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

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      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

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                  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.

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                                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.

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     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.

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                      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.

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     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.

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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.

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      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.

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                         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.

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     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.

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                                                                       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.

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                                                                            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.

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                                                                              13
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 \    Uniersity
Niagara University


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                                                  .  61804
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Niagara Steel
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Lafayette Ave.

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OW4 	 	
ithority Road
nun /f\
UWJ. f 1
OW2^^^7
OW3 'cftA.
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! -*@.STT."d61802 **\ STA.
| 61814
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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. 234.5.6.7

     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
REnJryf ' 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
REniryf ' 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

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                     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)








.

-------
                                                            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

-------
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

-------
                                                                   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

-------
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

-------
                                                                    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

-------
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

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                                                                       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 4C 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 4C 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.

-------
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 20C 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.

-------
                                                                        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 4C 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 200C  and septa  at 80C 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  (190C 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 105C (up to 200C) 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 190C 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 -20C.  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 60C initial and 170C final temperatures,
                     an 8C/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

-------
                                                               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 180C,  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 60C.



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 200C.  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.

-------
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"isapplicable 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 -
          4hJdroxJ-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
                 60C and held for 1 min.  after injection, then a temper-
                 ature program is initiated at 4C/min to 22C.  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  100C.  The injector temperature is 250C.
     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'aiTi125;
                          * 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
                         RCOU   (I;HICQ;T2;S;G:55:CO;E)
                         EPfiSE
                         L'aiT "IS
                         BEEP
                         BEEP
                         BEEP
                         E0ISE
                         ua;r 45
                         BEEP
                         EEE
                         ElflSE
                         IHIT s47
                         L'HIT o|2ll
                         SO.'IG  (OFF)
                         LMIT -12'J
                         iinn oisu
                         RCOU  (S:C) ,

-------
                                                                                     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) ;
   *
   PflSP  (I:H;E)
   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
                              *
                              SETO SI
                              EDOL  (-;U;E3
                              SETL
                              SET1 1
                              FILE  (K  PRIN.99/N:E)
                              PRRrt  (I;H:E)
                              CKRO  (I:H1.2aQa:4Q3:E)
                              PR IPOS
                                  * SET14 1;GETL *l
                                  * ;SE/V (I;S.t;V2t,e230:N2.1Q.5CO;D-2S.25;E)
                                  * ;F3!?07
                                  *
                                  SET14  e|

                                  SEfiR  (I;S;t;V200030;N2.1B.5GO;D-25.25:E)/V
                                  PRIP07
                                     * IF PP.IP07 *\. !14
                                     * ;PPIII  CQP2)
                                     * ;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
        PRIF03
           * FRIT04
           *  ;EDQL C-:N;*:fl;E>
           *

                   PRIP04  M6.PRIP04  .503

                       lI|?R:S::H1.2;n>5.3:C-4.4:D-S.5:E>
              >t  PS IPOS
               ;RETU PP.IP03

               IF PRIP04'16,PRlP04*5Ba

              CHRO  ' U;R:S; :K1.2;B>5.3;G-4.4;D-5.S;E)
              PR IPOS
                 *  IF PPIP05  "27.PRIP05
                 *  ;LIBR (!:C:DS:HS;E)

                  IF  PRIP05':r.PSIP05
                 LIBP  (I:C:DS;HS;E)
              RETU  P5IP03
            EDOL  t-:H;".n.E'
         LOOP
      EDLL  CB'1:E)
      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 80-90C 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
/ "i n
63.8
1C
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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-DiiWtl>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 POCEDU'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?
                       * ;EDSL YES (-: 1;LJ;E);EDSL NO C-;U:E>
                       * ;SETN PRIPOL
                       IK ;PR!P03
                       * ;FEED
                       * ;SEEP:S=?:S=cP
                       *
                       SETL SI
                       SETS 52
                       SETQ TEM?
                       EDSL YES  C-;1;U;E>
                       EDSL MO C-.-U.E)
                       SETM PRIPOL
                       PRIPOO
                          * GETH;PRIPOI:LOOP
                          IK
                          GETN
                          PRIF01
                             * ;EDOL SI  (-jU.-E).-SETL s8:SETI
                             * .-FILE  
                                    BEEP
                                    GEEP
                                    OEEP
                                    DEEP
                                    GEE?
                                    GEE?
                                    DEEP
                                    RETU I'KIPOl
                              srn.
                              SETHI '!:
                              PRIP02
                                   CCT1 'IU
                                   :ScTI I "0
                                   .-CETL
                                           (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
              IK
               IF PRIP04I I6.PRIPO<*50B
              SET!  !14
              EDOL   C-;U:E)
              CH50   (I:R:$;*:tl!.2:fl>5.3:C-4.4:D-5.5:E)
              EDDL  TEMP,SI  (Dfc2a,100;fi:E)
              PR IPOS
                 *  IF  PRIP35  I27.PRIP05
                 *  ;LIER t!:C:DS;HS;E)
                 *
                  IF PRIP05'27.FRIPOS
                 L1BR   CI.-C.-DS^.S.-E)
               RETU  PRIP03
            EDDL  SI  C-;N:=;fl:E)
         LOOP
      EDLL  (BM;E)
      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
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0.
vs
0.
vs
0.
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0.
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vs
0.
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0.
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0.
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0.
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0.
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0.
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0.
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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)rTHflNE
52  HEXflCKLOROoUTflDIENE
53  HEXflCHLOROCYCLOPENTflDIENE
54  1SOPHOROME
55  NflPHTHBLENE
56  NITROBENZENE
62  N-NITROSODIPHEMYLflniNE  (MEflS AS DIPH
63  N-NITROSODIPiCOPYLfirilllE
66  Dl-(2-ETHYLHEXYL)PHTHqLfTE
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
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.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
.48 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 130C 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 30-60C) - 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
      180C
       25
    3% OV-17
4 mm x 6'  glass
  on 60/80 GCQ
      200C  -
       80
   5% OV-210
2 mm x 6'  glass

      200C
       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
     200C
  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.

-------
                                                                                                   B-77-
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               _._.___ ..,,	^  	 -j rn,.._.-.."! 





-------
B-78
r  r  f  r  f   f  r   f  f  r  r  r  r  -
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     CM-  K

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-------
  T I :..E 1          C- . L?0
  ittJ  TEMP  4C3   135    275


   _; 7   I, = 71       i . 2 7
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  H ! ! r i  2 t     1 L!
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           STOP
                                                                                      B-79
                                                                  3.
                                                                                        o
STFiRT
HP F:
BOTTLE
flPEfi  *:

    PT

   0. 25
   0. 37
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   1 . 3

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   2. 23
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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.

-------