROCTIinilE
234 C2.CLG
0.203 U7.unO -O.CO
PP is- 13 i.i-DiciiLOPOCTiir,r;r
90 C2.H1.CL2
0.300 63. 000123. CO
pp 1.1 |.i |.|.2-TPICIIl.OfOCn'fl:iE
I32 C2.HJ.tL3
u.rc4 gr. oo.) i JO. oo
pp |5 13 I 1.2.2-TETPnCIILO"GSThnilE
ICG C2.H2.CL-i
O.'JCO
B3.(!0')IJJ.C3
FP IS- 1C CIILOrOCIH.l'.E
GJ C2.Hb CL
O.OG4 G4.UJUbL"J.CO
pp 17- 17 OlOCCHLUPOMETiril.)
|M 1.2 HJ.O Cl 3
1:26
PP
0:C8
B:C3
PP
2:12
PP
5:E8
PP
1:43
PP
3:45
PP
11:42
PP
18:04
PP
1:24
PP
I: r6
PP
PP
1:01
PP
2:23
HP
IE
3.19
PP
0. 1.
PP
0-CO
154
121
0
122
122
184
121
117
122
122
180
121
121
122
97
122
201
121
122
122
03
122
:22
79
B.
:S
e.
0.
vs
0.
vs
0.
:S
0.
VS
e.
vs
0.
:S
0.
:S
0.
VS
0.
VS
0.
:S
0.
VS
0.
VS
0.
VS
0.
vs
0.
0.003
e.812
0.003
i.asa
0.G30
0.125
B.COB
4.023
0.080
0.047
0.000
2.979
0.009
2.499
0.000
0.884
0.000
0.338
0.033
1.234
0.003
3.100
O.OCO
0.113
0.003
2.792
0.000
0.655
0.003
0.731
0.033
1.036
r mo
0.093
a.aao
0.000
0.080
0.000
0.000
0.0B8
B.000
0.030
B.COB
B.OQO
0.000
0.000
0.000
0.030
0.003
0. 3^0
-------
B-54
Attachment IV
Nfifl NUn: UT FORttULfl
PP 121: 188
pp 1: 154 C12.H10
PP 8: IBB C5.H3.CL3
PP 9: 282 CS.CL6
PP 12: 234 C2.CL6
PP 18: 142 C4.H8.0.CL2
PP 20: 162 C10.H7.CL
PP 25: 146 C6.H4 CL2
PP 26: 146 CS.H4.CL2
PP 27: 145 CS.H4.CL2
PP 23: 252 C12.HI9.N2.CL2
PP 36: 182 C7.H6.34.N2
PP 37: 182 C7.K6.04.N2
PP 38: 102 CI2.H10.H2
PP 40: 202 C16.H10
PP 41: 204 C12.H9.0.CL
PP 42: 248 C12.H9.0.3R
PP 43: 170 CS.412.0.CL2
PP 44: 172 C5.H10.02.CL2
PP 53: 258 C4.CL6
PP 54: 270 C5.CL5
PP 55: 138 C9.H14.0
PP 56: 128 Cia.HS
PP 57: 123 C6.H5.02.N
PP 63: 169 C12.H11.N
PP 64: 130 C6.HI4.0.N2
PP 67: 390 C24.H38.04
PP 68: 312 C18.H2EJ.0-i
PP 69: 278 C16.H22.04
PP 70: 390 C24.H33.04
PP 71: 222 C12.H14.04
PP 72: 194 CiO.H10.04
PP 73: 228 C1B.1H2
PP 75: 252 C20.H12
PP 76: 252 C20.H12
PP 77: 223 C13.H12
PP 78: 152 C12.H3
PP 79: 173 C14.H10
PP SI: 16G C13.H10
PP 82: 17C C14.H1U
PP 05: 202 C1S.H10
NflKE
DIS-qNTHRflCENE CINTERNflL STftNDfiRD)
Bl flCENflPHTHENE
08 1.2,4-TRICHLOROBENZENE
69 HEXflCHLOROBENZENE
12 HEXSCHLOROETHflNE
18 B!SC2-CKLOROETHYt.)ETHER
28 2-CHLORONSPHTHflLENE
25 I^-DICHLCKOSENZENE
26 1.3-DICHLC^OeEKZENE
27 1.4-D1CHLORGHENZENE
28 S.J'-DICHLCROBNEZIDINE
35 2.4-DINITSOTOLUESE
36 2.6-DINITROTOLUENE
37 1.2-DIPHENYLHYDRflZINE (PIEflS. flS RZ09
39 FLUC'flNTKENE
40 4-CHLOROPHENYL PHENYL ETHER
41 4-BROMOPHENYL PHEHYL E'lHER
42 B1SC2-CHLOROISOPROPYUETHER
43 81St2-CHLOROEThOXY)r£THflNE
52 HEXflCKLOROoUTflDIENE
53 HEXflCHLOROCYCLOPENTflDIENE
54 1SOPHOROME
55 NflPHTHBLENE
56 NITROBENZENE
62 N-NITROSODIPHEMYLflniNE (MEflS AS DIPH
63 N-NITROSODIPiCOPYLfirilllE
66 Dl-(2-ETHYLHEXYL)PHTHqLf»TE
67 BUTrL BENZYL PHTHflLflTE
68 DI-N-BUTYLPHTHflLftTE
69 DI-OCTYLPHTHRLrtTE
70 DIETHYLPHTHflLRTE
71 DIMETHYLPHTHflLflTE
72 BENZO(fl)fiNTHRflCENE
74 3.4-BEHZOFLbORflNTHEHE
75 BENZONKNFLUORflNTHENE
76 CHRYSEIIE
77 flCEMBPHTHYLENE
73 flNTHRflCEPE
80 FLUC^EME
81 PHEi-HNTKRENE
84 PYKEHE
-------
Attachment Va
B-5G
OUariTlTflTIOM REPORT
FILi: VSM135I4
DflTfl: VSM13S14.MI
8:68:89
SflttPLE: VOfl STD MIX R 13 MflY 31. 1973
SUBMITTED BY:
BrtJUNT-flREfl * REF.fiKNT/CREF.flSEIV' RESP.FRCT)
UEIGHT:
flCCT. NO.:
B.BBB
1 ~|.4-DICHLC'U)aUTf^
2 BRoracfLO!?orFTHro
3 14 BENiEI'E
4 06 CfiRBOMTcTRflCHLOR
5 07 CHLOR06ENZEME
6 10 1.2-DICHLORuETHfll
7 11 1.I.I-TRICHI.OROE
Q 13 . l-DICHLOROEIHfl
9 14 . 1,2-TRlCHLORQE
10 15 . 1.2.2-TETRflCHL
11 16 CHLOROETHftNE
12 23 CHLOROFORM
13 29 ,1-DICHLOROETHE
14 30 ,2-TRfiNS-DICHLO
15 32 ,2-DICHLOROPSO?
16 33fi CIS-1.3-DICHLORO
17 38 ETUYLCEIIZEi'c
18 44 METHYLEHsCHLORID
13 45 METHYL CHLORIDE
2B 46 METHYL BROMIDE
21 47 BROilOFORM
22 -IB BROMODICHLOROI1ET
23 49 TRICHLCROFLUOROn
24 51 DIEROMOCI'LOROIIET
25 85 TETRflCHLOROETHEh
26 06 TOLUEME
27 87 TR1CHLOROETIIEHE
2B 08 VIHYLCHLORIDE
HO n/E SCOH TII'E RE
1 55 203 3:23
2 49 55 0-53
3 78 132 2:12
4 117 100 1:40
5 112 225 3:<13
6 62 04 1:24
7 97 06 1:-G
Q 63 Gl I.HI
g 97 143 2.23
10 03 100 3 10
11 G-> 13 0:13
12 03 70 1:10
13 9G 67 1.07
|.l Gl C7 1:07
15 GJ 12.1 2 03
IS 75 111 2.^2
K (INTESMPL STRNDflRD)
4E (IHTERNFL STANDSRD)
IDE
IE
OlnliE
-------
3-56
Attachment Vb
NO
18
19
2B
21
22
23
24
25
25
27
28
NO
1
2
3
4
5
6
7
8
9
IB
11
12
13
14
IS
16
17
18
19
20
21
22
23
24
25
26
27
20
n/E SCR
84 2
SB
94
173 1?
83 11
131 3
129 14
129 19
91 20
133 13
62
REKL) R
3:23
8:55
2:12
1:40
3:45
1:24
1:36
1:01
2:23
3:19
0:13
1:18
1:07
1:07
2:03
2:22
4:19
0:25
0:05
0:07
2:53
1:51
0:33
2:23
3:15
3:23
2:12
0:09
1 T
5 B
5 B
7 B
3 2
1 1
9 B
3 2
5 3
3 3
2 2
9 0
fiTIO
.00
.no
.00
.00
.00
.oa
.00
.BB
.00
.oa
.00
.00
.00
.03
.00
.00
.03
.00
.00
.00
.03
.00
.(13
.00
.00
.00
.C9
.03
IMS REF
:25 1
:05 1
:07
-.53
:51
:39
:23
:I5
:23
:12
:09
RPTCL) R
1.003
0.271
0.650
0.493
1.103
B.414
B.473
0.303
8. 704
0.983
0.064
0.334
0.330
0.33D
0.606
0.700
1.276
0.123
0.025
0.034
0.852
0.547
0. 192
B.70«!
0.9G1
1.009
0 . b'-JU
0.04-1
RRT
0.123
B.B25
0.034
8.8=2
0.5J7
0.152
0.7-J4
0.951
1.0C3
0.6=:)
0.044
fiTIO
.00
.CO
.DO
.CO
.oe
.00
.00
.30
.00
.00
.00
.33
.00
.30
.Oil
.BQ
.33
.00
.00
.00
.03
.on
.O'J
.23
.3'J
.0.;
.01)
.00
A S3
A 83
A 83
A B9
A 83
A S3
A 83
A 53
ft 83
A 83
A 89
AfiNT
233.30
230.00
1 33. 00
103.00
103.80
130. 0B
IGC.00
103.03
100.00
1C0.03
sea. 00
103. BB
133.00
ICO. 00
100.00
leu.ea
ICC. 00
ICO. 00
583.00
590.00
109.00
133.03
100.03
103.00
ICS.00
103.03
1CL.CO
530.03
ARE4
221323.
288968.
5879S3.
57385.
2239S2.
151830.
128233.
122226.
316731.
I2423J.
56423B.
AMMTCL)
203.00
203. BB
100.30
103.00
100.03
1EO.B0
109.00
103.60
100.03
100.00
580.00
100.33
100.03
103.80
100.00
1B0.00
100.80
100.00
500.00
500.00
100.00
130.00
100.30
100.00
103.00
130.09
100.03
509. CO
AWJUNT
lea.eea UG/L
503.800 UG/L
5B8.0B9 UG/L
IBB. BOB UG/L
IBB. 090 UG/L
1CB.BOB UG/L
180.803 UG/L
100.030 UG/L
103.308 UG/L
• 100.000 UG/L
500.000 UG/L
R.FPC R.FACCL) RA
1.059 1.033
1.687 1.687
4.023 4.023
2.979 2.979
2.499 2.499
1.234 1.234
3.100 3.100
2.792 2.792
8.695 B.695
B.731 8.731
1.036 1.836
5.0S9 5.089
8.938 8.939
1.962 1.962
1.899 1.899
8.685 B.635
4.484 4.484
2.655 2.655
0.694 0.694
1.413 1.413
B.6E6 B.686
2. 668 2.689
.823 1.S23
.444 1.444
.4£8 1.468
3.954 3. £04
.452 1 . -'92
.356 l.:56
2TOT
2.17
10.87
IB. 87
2.17
2.17
2.17
2.17
2.17
2.17
2.17
10.87
TIO
.G3
.00
.00
.00
.08
.BB
.BQ
.80
.03
.00
.00
.80
.OB
.03
.03
.00
.00
.00
.00
.00
.00
.00
.00
.33
.00
.Oi]
.CO
.03
-------
B-57
Attachment Vc
Nfin NUM: UT FGRITJLa
PP 122:
PP 123:
PP 4:
PP 6:
PP 7:
PP 10:
PP 11:
PP 13:
PP 14:
PP 15:
PP 16:
PP 23:
PP 29:
PP 33:
PP 32:
PP 33:
PP 39-
PP 45:
PP 46:
pp 47:
PP 48:
PP 49:
PP SO:
PP 52:
PP 85:
PP 87:
PP 88:
PP 89:
B/3tJ/G0
NO SCflN
*1 203
*l 55
4 132
6 100
7 22b
10 04
11 95
13 61
14 M3
IS 199
16 13
23 78
29 G7
20 M
32 123
33 M2
33 259
45 25
<16 5
47 7
48 ITS
49 III
S3 3'J
52 K3
CG I?S
07 ZJj
co 1:2
C9 3
12S C4.H9.CL2
128 C.H2.CL.BR
78 C6.HS
152 C.CL4
112 CS.H5.CL
98 C2.H4.CL2
132 C2.H3.CL3
98 C2.H4.CL?
132 C2.H3.CL3
16S C2.H2.CL4
6J C2.H5.CL
US C.H.CL3
95 C2.h2.CL2
96 C2.H2.CL2
112 C3.H6.CL2
110 C3.H4.CL2
106 C8.HIO
84 C.H2.CL2
50 C.H3.CL
54 C.H3.BR
250 C.H.BR3
162 C.H.CL2.BR
136 C.CL3.F
286 C.H.CL.BR2
164 C2.CL4
92 C7.H3
130 C2.H.CL3
62 C2.H3.CL
B:00:G0 IDENTIFICaTIQM
PUniTY FIT
353 870
035 952
429 954
92 1 993
653 922
630 981
611 SOI
254 957
29 1 935
322 S59
539 930
070 941
764 973
7-*a 95G
651 93S
3CO C7-I
65-1 98 1
777 9<".3
39H 976
503 987
6'J.J 9"J
Oii'j 305
451 960
3-^1 ono
? r>t o i j
•i?i 972
4,2'J 92-1
.-".1 SG3
04
06
B7
10
1 1
i **
13
14
15
• f
ID
23
29
30
32
33f
*3O
38
44
45
46
47
43
49
51
QC
85
DC
66
87
88
PIPORT
1 4-DICHLOPQBUTftNE (INTERNflL STrNDflR
BROraCHLOROtlETHflNE C1NTERNRL STfiNDflR
BENZENE
CRRBONTETRflCHLORIDE
CHLOROBENZENE
1.2-DICHLOROETKRNE
l.l.l-TRICHLOROETHQNE
l.l-DICKLGPCETHPNE
l.l.Z-TRICHLOSQETHPNE
1.1.2.2-TETRflCHLOROEThflNE
CHLOSGETrifiNE
CHLOROFORM
1,1-DICHLOfiOETHENE
l.2-TRfiNS-DICHL030ETHYLEME
1.2-DICHLGRGPROPaNE
330 CIS-I.3-DICHLOROPROPENE
ETHYLBtNZEHE
METMYLENECHLORIDE
METHYL CHLORIDE
METHYL BROMIDE
8ROHQFOSM
BRGnODICHLOSOKETKfiNE
TRICKLOROFLUOSOrSTHRNE
DIBROnOCHLOROfETVIflHE
TETR1CHLOROETHENE
TOLUENE
TRIChLOROETHENE
VINYLCHLORIDE
FILE: D:VSM13314.MI
-------
B-59
METHOD FOR QRGANOCHLORINE PESTICIDES IN ENVIROMENTAL WATER SAMPLES
NATIONAL ENhORCEHENT INVESTIGATIONS CENTER
1. SCOPE AMD APPLICATION
1.1 This method is an adaptation of that described in ref. 1
and covers the determination of various organochlorine pesti-
cides, including some pesticidal degradation products and
related compounds in industrial effluents. Such compounds
are composed of carbon, hydrogen, and chlorine, but may
also contain oxygen, sulfur, phosphorus, nitrogen or other
halogens.
1.2 The following compounds may be determined individually by
this method with a sensitivity of at least 1 ug/liter:
BHC, lindane, heptachlor, aldrin, heptachlor epoxide, di-
eldrin, endrin, DDE, ODD, DDT, methoxychlor, endosulfan,
mirex, trifluralin, endrin aldehyde, and endosulfan sulfate.
Under favorable circumstances, Strobane, toxaphene, chlordane
(tech) and others may also be determined. The usefulness
of the method for other specific pesticides must be demon-
strated by the analyst before any attempt is made to apply
it to sample analysis.
1.3 When organochlorine pesticides exist as complex mixtures,
the individual compounds may be difficult to distinguish.
High, low, or otherwise unreliable results may be obtained
through misiclentification and/or one compound obscuring
another of lesser concentration. Provisions incorporated
in this method arc intended to minimize the occurrence of
such interferences.
-------
C-60
2. SUMMARY
2.1 The method offers several analytical alternatives, dependent
on the analyst's assessment of the nature and extent of (
interferences and/or the complexity of the pesticide mixtures
found. Specifically, the procedure describes the use of an
effective co-solvent for efficient sample extraction; provides,
through use of column chromatography and liquid-liquid parti-
tion, methods for elimination of non-pesticide interferences
and the pre-separation of pesticide mixtures. Identification
is made by selective gas chromatographic separations and
may be corroborated through the use of two or more unlike
columns. Detection and measurement is accomplished by elec-
tron capture, microcoulometric or electrolytic conductivity
gas chromatography. Results are reported in micrograms per
liter.
2.2 "This method is recommended for use only by experienced pesti-
cide analysts or under the close supervision of such qualified
persons.
3. INTERFERENCES
3.1 Solvents, reagents, glassware, and other sample processing
hardware may yield discrete artifacts and/or elevated base-
lines causing misinterpretation of gas chromatograms. All
of these materials must be demonstrated to be free from
interferences under the conditions of the analysis. Speci-
fic selection of reagents and purification of solvents by
distillation in all-glass systems may be required.
3.2 The interferences in industrial effluents are high and varied
and often pose great difficulty in obtaining accurate and
precise measurements of organochlorine pesticides. Sample
clean-up procedures are generally required and may result
-------
B-fil
in the loss of certain organochlorine pesticides. Therefore,
great care should be exercised in the selection and use of
methods for eliminating or minimizing interferences. It is
not possible to describe procedures for overcoming all of
the interferences that may be encountered in industrial
effluents.
3.3 Polychlorinated Biphenyls (PCB's) - Special attention is
called to industrial plasticizers and hydraulic fluids such
as the PCB's which are a potential source of interference
in pesticide analysis. The presence of PCB's is indicated
by a large number of partially resolved or unresolved peaks
which may occur throughout the entire chromatogram. Parti-
cularly severe PCB interference will require special separa-
tion procedures (2,3).
3.4 Phthalate Esters - These compounds, widely used a plasticizers,
respond to the electron capture detector and are a source of
interference in the determination of organochlorine pesticides
using this detector. Water leaches these materials from
plastics, such as polyethylene bottles and tygon tubing.
The presence of phthalate esters is implicated in samples
that respond to electron capture but not to the microcoulo-
metric or electrolytic conductivity halogen detectors or to
the flame photometric detector.
3.5 Organophosphorus Pesticides - A number of organophosphorus
pesticides, such as those containing a nitro group, e.g.,
parathion, also respond to the electron capture detector
and may intefere with the determination of the organochlorine
pesticides. Such compounds can bo identified by their res-
ponse to the alkali flame ionization or flame photometric
detectors.
3.6 Anaerobic extracts may contain gross interference due to
the presence of sulfur compounds. This interference can be
removed by reacting the extract with a small amount of metal-
-------
B-62
lie mercury to precipitate the sulfur compounds. After
alumina column cleanup, the sulfur interferences are con-
fined to the first fraction, and only this fraction need be
reacted with metallic mercury (4).
4. APPARATUS AND MATERIALS
4.1 Gas Chromatograph - Equipped with glass lined injection
port.
4.2 Detector Ootions:
4.2.1 Electron Capture - Radioactive (tritium or nickel
63)
4.2.2 Microcoulometric Titration
4.2.3 Electrolytic Conductivity
4.3 Recorder - Potentiometric strip chart (10 in) compatible
with the detector.
4.4 Gas Chromatographic Column Materials:
4.4.1 Tubing - Pyrex (180 cm long x 4 mm ID)
4.4.2 Glass Wool - Silanized
4.4.3 Solid Support - Gas-Chrom Q (60-80 mesh)
4.4.4 Liquid Phases - Expressed as Weight percent coated
on solid support.
4.4.4.1 OV-101, 3%
4.4.4.2 OV-210, 5%
4.4.4.3 OV-17, 3% or any column yielding equiva-
lent separation
4.5 Kuderna-Danish (K-D) Glassware (Kontes)
4.5.1. Snyder Column - three ball (macro)
4.5.2 Evaporative Flasks - 500 ml
4.5.3 Receiver Ampuls - 10 ml, graduated
4.6 Chromatographic Column - pyrex (approximately 340 mm long
x 20 mm ID) with coarse fritted place on bottom (Kontes
-------
B-63
K422000) modified to include a reservoir for 50 ml of solvent
and fitted with a ball joint.
4.7 Micro Syringes - 10, 25, 50 and 100 |jl
4.8 Separatory Funnels - 125 ml, 1000 ml and 2000 ml with
Teflon stopcock.
4.9 Graduated cylinders - 100, 250 and 1000 ml."
4.10 Florisil - PR Grade (60-100 mesh); purchase activated at
1250 F and store in dark in glass containers with glass
stoppers or foil-lined screw caps. Before use, activate
each batch overnight at 130°C in foil-covered glass container.
4.11 Alumina, Basic, Brockman Activity I; 80-200 mesh. The amount
of water needed for proper deactivation is determined by
the elution pattern for a technical chlordane standard. A
1.75% deactivation is usually sufficient to yield the correct
elution pattern (see Table IV).
5. REAGENTS, SOLVENTS. AND STANDARDS
5.1 Ferrous Sulfate - (ACS) 30% solution in distilled water.
5.2 Potassium Iodide - (ACS) 10% solution in distilled water.
5.3 Sodium Chloride - (ACS) Saturated solution in distilled
water (pre-rinse NaCl with hexane).
5.4 Sodium Hydroxide - (ACS) 10 N in distilled water.
5.5 Sodium Sulfate - (ACS) Granular, anhydrous (conditioned at
300 °C for 4 hours).
5.6 Sulfuric Acid - (ACS) Mix equal volumes of cone. H2S04 with
distilled water.
5.7 Diethyl Ether - Nanograde, redistilled in glass, if necessary.
5.7.1 Must contain 2% alcohol and be free of peroxides
by following test: To 10 ml of ether in glass-stop-
pered cylinder previously rinsed with ether, add
one ml of freshly prepared 10% KI solution. Shake
-------
B-64
and let stand one minute. No yellow color should
be observed in either layer. Alternately the
TM
peroxide test may be done with EM Quant Ether
Peroxide - Test stacks. The peroxide level must
be less than 1.5 ppm.
5.7.2 Decompose either peroxides by adding 40 g of 30%
ferrous sulfate solution to each liter of solvent.
CAUTION: Reaction may be vigorous if the solvent
contains a high concentration of peroxides.
5.7.3 Distill deperoxidized ether in glass and add 2%
ethanol.
5.8 Acetonitrile, Hexane, Methylene Chloride, Petroleum Ether
(boiling range 30-60°C) - nanograde,redistill in glass if
necessary.
5.9 Pesticide Standards - Reference grade: sources
5.9.1 Quality Assurance Section, Environmental Toxi-
cology Division, EPA, HERL, Research Traingle
Park, N.C. 27711, MD-69
5.9.2 Pesticides Reference Standards Section, Bldg 048
Range 3 and 3rd Street, BARC, West, Beltsville,
MD 20705
5.9.3 Nanogens, P.O. Box 1025, Watsonville, CA 95076
6. CALIBRATION
6.1 Gas chromatographic operating conditions are considered
acceptable if a Standard Mix B elutes from the GC with
correct retention times and sensitivity. Standard Mix 8
consists of 0.025 pg/ml Undone, 0.050 pg/ml heptachlor,
0.075 [jy/ml aldrin, 0.100 |jg/ml y chlordane, 0.125 ug/ml
dieldrin, 0.250 (jg/ml o, p'-DDT and 0.250 ug/ml p,p'-DDT
-------
8=^65
in hexane. The chromatographic conditions chosen should
yield at least 30% full-scale deflection for all of the
components of Std. Mix B (see Figures 1 through 3). For
all quantitative measurements, the detector must be operated
within its linear response range and the detector noise
level should be less than 2% of full-scale.
6.2 Standards are injected frequently as a check on the stability
of operating conditions. Gas chromatograms of several stan-
dard pesticides are shown in Figures 1, 2 and 3 and provide
reference operating conditions for .recommended columns.
6.3 The elution order and retention ratios of various organo-
chlorine pesticides are provided in Table I, as a guide.
The sensitivity of these compounds is given in Table II.
7. QUALITY CONTROL
7.1 Replicate and spiked sample analyses are recommended as
quality control checks. At a minimum, one replicate and
one spiked analysis should be included per 20 sample anal-
yses. If less than 20 sample analyses are required, one
duplicate and one spiked analysis should still be included.
Data for recovery of specific organochlorine pesticides
from water is given in Table III.
7.2 In addition, one method blank is required per 20 sample
analyses. If less than 20 sample analyses are required,
one method blank should still be included.
7.3 One sample should be injected in replicate into the gas
chromatograph per 20 samples analyzed. If less than 20
sample analyses arc required, a replicate GC injection
should sti11 be made.
-------
B-66
8. SAMPLE PREPARATION
8.1 Shake the sample if suspended matter is present and adjust pH
to near neutral (pH 6.5-7.5) with 50% sulfuric acid or 10 N
sodium hydroxide.
8.2 Quantitatively transfer 1 liter of sample into a two-liter
" separatory funnel. Less sample may be analyzed if necessary,
with the realization that detection limits will be affected.
9. EXTRACTION
9.1 Add 60 ml of 15% methylene chloride in hexane (v:v) to the
sample in the separatory funnel and shake vigorously for two
minutes.
9.2 Allow the mixed solvent to separate from the sample, then
draw the water into a one-liter beaker. Pour the organic
layer into a 250 ml beaker. Return the water phase to the
separatory funnel. Rinse the one-liter beaker with a second
60 ml volume of solvent; add the solvent to the separatory
funnel and complete the extraction procedure a second time.
Perform a third extraction in the same manner.
9.3 Transfer the combined solvent extract to a 500 ml Kuderna-
Danish evaporative concentrator by passing it through a
funnel plugged with glass wool and filled with sodium sulfate
which has been prewashed with hexane.
9.4 Concentrate the extract to 10 ml in the K-D evaporator on a
hot water bath.
9.5 Analyze by gas chromatography unless a need for cleanup is
indicated (see Section 10).
-------
B-67'
10. CLEAN-UP AND SEPARATION PROCEDURES
10.1 Interferences in the form of distinct peaks and/or high
background in the initial gas chromatographic analysis, as
well as the physical characteristics of the extract (color,
cloudiness, viscosity) and background knowledge of the sam-
ple will indicate whether clean-up is required. When these
interfere with measurement of the pesticides, or affect
column life or detector sensitivity, proceed as directed
below.
10.2 Acetonitrile Partition - This procedure is used to isolate
fats and oils from the sample extracts. It should be noted
that not all pesticides are quantitatively recovered by
this procedure. The analyst must be aware of this and demon-
strate the efficiency of the partitioning for specific pesti-
cides.
10.2.1 Quantitatively transfer the previously concentrated
extract to a 125 ml separatory funnel with enough
hexane to bring the final volume to 15 ml. Extract
the sample four times by shaking vigorously for
one minute with 30 ml portions of hexane-saturated
acetonitrile.
10.2.2 Combine and transfer the acetonitrile phases to a
one-liter separatory funnel and add 650 ml of dis-
tilled water and 40 ml of saturated sodium chloride
solution. Mix throughly for 30-45 seconds. Extract
with two 100 ml portions of hexane by vigorously
shaking about 15 seconds.
10.2.3 Combine the hexane extracts in a one-liter separa-
tory funnel and wash with two 100 ml portions of
distilled water. Discard the water layer and
pour the hexane layer into a 500 ml K-D flask
-------
B-68
through a funnel plugged with glass wool and
filled with sodium sulfate which has been pre-
washed with hexane. Rinse the separatory funnel
and column with three 10 ml portion of hexane.
10.2.4 Concentrate the extracts to 10 ml in the K-D eva-
porator in a hot water bath.
10.2.5 Analyze by gas chromatography unless a need for
further clean-up is indicated.
10.3 Florisil Column Adsorption Chromatography
10.3.1 Adjust the sample extract volume to 10 ml with
hexane.
10.3.2 Prepare a 20 mm I.D. column that contains 4 inches
(after settling) of activated Florisil topped
with 0.5 inch anhydrous sodium sulfate.
10.3.3 Pre-elute the column with 50-60 ml of petroleum
ether. Just prior to exposure of the sulfate
layer to air, quantitatively transfer the sample
extract onto the column. Just prior to exposure
of the sodium sulfate layer to air, add the first
eluting solvent, 200 ml of 6% ethyl ether in petro-
leum ether. Collect the eluate in a 250 ml beaker.
Perform the second elution with 200 ml of 15%
ethyl ether in petroleum ether, the third elution
with 200 ml of 50% ethyl ether-petroleum ether,
and the fourth elution with 200 ml fo 100% ethyl
ether. (See Eluate Composition 10.3.6).
10.3.4 Concentrate the eluates to 10 ml in a K-D in a
hot water bath. Fifty mis of petroleum ether
must be added to the fourth fraction prior to
concentration to eliminate the ethyl ether from
the concentrated extract.
10.3.5 Analyze by gas chromatography.
-------
B-69
10.3.6 Eluate Composition - The composition of the eluate
should ue checked for each new batch of Florisil
with a standard mix consisting of gamma-BHC (lindane)
heptachlor, endosulfan A and B. If the composition
of the eluate varies from that given below, the
amount of Florisil used in the column should be
altered i.e., an increase in the amount of Florisil
will increase the amount of solvent needed to
elute compounds from the column. The majority of
the compound should elute in the fraction listed
below.
6% Eluate
Aldrin DDT
BHC ~ Heptachlor
Chlordane Heptachlor Epoxide
ODD Lindane
Endosulfan A Mi rex
Toxaphene PCB's
DDE Methoxychlor
15% Eluate 50% Eluate
Endrin Endosulfan B
Dieldrin
Phthalate esters
Certain thiophosphate pesticides will occur in
each of the above fractions as well as the 100%
fraction. For additional information regarding
eluate composition, refer to the FDA Pesticide
Analytical Manual (5).
10.4 Alumina Column Adsorption Chromatography (6).
10.4.1 Adjust the sample extract volume to 10 ml with
hexane.
10.4.2 Prepare a 15 cm (after settling) x 2 cm column
of properly deactivated alumina (see 4.11). The
alumina should be settled by tapping the column.
-------
B-70
10.4.3 Pre-eluate the column with 40-50 ml of hexane.
Adjust the flow of the solvent through the column
to 5 ml/min with air. Just prior to exposure of
the alumina surface to air, quantitatively trans-
fer the sample extract to the column using several
hexane washes. This transfer should be done with-
out disturbing the surface of the alumina.
10.4.4 Just prior to the exposure of the alumina surface
to air, add 50 ml of a 10% ethyl ether in hexane
solution. Collect the eluate in a 50 ml beaker.
Ten 50 ml fractions are collected in like manner
and each fraction is concentrated to 10 ml on a
hot plate under a gentle stream of air.
10.4.5 Analyze by gas chromatography.
10.4.6 Eluate Composition. The composition of the eluate
should be checked for each new batch of alumina
with a technical chlordane standard. If the composi-
tion of the eluate varies from that given in Table
IV, the amount of water added to the alumina should
be altered, i.e., an increase in the amount of
water will decrease the amount of solvent needed
to elute compounds from the column.
11. CALCULATION OF RESULTS
11.1 Determine the pesticide concentration by using the absolute
calibration procedure described below:
(1) Micrograms/lHer = (A) (B) (V
-------
B-71
12. REPORTING RESULTS
12.1 Report results in micrograms per liter without correction
for recovery data. When duplicate and spiked samples are
analyzed, all data obtained should be reported.
-------
B-72
REFERENCES
1 "Method for Organochlorine Pesticides in Industrial Effluents",
Natinal Pollutant Discharge Elimination System, Appendix A, Federal
Register, 38, No. 75, Pt. II.
2 Monsanto Methodology for Arochlors - Analysis of Environmental
Materials for Biphenyls, Analytical Chemistry Method 71-35, Mon-
santo Company, St. Louis, Missouri, 63166, 1970.
3 "Method for Polychlorinated Biphenyls in Industrial Effluents,11
Environmental Protection Agency, National Environmental Research
Center, Cincinnati, Ohio, 45268, 1973. (Also NPDES, Appendix A,
Fed. Reg., 38, No. 75, Pt. II.)
4 Goerlitz, D.F. and Law, L.M., "Notes on the Removal of Sulfur
Interferences from Sediment Extracts for Pesticide Analysis,
Bulletin of Environmental Contamination and Toxicology, Vol. 6,
No. 1, 1971.
5. "Pesticide Analytical Manual," U.S. Dept. of Health, Education
and Welfare, Food and Drug Administration, Washington, D.C.,
Vol. I, 211.14 (d).
6. Boyle, H.W., Burttschell, R.H., and Rosen, A.A., "Infrared Iden-
tification of Chlorinated Insecticides in Tissues of Poisoned
Fish," Organic Pesticides in the Environment, Advances in Chemistry
Series, No. 60, A.C.S., Washington, D.C., 1966.
-------
B-73,
Table I
RETENTION TIMES OF ORGAMOCHLORINE PESTICIDES RELATIVE TO ALDRIN
Liquid Phase
Solid Support
Column Temperature
Flow rate (ml/min)
3% OV-101
2 mm x 6' glass
on 60/80 GCQ
180°C
25
3% OV-17
4 mm x 6' glass
on 60/80 GCQ
200°C -
80
5% OV-210
2 mm x 6' glass
200°C
37
Pesticide
aldrin (min absolute)
RRT
3.80
RRT
2.28
RRT
a-BHC
B-BHC
y-BHC (lindane)
o-BHC
heptachlor
aldrin
heptachlor epoxide
y-chlordane
Endosulfan A
cr-chlordane
dieldrin
p p' DDE
r > r* wi^i-
endrin
Endosulfan B
o,p' DDT
\S y ff *f w
ODD
Endrin aldehyde
endosulfan sulfate
D D1 DDT
r » K " **
methoxychlor
0.40
0.44
0.48
0.50
0.80
1.00
1.26
1.44
1.60
1.62
1.88
1.96
2.11
2.20
{fe=33? -?.&<<
2.52
2.52
2.99
3.37
5.31
0.45
0.49
-0.53
0.54
0.82
1.00
1.19
1.38
1.47
1.50
1.73
1.68
1.89
1.93
2.25
2.10
2.10
2.46
2.77
4.01
0.68
0.96
0.83
1.54
0.88
1.00
IT 1
.71
1.64
2.16
If A
.64
2 IT C
. 55
1-»O
.78
2.97
3T O
.72
2O f\
.22
2.94
5.76
8.42
3M /«
.18
4.60
1.74
a Argon 10% methane, RRT for other columns are given in ref. 1,
Table I.
-------
B-74
Table II
SENSITIVITY OF ORGANOCHLORINE PESTICIDES USING
ELECTRON CAPTURE (EC) DETECTOR
Instrument
Liquid Phase
Solid Support
Column Temperature
Flow Rate
Injection Size
Tracer MT-220
3% OV-17
4 mm x 6' glass
60/80 GCQ
200°C
81.6 ml/min
2 pi
Pesticide
Lindane
Heptachlor
Aldrin
y-Chlordane
Dieldrin
o.p1 DDT
p.p1 DDT
r i n
a-BHC
endosulfan A
p,p' DDE
r 1 r
endosulfan B
ODD
endosulfan sulfate
p-BHC
Heptachlor Epoxide
Endrin
Endrin Aldehyde
cone.
(ljg/ml)
0.025
0.05
0.075
0.10
0.125
0.250
0.250
0.05
0.10
0.10
0.10
0.10
0.50
0.050
0.100
0.100
0.100
att.
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
peak height
(mm)
79
113
140
132
136
95
92+
256
77
104
60
46
215
79
134
C rt
58
31
-------
B-75
Table III
RECOVERY DATA FOR SELECTED ORGAMOCHLORIME PESTICIDES
(EXTRACTION FROM WATER ONLY)
Spiking Number of Average % Standard
Compound Level (ug) Determinations Recovery Deviation
lindane
heptachlor
aldrin
•y-chlordane
dieldrin
o.p1 DDT
P,P' DDT
ODD
L/L/Ls
Endosulfan A
Endosulfan B
crBHC
P,P' DDE
Endosulfan sulfate
p-BHC
heptachlor epoxide
endrin
endrin aldehyde
0.25
0.50
0.75
1.00
1.25
2.50
2.50
1.00
1.00
1.00
0.50
1.00
5.00
0.50
1.00
1.00
1.00
12
12
12
12
12
12
11
11
12
12
9
12
11
8
9
7
8
110
89
91
97
100
98
109
100
99
95
102
98
107
103
99
115
89
8.3
7^
.6
12.4
2r
.5
3.8
6/i
. 4
5.5
14.8
4.3
6n
. 0
3.8
4«
.1
11.6
5 si
. 2
6.2
12.2
7r*
.2
-------
B-76
Table IV
ORDER OF ELUTION OF CHLORINATED INSECTICIDES
FROM ALUMINA ADSORPTION COLUMN3 (6)
Insecticide
DDE
Aldrin
Heptachlor
Tech. Chlordane
Toxaphene
DDT
•y-Chlordane
a-Chlordane
ODD
Lindane
Endrin
Heptachlor Epoxide
Dieldrin
Methoxyclor
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
Lindane
Lindane
50
1
95
93
75
30
15
5
100
98
95
95
(Acid Al
(Neutral
ml Eluate
2 3
5
7
25
30 35
55 30
95
2 80
95
60
35
2
5
5
umina)
Alumina)
Fractions - % of Total Recovered
4 5 6 7 8 9 10
5
Trace
18
5
40
65
45 55
35 50 15
20 40 20 15 5
5 30 50 10 5
25 60 15
3 75 20 2
% Recovery
94
97
96
f\f\
99
93
94
99
rt ~i
97
93
40
95
95
96
96
100'
100
100
100
100
91
a 9/1 Hexane/Ethyl Ether Eluting Solvent.
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B-77-
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-------
B-80
Quality Control Data
Pesticides and PCB
Sample 05 was analyzed after spiking with seven pesticide components,
with average recovery of 91%.
Sample 08 was analyzed in replicate. Two components, alpha-BHC and gamma-
BHC were detected, with an average deviation of 5 percent.
Table 1
Pesticides-PCB's-QC Results
Spiked Sample: 05
Component Recovery, percent
Aldrin 90%
Gamma-Chlordane 82
o.p'-DDt 85
p.p'DDT 93
Dieldrin 92
Heptachlor 94
Lindane 99
Duplicate Sample: 08
Component Analysis 1 Analysis 2
Alpha-BHC 170 ug/1 188
Gamma-BHC 61 55
-------
APPENDIX C
NON-PRIORITY POLLUTANTS
QUALITATIVE DATA SUMMARY
-------
APPENDIX C
NON-PRIORITY POLLUTANTS (QUALITATIVE DATA SUMMARY)3
HOOKER CHEMICALS AND PLASTICS CORPORATION
WASTE DISPOSAL SITES/NIAGARA FALLS, NEW YORK
July 12-September 7, 1979
Relative Values
Chemical Name Station No. 01 02 03 04 05 06 07 08 09 10
Aminobenzotrifluoride isomer
Chlorobenzaldehyde isomer
2,4-dichlorotoluene
Dichlorotoluene isomer (other than 2,4)
Trichlorobenzene isomer (other than 1,2,4)
Chlorobenzoic acid, methyl ester isomer - #1
Chlorobenzoic acid, methyl ester isomer - #2
Dichloro-alpha-chlorotoluene isomer - #1
Dichloro-alpha-chlorotoluene isomer - #2
Tetrachlorobenzene isomer - #1
Tetrachlorobenzene isomer - #2
Pentachlorobenzene isomer
Chlorobenzoic acid isomer
Tetrachlorotoluene isomer - #1
Tetrachlorotoluene isomer - #2
NDb
ND
39
ND
ND
3
ND
8
ND
ND
9
MS
9
1
2
ND
3
1
ND
ND
6
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1
ND
ND
ND
ND
1
ND
MS
MS
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
3
ND
ND
ND
ND
ND
ND
ND
NDr
MSC
ND
ND
ND
ND
ND
82
MS
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
MS
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
8
36
ND
ND
ND
ND
a This information includes the results of the NEIC Qualitative Evaluation of
samples collected July 12, 1979 for other non-priority pollutants. The data
format is the same as previously reported data. The results are shown as
relative quantities. Because the same respone factors were used as for the
previous data, these data may be directly compared.
b ND means not detected.
c MS means the compounds was identified by mass spectrometry but was below the
quantisation detection limit.
------- |