-------
MASS BALANCE IN LB8. PER PAY
PLANT 14
A
PARAMETER
OOP
TOTAL SUSP.
COD
OIL I GREASE
SOLIDS
TOTAL PHENOLS
TOTAL SOLIDS
TOTAL DISS. SOLIDS
TOTAL VOLATILE SOLIDS
VOLATILE DISS. SOLIDS
TOTAL VOL. 8U9. SOLIDS
AMMONIA HITROOEH
TOC
BENZENE
CARBON TETRACHLOR1DE
CHLOROBENZEHE
,2-DICHLOROETHANE
.t.1-TRICHLORUETHAHE
.1-DICHLORDETHAHE
rIt2-TRICHLOROETHAHE
,1.2r2-TETRACHLOROETHANE
HLOROFORH
rl-DICHLOROETHYLEHE
r2-TRANB-DICHLOROETHYLENE
r2-DICHLOROPROPANE
ETHYLBEHZEHE
METHYLEHE CHLORIDE
METHYL BROHIDE
DICIILOROBROHOHE THAHE
TRICHLOROFLUORUHE THAHE
TETRACHLOROETHYLEHE
TOLUEHE
TRICHLOROETHYLENE
VINYL CHLORIDE
2•4.4-TRICHLOROPHENOL
2t4-DICHLOROPHEHOL
2>4-DIHETHYLPHEHOL
PEHTACHLOROPHEHOL
PHEHOL
lr2-DICHLOROBENZENE
1>3-DICHLOROBENZENE
1> 4-DICHLORODENZEHE
FLUORAHTHENE
NAPHTHALEHE
BIS(2-ETHYLHEXYL> PHTHALATE
BUTYL BEHZYL PHTHALATE
DI-H-BUTYL PHTHALATE
DIETHYL PHTHALATE
POLLUTANTS NOT LISTED MERE NOT DETECTED
L-LESS THANI N-D NOT DETeCTEDI
PRELIMINARY DATA ONLY TO BE VERIFIED
INFLUENT
1
203243
205434
524703
30562
34.0
198234
434428
270728
44724
195040
14120
7933B
.9
1.4
M-D
.2
19.4
.2
.3
N-D
34.8
H-D
.9
N-D
5.8
34.3
N-D
.2
N-D
43.4
31.3
12.3
N-D
N-D
.8
N-D
2.8
29.9
14. B
N-D
2.5
N-D
.8
24.1
3.3
2.5
5.8
INFLUENT
2
73187
31224
172914
8489
10.4
185712
137814
81703
19929
39511
3134
37307
.3
97.7
N-D
L 0.1
13.4
.4
N-D
N-D
10.4
L Oil
2.2
N-D
13.1
23.9
1.7
L 0.1
1.2
35.8
33.9
44.3
2.9
.5
.3
2.4
4.4
24.4
20.4
4.3
9.4
N-D
12.1
11.9
1.2
2.9
1 .5
TDTAL IN
274430
254482
497419
47251
44.4
883944
594242
352431
44455
194551
19274
114445
1.2
99.1
N-D
.2
33.0
.8
.3
N-D
47.4
L O.I
3.1
N-D
18.7
40.2
1.7
.2
1.2
79.4
45.2
54.4
2.9
.5
1.1
2.4
7.2
54.5
37.4
4.3
12.1
N-D
12.9
38.0
4.5
5.4
7.3
TOTAL OUT
44770
149371
242432
25944
13.7
417095
-
213834
-
134493
10935
31728
L 0.1
.8
.2
N-D
.4
.8
.2
.4
8.1
N-D
1.4
L 0.1
1.0
4.0
H-D
N-D
H-D
1.5
1.1
3.4
N-D
H-D
N-D
N-D
4.8
.1
1.8
.2
4.4
.4
4.3
11.8
1.3
1.7
N-D
TERTIARY
EFFLUENT
13284
3032
74483
14089
13.0
511433
537394
132034
40583
3422
10447
22542
N-D
.8
.2
H-D
.4
N-D
.2
.4
8.1
N-D
N-D
H-D
.4
5.8
N-D
H-D
H-D
1.2
.4
.4
H-D
H-D
H-D
H-D
4.8
H-D
1.8
H-D
H-D
H-D
H-D
4,2
H-D
.4
N-D
COMBINED
SLUDGE
25144
84437
79844
5705
.2
50059
NOT RUN
38789
NOT RUN
49042
190
4391
L 0.1
N-D
L 0.1
H-D
H-D
I 0.1
H-D
H-D
L 0.1
H-D
.5
L 0.1
.1
.1
H-D
N-D
N-D
L 0.1
.2
.4
N-D
H-D
N-D
H-D
H-D
H-D
H-D
.2
1.9
L 0.1
.4
3.7
.4
.3
M-D
COMBINED
SLUDGE 2
24322
77702
104093
4172
.5
55403
NOT RUN
43011
NOT RUN
44009
78,4
4795
t 0.1
H-D
I 0.1
H-D
N-D
,7
H-D
N-D
L 0.1
N-D
.9
t 0.1
.5
.1
N-D
H-D
H-D
.3
.5
2.4
H-D
H-D
H-D
H-D
N-D
N-D
N-D
L 0.1
4.7
.3
3.9
3.9
.7
1.0
) N-D
-------
nflbi VALANCE IN LtB. PER DAY
PLANT
o
05
A
PARAMETER
I'2-BENZAHTIIRACENE
BEM20 (A)PYRENE
CIIRYSCNE
ANTHRACENE
PMENANTIIRENE
PYRENE
4.4--DOD
ALPHA-BMC
OAHMA-BMC
ANTIMONY
ARSENIC
BERYLLIUM
CADMIUM
CHROMIUM
COPPER
CYANIDE
LEAD
MERCURY
NICKEL
SELENIUM
SILVER
2INC
ALUMINUM
BARIUM
CALCIUM
IRON
MAGNESIUM
HANOANE8E
UODIUH
INFLUENT
1
N-0
N-D
N-D
N-D
N-D
N-D
N-0
L O.I
L O.I
M-D
24.6
N-D
4.4
37. a
124
249
108
.4
72.4
N-D
4.8
203
1301
138
308IQ
1221
3931
44.8
83131
INFLUENT
2
N-D
N-D
N-D
N-D
N-D
N-D
N-D
L O.I
N-D
N-D
N-B
N-D
7.1
44.2
47.4
79.4
34.2
.4
24.0
N-0
17.8
89.2
210
30.4
9440
432
1297
14.7
18414
TOTAL IN
N-0
N-D
N-D
N-D
N-D
N-0
N-D
.1
1. 0,1
M-D
24.8
M-D
11.9
122
172
349
144
1.0
94.4
N-D
24.4
292
1311
189
40438
1439
3248
41.9
101947
TOTAL OUT
. 1
.1
.7
.7
.2
L 0. 1
L O.I
.2
.8
1.7
L O.I
4.2
34.9
91.4
230
83.0
.4
74.3
39.4
1.9
123
_
-
-
.
-
-
-
TEKIIAKY
EFFLUENT
N-D
N-D
N-D
N-D
N-D
N-D
L O.I
I 0.1
.2
N-D
N-D
M-D
N-D
23.8
4.0
172
4.8
.2
49.4
N-D
M-D
37.2
18.9
12.9
19429
132
4831
38.2
98421
COMDINED
SLUDGE
L 0.1
N-D
L 0.1
.3
.1
L 0.1
N-D
N-D
N-D
.9
1.4
L O.I
.9
7.8
17.2
32.4
41.8
L O.I
4.1
.2
.2
30.9
NOT RUN
HOT RUN
NOT RUN
NOT RUN
NOT RUM
NOT RUM
MOT RUN
COMBINED
SLUDGE 2
.1
N-D
. I
.4
.4
, 1
M-0
N-D
N-D
.1
.3
L O.I
1.3
24.9
28.2
49.4
34.4
t. 0.1
4.4
39.2
1.7
94.4
NOT RUN
NOT RUN
NOT RUN
NOT RUM
NOT RUN
NOT RUN
NOT RUN
POLLUTANTS NOT LISTED UERE NOT DETECTED
L tESS THAN! N-D NOT DETECTED!
PRELIMINARY DATA ONLY TO bE i/EKIFIED
-------
PERCENT OCCURRENCE OF POLLUTANT PARAMETERS
PLANT 16
PARAMETER
If If1-TRICHLOROETHANE
CHLOROFORM
METHYLENE CHLORIDE
TETRACHLOROETHYLENE
TOLUENE
TRICHLOROETHYLENE
BI8<2-ETHYLHEXYL> PHTHALATE
DIETHYL PHTHALATE
CADHIUH
CHROMIUM
COPPER
CYANIDE
LEAD
MERCURY
NICKEL
SILVER
ZINC
BENZENE
ETHYLBENZENE
J.2-TRAN8-DICHLOROETHYLENE
PHENOL
1.2-DICHLOROBENZENE
BUTYL BENZYL PHTHALATE
DI-N-BUTYL PHTHALATE
CARBON TETRACHLORIDE
NAPHTHALENE
8AMHA-BHC
ARSENIC
1f2-PICHLOROETHANE
It1-DICHLOROETHANE
1>1r2-TR1CHLOROETHANE
DICHLOROBROHOHETHANE
2f4-DICHLOROPHENOL
PENTACHLOROPHENOL
1f 4-DICHLOROBENZENE
ALPHA-BHC
CHLOROBENZENE
1r1t2t 2-TETRACHLOROETHANE
It1-D1CHLOROETHYLENE
1f2-BICHLOROPROPANE
METHYL BROMIDE
TRICHLOROFLUOROMETHANE
CHLORODIBROHOMETHANE
VINYL CHLORIDE
2f4r6-TRICHLOROPHENOL
2f4-DIMETHYLPHENOL
1r 3-DICHLOROBENZENE
FLUORANTHENE
1f 2-BENZANTHRACENE
BENZO (A)PYRENE
CHRY8ENE
POLLUTANTS NOT LISTED WERE NOT DETECTED
UNCONFIRMED PESTICIDES HERE ASSUMED NOT
NUMBERS IN PARENTHESES ARE THE NUMDER OF
PRELIMINARY DATA ONLY-TO BE VERIFIED
JNFL- OTHER SEC. TERT. COMB. COMB, TAP
UEMT INFL. EFFL EFFL, BLPB SLDG-2 MATER
100
100
100
100
100
too
too
100
100
100
100
100
100
too
100
100
too
83
B3
67
47
67
67
SO
33
33
33
33
17
17
17
17
17
17
17
17
0
O
0
0
0
0
0
0
0
0
0
0
0
0
0
4> 67
4) 10O
4) 100
4) 100
4) 83
4> 100
4> 100
4) 10O
At 100
4) 100
4) 100
4) 100
4) 100
4) 100
6) 100
4) 100
4) 100
4) 47
4) 100
4) 47
4) 100
4> 100
4) 100
4> B3
4) 67
6> 100
6) 0
4) 0
6) 17
6) 100
6> 0
6) 17
6) 17
6> 67
6) 67
6) 17
6) 0
4) 0
6) 33
6) 0
6) 33
6> 67
4) 0
6) 33
6) SO
4) 17
6) SO
6) 0
6) 0
4) 0
6) 0
6> 17 ( 6) 33
6) 100 < 6) 50
4) 100
6) 10O
6) 83
6) 67
4) 100
4) 17
f > SO
4) 100
i) 100
») 10O
6) SO
6> 83
4) 100
4) 100
6) 100
4> 0
6) 33
6) 0
4) 17
6) 33
4) 0
6) 83
6) 100
6) 0
6) SO
6) 17
6) 0
6) 0
4> 0
6) 33
4) 0
6) 17
6) 0
6) 83
4) 17
6) 17
6) 0
6) 0
6) 0
4) 0
6) 0
6) 0
6> 0
4) 17
6) 0
6) 0
6) 0
4) 0
4) 100
6) SO
4) 33
4) 33
6> 50
6> 0
4> 0
6> 10O
6> 63
6) 100
6) 17
6) 100
6> 100
6) 0
4) 100
6> 0
4) 0(6) 0
6) 17 ( 4> 50
4) 100
4) SO
6) 83
6) 100
4) 100
6) 0
6) 100
6) 100
4) 100
6) 100
6> 100
6) 67
6> 100
6> 100
6> 100
6) 100
6) 33 < 6> 100
6) 0 < 6) 100
6) 0 ( 6» 0
6) 17
6) 0
6) 17
6) 17
6) 0
6) SO
4) 0
6) 0
6) 0
4> 17
4) 0
6) 0
6> 33
4) 0
6) 50
6) 17
4) 17
6) 0
6) 0
6> 0
6> 0
4) 0
6) 0
4) 0
6) 0
6) 0
6) 0
4) 0
6> 0
6) 0(6) 0
4) 0
4) 100
4) 100
6) 0
4) 83
6) 0
6) 100
4) 0
6) 100
4) 0
6) 0
6) 0
6) 0
4) 17
4) 0
6) 67
4) 0
6) 0
6> 17
6) 0
6) 0
6) 0
4) 0
4) 0
4) 0
6) 17
6) SO
4) 17
6) 0
4) 100
4) 100
4) 100
4) 100
4) 100
4) 0
6) 100
4 > 1 00
41 100
4) 100
4) 100
4) 67
4) 100
6) 100
4) 10O
6) 100
4> 100
4> 100
4) SO
6) 0
4) 100
6) 100
4> f
4) 100
4) 0
4) 100
4) 0
4) 100
4) 0
4) 0
4) 0
6) 0
4) SO
4) 0
4) SO
6) 0
4) 0
6) 33
4) 0
4) 0
4) 0
6) 0
6> 0
6> 0
6) 0
4> 100
4) 83
6) 17
4) 17 < 4) 83
4) 0
6> 100
4) 0
6) 0
6) 0
6) 0
4) 0
6) 0
4) 0
6) 0
6) 0
6> 0
6) 0
4) 0
6) O
4) 0
6) 0
6) 0
6) 0
4) 0
6> 0
6) 0
6) 0
4) 0
6) 0
6) 0
4) 0
4) 0
4) 0
6) 0
4) 0
4) 100
6) 0
6) 0
6) 0
6> 0
6) 0
4) 0
6> 0
6) 0
6) 0
6) 0
6) 100
4> 0
6) 0
6> 0
6) 0
6) 0
6) 0
6> 0
6) 0
1)
1)
|
1
1
t
>
>
1)
i>
1)
)
>
)
)
1)
)
)
>
1)
1>
1)
1)
)
>
>
)
1)
1)
I)
1)
1)
1)
1)
1)
>
)
CTED AT ANY 8AHPLE POINT
NOT DETECTED
ER OF SAMPLES TAKEN
-------
f'ERCENJ OCCURRENCE Of POLLUTANT PARArtETlRb
PLANT 14
PARAMETER
ANIIIRACCNE
f HENANTHRENE
IrKtNE
H. « ' -flllll
ANTIMONY
BERYLLIUM
SELENIUM
INFL-
UENT
0 (
0 I
0 (
0 (
0 (
0 (
0 (
4)
4)
4)
4)
4)
4)
4)
OTHER
INFL.
0
0
0
0
0
0
0
4)
4)
4)
4)
4)
4>
4)
SEC.
EFFL
0
0
0
0
0
0
0
li)
4)
4)
4)
1ERI
EFFL
0
0
0
17
0
0
0
.
< 4)
( 4)
( 4)
( 4>
( 4)
< 4)
< 4)
COMB.
SLOG
100
100
SO
0
100
47
eo
4)
4)
4)
4)
S>
4)
3)
COMb
Sl-liO-
100
too
83
0
too
so
too
T
4)
4)
4)
4>
5)
4)
3>
TAf
WAT
0
0
0
0
0
0
0
en
01
HIIIIHANTS NOT LISIEb UEKE NOT DETECTED AT AN* SAMPLE POINT
nm.ONf IfvMtti PESTICIDES WERE ASSUMED NOT I'EIECIED
miHbt-'KS IN PARENTHESES ARE THE NUMBER OF SAMPLES TAKEN
l-KELIMINAftr [(ATA ONLY-TO b£ VERIFIED
-------
SUMMARY OF ANALYTICAL DATA
PLANT II
FRACTION PARAMETER
CONY. BOD
TOTAL SUSP. SOLIDS
COD
UIL C GREASE
NON-CONV. TOTAL PHENOLS
TOTAL SOLIDS
TOTAL DISS. SOLIDS
SETTLEAULE SOLIDS
TOTAL VOLATILE SOLIDS
VOLATILE DISS. SOLIDS
TOTAL VOL. SUS. SOLIDS
AMMONIA NITROGEN
IOC
VOLATILES BENZENE
CARBON TETKACHLORIDE
.I.1-TRICHL010ETHANE
il-DICHLUROETHANE
tn ,1.2,2-TETRACHLOROETHANE
01 HLUROFURH
i2-TRANS-DlCHLOROETHYLENE
,2-DICHLOROPROPANE
ETHYLDENZENE
HETHYLENE CHLORIDE
METHYL CHLORIDE
DICHLORODIF LUOKOME THANE
TETRACHLOROETHYLENt
TOLUENE
TR1CHLOROETHYLENE
ACIDS. PENTACHLOROPHENOL
PHENOL
BASE-NEUT. FLUORANTHENE
NAPHTHALENE
BISJ2-ETHYLHEXYL) PHTMALAlE
BUTYL BENZYL PHIHALATE
DI-N-BUTYL PHTHALATE
DIETHYL PHTHALATE
1,2-BEN/ANTHRACENE
POLLUTANTS NOT LISTED HERE NEVER DETECTED
L-LESS THANJ N-0 NOT DETECTED!
PRELIMINARY DATA ONLY---TO BE VERIFIED
UMTS
HG/L
HG/L
MG/L
HG/L
UG/L
HG/L
HG/L
ML/L
HG/L
Ht/L
HG/L
HG/L
HG/L
UG/L
UG/L I
UG/L
UG/L
UG/L I
UG/L
UG/L
UG/L L
UG/L
UG/L
UG/L L
UG/L I
UG/L
UG/L
UG/L
UG/L
UG/L
UG/L L
UG/L
UG/L
UG/L
UG/L
UG/L
UG/L L
IMLUINT
19*
129
77C
35
39
629
4t2
25
237
U'J
95
30
95
1
1
5*
1
1
2
3
1
31
22
25
20
124
7<
12
29
16
3
3
24
3
2
4
5
L
L
I
L
L
L
L
L
L
L
L
L
L
L
I
L
StCObDAKY
tFFLUtNT
13
9
127
21
22
441
444
1
ae
eo
t
IB
28
6
25
20
4
2
L
IB
1
3
2
9
2
3
3
5
PCNT
REM.
93
93
84
40
44
30
4
96
63
27
94
53
71
100
67
97
73
»7
97
92
38
94
33
63
33
25
L
L
L
L
L
L
L
I
I
L
L
I
L
L
OTHER
EFFLUENT
9
e
170
16
16
425
419
1
74
63
7
21
25
1
1
5
1
1
1
1
1
3
16
25
20
22
e
I
19
1
3
2
5
2
3
3
5
PRIMARY
SLUCGE
1695
1603
3320
152
66
2328
NOT RUN
97
1619
NOT RUN
1321
26
283
1
1
4
14
NTD
N-D
97
N-0
15
50
17
3
1
40
15
N-D
1B5
N-D
N-D
461
27
M-0
N-0
N-0
COMBINED
SLUDGE
45536
169167
64067
6817
448
55264
NOT RUN
1000
42101
NOT RUN
12V36J
108
4270
7
N-D
73
65
32
N-0
1620
79
307
479
N-D
47
14
517
20
177
63
169
707
5956
910
239
N-0
111
SECONDARY
SLUO&E
2819
3893
5687
488
173
3996
HOT RUN
913
2974
NOT RUN
3500
24
1179
0
N-D
N-D
N-D
N-D
N-D
51
N-0
21
1
N-D
5
N-D
833
2
N-D
580
N-0
112
1395
N-D
7
N-D
N-0
-------
SUHKAkY Of ANALYTICAL UAlA
PLANT 17
I-RACIIUN PARAMEUK
BASE-NEUI.
ANIHMACLhE
PHLNANTHKENc
CO
A
PESTICIDES MEPlACHLOk
ALPHA-UHC
6EIA-6HC
CAMMA-bHC
HEIALS ANTIMONY
ARSENIC
CAOMIUM
CHROHIUH
COPPLR
CYANIDE
LEAU
MtKCURY
NICKEL
SELENIUM
SILVER
/INC
N-C HEIALS ALUMINUM
bARIUM
CALCIUM
1KUN
MAGNESIUM
MANGANESE
SODIUM
UMIS
UC/L
OC/L
UG/L
UG/L
NG/L
NC/L
NC/L
NC/L
UG/L
UC/L
UC/L
UC/L
UC/L
UG/L
UC/L
NC/L
UG/L
UC/L
UG/L
UG/L
UG/L
UC/L
MG/L
UG/L
MG/L
UC/L
MG/L
H.fLUtNI
L 5
L 3
I 3
I 3
2to
10
L 400
22
I 5C
I 50
27
100
1U5
277
ai
350
34
I 50
2C
272
956
110
55
1103
9
130
53
L
L
L
L
L
L
L
L
L
L
I
SECONDARY
IffLbtlH
5
3
3
a
100
50
20
21C
50
50
4
34
35
133
11
200
22
50
2
51
116
39
50
216
*
104
54
PCNT
HEM.
65
69
61
52
66
43
35
90
dl
66
65
9
60
20
OHiER
EFFLUEN
L 5
L 3
L 3
L 3
I 200
26
12
L 120
I 50
L 50
L 2
34
12
54
I 20
L 200
44
L 50
I 2
30
76
47
52
161
«
107
54
PRIMARY
I SLUDGE
N-0
31
31
N-0
N-0
N-0
N-0
N-0
L 50
16
78
177
596
537
592
19167
104
L 100
05
1163
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT HUN
COM81NEO
SLUDGE
111
460
460
165
N-0
N-0
N-0
N-0
156
282
1362
S717
16100
67517
12300
47000
1592
166
2900
31233
NOT RUN
NOT RUN
NOT RUN
NUT RUN
NOT RUN
HOT RUN
NOT RUN
SECONDARY
SLUDGE
N-0
N-D
N-0
N-D
N-0
N-0
N-0
N-0
L 50
16
357
610
1663
960
1167
24167
284
L 100
277
3317
NOT RUN
NOT RUN
NUT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
H1ILLUIANIS NO I LISIEO MERE NEVE.K OLULTIU
L-ltSS IMANI N-0 NOT OtlLCHL/i
PRLLIIIINAKY UAIA UNL Y 10 6E VtKIMU
-------
MASS BALANCE IN LBB. PER DAY
PLANT 17
FRACTION
CONVENTIONALS
NON-CONVENTIONALB
VOLATILES
CO
PARAMETER
BOD
TOTAL 6USP. SOLIDS
COD
OIL I OREASE
TOTAL PHENOLS
TOTAL SOLIDS
TOTAL DIBS. SOLIDS
TOTAL VOLATILE SOLIDS
VOLATILE DISS. SOLIDS
TOTAL VOL. BUS. SOLIDS
AMMONIA NITROGEN
TOC
DENZENE
CARBON TETRACHLORIDE
lrl>l-TRICHLOROETHANE
1 r 1 -DICHLpROETIIANE
CHLOROFORM
I.2-TRANS-DICHLOROETHYLENE
ETHYLBENZENE
HETHYLENE CHLORIDE
NETHYL CHLORIDE
DICHLORODIFLUOROHETHANE
TETRACHLOROETHYLENE
TOLUENE
TRICHLOROETHYLENE
PENTACHLOROPHENOL
PHENOL
NAPHTHALENE
BIS(2-ETHYLHEXYL> PHTHALATE
BUTYL BENZYL PHTHALATE
DI-N-BUTYL PHTHALATE
DIETHYL PHTHALATE
ANTHRACENE
PHENANTHRENE
HEPTACHLOR
ALPHA-DHC
BETA-DHC
OAMHA-BHC
ARSENIC
CADMIUM
CHROMIUH
COPPER
CYANIDE
LEAD
MERCURY
NICKEL
POLLUTANTS NOT LISTED WERE NOT DETECTED
L-LESS THAN) N-D NOT DETECTEDI
PRELIMINARY DATA ONLY TO BE VERIFIED
ACID EXTRACT
BASE-NEUTRALS
PESTICIDES
METALS
INFLUENT
23715
15733
95224
4245
4.7
77042
36392
29021
13327
lisa*
4494
11474
.1
N-P
4. 6
,1
.3
,4
3.0
2.7
H-D
N-D
IS. 2
9.8
1.5
3,4
2.0
.4
2.9
.3
.2
.3
N-D
N-D
L 0.1
L O.I
N-D
L O.I
N-D
3.3
13.2
22.4
33.9
9.9
L O.t
4.2
TOTAL OUT
12031
12447
34248
37BI
3.1
48493
-
21121
-
10499
2338
4057
I 0.1
I 0.1
L O.I
L 0.1
.4
.3
I 0.1
1.0
L 0.1
L O.I
.3
1.4
L o.i
2.1
1.4
.1
4.7
.1
.4
N-D
.1
.1
N-D
N-D
L 0.1
N-D
L 0.1
1.2
5.9
8.8
19.6
5.3
.1
3.5
SECONDARY
EFFLUENT
1392
1041
13392
2351
2.4
34001
34327
10794
9794
735
2204
3429
N-D
N-D
L 0.1
N-D
,4
N-D
N-D
,8
N-D
N-D
.5
42
N-D
2.1
L 0.1
N-D
1.1
N-D
,4
N-D
N-D
N-D
N-D
N-D
I 0.1
N-D
N-Ii
.3
4.2
4.3
14.2 "
1.4
N-D
2.7
PRIMARY
SLUDOE
4917
4542
IJ55I
420
.3
9501
NOT RUN
4409
NOT RUN
3391
104
1133
L 0.
L 0.
L 0.
L 0.
N-
.
L 0.
.
L 0.
L 0.
L 0.
.2
L 0.1
N-D
.8
N-D
1.9
.1
N-D
N-D
.1
.1
N-D
N-D
N-D
N-D
L 0.1
.3
.7
2.4
2.2
2.4
L 0.1
,4
SECONDARY
SLUDOE
3522
4844
7105
610
.2
4993
NOT RUN
3714
NOT RUN
4373
30.0
1473
L 0.1
N-D
N-D
N-D
N-D
L 0.1
L O.t
L 0.1
N-D
L 0.1
N-D
1.0
L 0.1
N-D
.7
.1
1.7
N-D
L O.i
N-D
N-D
N-D
N-D
N-D
N-D
N-D
L 0.1
.4
1.0
2.1
1.2
1 .3
L 0.1
.4
-------
MASS BALANCE IN L§8, ft ft DAY
thAt 11 OH
MEIALS
NUN-CONV. METALS
PARAMETER
SILVER
ZINC
ALUMINUM
BARIUM
CALCIUM
IKON
MAGNESIUM
MANGANESE
SODIUM
PLANT 17
INFLUENT
TOTAL OUT
SECONDARY
EFFLUENT
PRIMARY
SLUDGE
2.4
33.3
117
13.4
4753
135
1102
is.»
4310
15.0
.2
4.2
14.2
4.7
6143
24.4
12.8
4592
.3
4.7
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
SECONDARY
SLUDOE
.3
4.1
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
M
A
I (II IIIIA/IIS NOT LISTED Ut kt NO! l>tltCIt[i
L-IESS THAN* HI) NOT DETECTED)
f h'tLIMINAhV DATA ONLY TO &£ VERIFIED
-------
PERCENT OCCURRENCE OF POLLUTANT PARAMETERS
PLANT 17
fg
PARAMETER
1>1i1-TRICMLOROETHANE
CHLOROFORM
1>2-TRANS-DICHLOROETHYLENE
ETHYLRENZENE
HETHYLENE CHLORIDE
TETRACMLOROETHYLENE
TOLUENE
TRICHLOROETHYLENE
PHENOL
BIS<2-ETHYLIIEXYL) PHTHALATE
CADMIUM
CHROMIUM
COPPER
CYANIDE
LEAD
MERCURY
SILVER
ZINC
PENTACHLOROPHENOL
NICKEL
BUTYL BENZYL PHTHALATE
DIETHYL PHTHALATE
1i1-DICHLOROETHANE
NAPHTHALENE
BENZENE
DI-N-BUTYL PHTHALATE
HEPTACHLOR
ALPHA-BHC
8AHHA-BHC
CARBON TETRACHLORIDE
1>1r2.2-TETRACHLOROETHANE
1r 2-DICHLOROPROPANE
METHYL CHLORIDE
DICHLORODIFLUOROMETHANE
FLUORANTHENE
4•2-BENZANTHRACENE
CHRYSENE
ANTHRACENE
PHENANTHRENE
PYRENE
BETA-BHC
ANTIMONY
ARSENIC
SELENIUM
INFL-
UENT
too
100
100
100
100
100
100
100
100
100
100
100
100
100
too
100
100
100
83
83
67
67
SO
30
33
33
17
17
17
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
SEC.
EFFL.
4) 33
4> 100
6> 0
6} 0
4) 100
4) 100
4) 67
( 6) 0
( 4) 47
( 41 100
4) 47
4) 63
4) 100
61 100
4) 33
4> 0
4) 33
4) 100
4) 47
4) 83
4) 0
4) 0
4> 0
4) 0
4> 0
4) 83
6) 0
4) 0
6) 0
4) 0 ,
4) 0 *
4) 0
4> 0
4) 0
4) 0
6) 0
4) 0
61 0
4> 0
4) 0
61 33
4) 0
6) 0
4) 0
OTHER
EFFL
4) 100
4) B3
4) 0
At 67
4) 100
4) 100
4) SO
4> 47
4) SO
4) 100
61 0
4) 100
4) 100
4) 100
4) 0
4) 0
4) 0
4) 83
4) 67
4) 100
4) 0
6) 0
4) 0
4) 0
4) 0
4) 83
4) 0
4) 17
4) 0
61 0
61 0
4) 0
4) 0
61 0
4) 0
4) 0
4) 0
4) 0
4) 0
4) 0
4) 17
4) 0
4) 0
4) 0
PR I M .
SLtiO.
4) 17
4) 0
4) 100
4) 100
4) SO
4) 17
4) 100
4) 100
4) 33
4) 100
4) 100
61 SO
4) 100
3> 100
4) 100
4) 33
4) 83
61 100
4) 0
61 100
4) 17
4» 0
61 100
61 0
4> 33
4» 0
4) 0
4) 0
61 0
4) 17
4) 0
4) 0
61 33
4> 17
4) 0
4) 0
61 0
4) 33
4) 33
61 0
4) 0
4) 0
4) 33
61 0
COMB.
SI. DO
4) 50
4) 0
4> 100
4) 100
4> 03
61 SO
4> 100
4) 17
4) SO
61 100
61 100
61 100
4) 100
4) 100
SI 100
4) 100
61 100
4) 100
4) 33
4) 100
4) 100
4) 0
4) 83
61 S3
4) SO
61 100
4) 0
4) 0
4) 0
4) 0
4) 33
4> 100
4) 0
4) 33
4) 100
4> 83
4> 83
4) 83
61 83
4) 100
4) 0
S) 100
4) 100
5) 100
SEC.
51 DO
4) 0
4) 0
4> 83
4> 63
4> 17
4) 0
6) 100
4) 17
4) 47
4) 83
4> 100
4) 100
4) 100
4) 100
4) 100
4) SO
4) 100
4 ) 1 00
4) 0
4) 100
4) 0
6) 0
4> 0
4) 17
61 17
4) 17
4) 0
4) 0
4) 0
4) 0
4) 0
4) 0
4> 0
4) 17
4) 0
4> 0
4) 0
4) 0
4) 0
4) 0
( 4) 0
( 5> 0
( 4) 17
( S) 0
TAP
WATER
4) 0 <
4> 100
4> 0
61 0
61 0
4) 0
4) 0
4) 0
4> 0
4) 0
4> 0
4) 0
4) 100
4) O
4> 0
4) 0
4) 0
4) 0
4) 0
4) 0
4) 0
4> 0
4> 0
4) 0
4) 0
4) 100
4) 0
4) 0
4) 0
4> 0
4) 0
4) 0
61 0
4) 0
4) 0
4) 0
4) 0
4) 0
4) 0
4) 0
( 4) 0
( S) 0
( 4) 0
( S) 0
1 )
1)
1)
1)
1)
11
\ >
1)
1)
1)
1>
1)
1)
>
1)
1)
1)
I)
t>
1)
1>
1)
1)
1)
1)
1)
1)
1)
1)
t)
1)
1>
1>
1)
1)
1)
1)
1)
1>
1)
1)
1)
1)
( 1)
POLLUTANTS NOT LISTED WERE NOT DETECTED AT ANY SAMPLE POIMT
UNCONFIRMED PESTICIDES WERE ASSUMED NOT DETECTED
NUMBERS IN PARENTHESES ARE THE NUMBER OF SAMPLES TAKEN
PRELIMINARY DATA ONLY-TO BE VERIFIED
-------
SUHMAKY Of ANALYTICAL DATA
PLAN1 16
CONVENT|ONALS
NUN-CUNVLNlIONALS
VULAIILES
BOO
TOTAL SUSP. SULIDS
COO
OIL C CREASE
TOTAL PHENOLS
10IAL SOLIDS
TOTAL OISS. SOLIDS
SETILEABLL SULIOS
TOIAL VOLAI ILL SOLIDS
VOLATILE UISS. SOLIDS
TOTAL VOL. SUS. SOLIDS
AHHONIA HI IROCEN
TOC
DEH2ENE
1 ,2-OICHLUfcUEIrUI*(:
1,1.1-TRlCHLONOEIHANL
1. I-OICHLOKOt IHAUt
1,1,2,2-TETKACHLGfcOElHANE
CHLOROFORM
1 ,2-TRANS-OICilLO^OLlHYLENl
MtltmCNt CHLOHIOL
TRICHLOKOFLUOKOHLlHANt
lEIHACllLOKOLlHYLExE
IQlUtt.t
IRICHLOKQtlMYLLNL
2-CHLUHOPHENOL
2 ,4-DICIILOkOPllLNLL
2,4-OlMEIIIYLPIIEIlLlL
ACID EXINACI
BASt-NLUIKALS NAPHIMALthL
B1S12-E IHYLHLXYLI PHIIIALAIt
ttUlYL BENiYL PHlMALAIt
01 -N-BUFYl CM1IIAI AIL
111 -N-UCI n HII MM Alt
UlLlllYL flllllUAlc
HIIL I HI 41.1 1, Nil) lliHU titKL NLVtK UtllCHO
1-llbS IIUNi N-U Illll bill I HIM
I Ml Inn.AKY ii4i* i./.i* 10 hL vlklMUi
UNITS
MC/L
MC/L
HC/L
MC/L
UC/L
MC/L
MC/L
ML/L
MC/L
MC/L
MC/L
MC/L
MC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
SECONDARY PCNJ
INFLUENT EFFLUENT KEM.
20B
260
717
46
5b
47b
216
11
l«,e
102
152
10
162
9
0
63
2
L 1
2
L t
12
SO
0
9
34
23
0
2
0
1
20
2
70
4
s
3U
I J
37 82
21 92
82 89
17 63
12 79
279 42
239
t 1 91
42 79
57 44
15 90
7 30
36 78
I
L
L
L
L
L
L
L
L
tt9
86
50
100
92
3 74
56
97
a?
50
L 2
I 5
0 100
L 2
4b 31
L 2 50
2 50
2 l>5
L 3
PRIMARY
SLUOCE
25243
162900
97333
9100
624
84607
NOT fcUN
997
44464
NOT *UN
96700
67
662
44
N-0
174
15
277
19
227
832
44
44
N-0
3V 8
245
20
144
N-0
N-0
113
311
4225
1231
35 J
94
H-D
SECONDARY
SLUDGE
6554
17933
17547
653
61
11039
NOT RUN
994
7511
NOT RUN
12866
10
369
1
N-0
N-0
4
12
N-0
4
6
2
N-0
N-0
31
3
N-0
N-0
t>-0
N-D
223
N-0
HO 72
44
J7
111
131
-------
SUMMARY OF ANALYTICAL DATA
PLANT 16
BASE-NEUTRALS
^PESTICIDES
METALS
r\>
NON-CONV. METALS
PARAMETER
U2-BENZANTHRACENE
CHRYSENE
ANTHRACENE
FLUORENE
PHENANTHRtNE
PYRENE
CHLORDANE
ALPHA-BMC
GAHHA-BHC
ANTIMONY
ARSENIC
CADMIUM
CHROMIUM
COPPER
CYANIDE
LEAD
MERCURY
NICKEL
SELENIUM
SILVER
ZINC
ALUMINUM
BARIUM
CALCIUM
IRON
MAGNESIUM
MANGANESE
SODIUM
UNITS
UG/L L
UC/L L
UC/L I
UC/L I
UG/L L
UG/L I
NC/L I
NG/L
NG/L
UG/L L
UG/L I
UG/L
UC/L
UC/L
UG/L
UG/L
NG/L
UG/L
UG/L L
UG/L
UG/L
UG/L
UG/L
HG/L
UG/L
MG/L
UG/L
HG/L
INFLUENT
5
5
3
3
3
3
2000
25
12
SO
SO
2
51
117
169
136
517
2*
50
15
330
4910
111
16
4103
4
162
45
L
I
I
L
L
L
L
L
L
L
SECONDAKY
EFFLUENT
5
5
3
3
3
3
33
52
63
50
50
2
11
6
11J
23
200
14
50
3
75
417
17
13
366
3
93
49
PCNT
HEM.
13
78
95
33
83
61
42
80
77
92
85
19
91
25
43
PRIMARY
SLUDGE
137
137
1123
214
1123
109
N-D
N-D
N-D
223
350
347
3350
14733
25250
25500
203333
1348
123
1078
32333
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
SECONDARY
SLUDGE
N-0
N-D
N-0
N-0
K-D
N-D
N-D
N-D
N-D
50
57
143
563
3283
5233
5200
4833
352
L 100
558
13950
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
POLLUTANTS NOT LISTED HERE NEVER DETECTED
L-LESS THANI N-D NOT DETECUDI
PRELIMINARY DATA ONLY---TO BE VERIFIED
-------
MASS BALANCE IN LBS. PER DAY
PLANT 18
F Ft ACT I OH
CONVENTIONAL8
MON-CONVENTIONAL8
VOLATILES
¥ K
A <**
ACID EXTRACT
BASE-NEUTRALS
I Ifal ft ll't H
Ml IAI S
PARAMETER
BOD
TOTAL SUSP, SOLIDS
COD
OIL I GREASE
TOTAL PHENOLS
TOTAL SOLIDS
TOTAL DISS. SOLIDS
TOTAL VOLATILE SOLIDS
VOLATILE DISS. SOLIDS
TOTAL VOL. SUB. SOLIDS
AMMONIA NITROGEN
TOC
BENZENE
Ir2-DICHLOROETHANE
If I>|-TRICHLOROETHANE
ItI-DICHLOROETHANE
It If2f2-TETRACHLOROETHANE
CHLOROFORM
1f2-TRANB-DICHLOROETHYLENE
EIHYLBENZENE
HETHYLENE CHLORIDE
TRICMLOROFLUOROMETHANE
TETRACHLOROETHYLENE
TOLUENE
TRICHLOROETHYLENE
2-CHLOROPHENOL
2f4-DICHLOROPHENOL
2t 4-DIMETHYLPHENOL
PEHTACHLOROPHENOL
PHENOL
NAPHTHALENE
BIS(2-ETHYLIIEXYL » PHTHALATE
BUTYL BENZYL PHTHALATE
DI-N-BUTYL PHTHALATE
DI-N-OCTVL PHTHALATE
DIETHYL PHTHALATE
I,2-BENZANTHRACENE
CHRYSENE
ANTHRACENE
FLUORENE
PHENANHIfttNE
PYKENE
CHI OKhANE
Al CHA-6IIC
CAMHA-DHC
ANTIMONV
INFLUENT
108374
139444
373712
23813
30.3
249257
112609
103249
33189
790S3
S215
84213
4.8
I O.I
32.4
.9
N-D
.9
N-D
4.3
24.0
L 0.1
4.S
17.4
11.7
L 0.1
1.0
.2
.7
10. S
.9
34.4
1 .8
1.9
19. 8
N-D
N-D
N-D
N-D
N-D
N-D
N-0
H-0
I 0,1
L O.I
NO
TOTAL OUT
84984
300539
230814
22928
7.4
291139
-
103443
-
177384
3597
21342
L 0.1
N-0
S.I
L 0.1
.3
, i
.3
1 .0
7.0
L O.I
2.2
.4
2.0
L 0.1
.3
N-D
N-0
1 .1
.4
44.0
1 .4
1 .3
2.3
.4
.2
.2
1 .3
.2
1 .1
, 1
L O.I
L O.I
L O.I
. 5
SECONDARY
EFFLUENT
19207
1IOSS
42740
8491
4.3
143374
124428
21901
29723
7822
3474
18484
N-0
N-D
4.9
N-D
N-0
L 0.1
N-0
N-0
4.9
N-D
2.2
N-D
1 .7
N-0
.3
N-0
N-D
I O.I
N-D
24.8
N-0
.8
I.I
N-D
N-D
N-D
N-D
N-D
N-D
N-U
L 0.1
I O.I
L O.I
N-D
PRIMARY
SLUDGE
29438
213298
113310
10412
1.0
98449
NOT RUN
31834
NOT RUN
115104
78.3
1003
I O.I
N-0
.2
L 0. 1
.3
L O.I
.3
1 .0
L O.I
L 0.1
N-D
.5
,3
L 0.1
.2
N-D
N-D
. 1
.4
4.9
1 .4
.4
. 1
N-D
.2
.2
1 .3
.2
1 .3
. 1
N-D
N-D
N-D
.3
SECONDARY
SLUDGE
34341
74184
74344
3423
.3
44894
NOT RUN
31910
NOT RUN
34440
43.2
1431
L 0,1
N-0
N-D
L 0.1
L 0.1
N-0
L 0. I
L O.I
L 0.1
N-D
N-0
.1
t 0.1
N-0
N-0
N-0
N-D
.9
N-0
34.3
.2
.3
1.3
.4
N-D
N-D
N-D
N-D
N-D
N-D
N-D
N-D
N-D
.2
HIIIUIANTB NOT LISTED UEKE NOT DETECTED
I ItSS III AH I N-D NOT DETECTED!
rhll IMINAKY DATA ONLY TO BE VEMFILi'
-------
FRACTION
NETALS
NABS BALANCE IN LDS. PER DAY
PLANT IB
NON-CONV. METALS
PARAMETER
ARSENIC
CADMIUM
CHROMIUM
COPPER
CYANIDE
LEAD
MERCURY
NICKEL
SELENIUM
SILVER
ZINC
ALUMINUM
BARIUM
CALCIUM
IRON
MAGNESIUM
MANGANESE
60DIUN
INFLUENT
N-D
1.2
24.7
61. t
88.0
70,7
.3
12.4
N-D
7.6
172
2560
5B.O
8343
2140
1912
84.3
23205
TOTAL OUT
.4
1.0
12.1
34.4
110
63.9
.3
10.4
.1
S.O
13*
_
-
-
-
-
-
-
SECONDARY
EFFLUENT
N-D
N-D
3.4
3.3
58.9
12.1
.1
7.3
N-D
1.3
38.8
218
8.8
4844
191
1391
48.4
25438
PRIMARY
SLUDOE
,4
.4
4.1
17.2
29.4
29.7
.2
1.4
.1
1.3
37.7
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
SECONDARY
SLUDGE
.2
.4
2.4
13.9
22.2
22.1
L 0.1
1.3
N-D
2.4
S9.3
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
8
O
CTl
POLLUTANTS NOT LISTED MERE NOT DETECTED
L-LEBS THANI N-D NOT DETECTED)
PRELIMINARY DATA ONLY TO BE VERIFIED
-------
PERCENT OCCURRENCE OF POLLUTANT PARAMETERS
PLANT 18
to
to
FARAHETER
1,1,1 TRICUIOKOETHANE
HEIHYLENE CHLORIDE
TE1RACHLOROETHYLENE
IOLUENE
IKILItl OkOEIHYLEME
CHROHIIIH
COPPER
CVANIbE
I EAb
HERCUKY
NICKEL
ZINC
BENZENE
CHLOKOFORH
ETHYLBENZENE
PHENOL
BI8(2-ETHYLHEXYL> PIIIHALAIE
BUHL BEN2YL PHTMALATE
SILVER
GAMMA bllC
CAbMlUH
If1-DICHLOROETHANE
NAPHIIIALENE
bl-N bUTYL PHIHALATE
til-N OCIYL PHIHALATE
1 .2-blCHLOROETHANE
IR1 CHIOROFLU080HE THANE
2 CHI OfcOPHENOL
2.4 -bICHLOfcOPHENOL
2>4-bIHETHYLPH£NOL
PtHIACIIC QHOPHEHOL
A1PIIA bllC
1iI.2.2 lETRACHLOROEIHAHE
1.2-TRAN8-DICHLOROETHYLENE
blEIHYL PHTIIALATE
1,2 llLH/ANIIIRACENE
CHRY8ENE
ANMIRACENE
U (/UhtHE
PHENANTHRENE
PYRENE
CHLOKbANE
AN1 IHIINY
AKSENIC
bll ENIUH
INFL-
UENT
100
100
100
100
100
100
100
100
100
100
100
100
63
83
63
83
63
63
63
67
SO
33
33
33
33
17
17
17
17
17
17
17
0
0
0
0
0
0
0
0
0
0
0
0
0
( 4>
( 4t
< 4>
< 4)
I 4>
( 4)
< A)
( A>
( A>
< 4>
< A)
< 4)
( 4>
( 4>
< 4)
I A>
< 4)
< 4>
( 4>
( 4>
( 4»
< 4>
< 6)
< 4>
( 6)
( 4>
< A)
( A)
( 4)
( A)
( At
< 4»
( A)
< 4)
< 4»
( 6)
( 4>
< 6)
( 4>
( A)
( 6)
( A)
( A)
( A)
( A)
SECONbAKY
EFFL.
100
63
too
0
too
too
63
100
47
S3
83
too
0
17
0
17
63
0
47
too
0
0
0
47
17
o
Q
Q
17
0
o
33
o
Q
o
o
Q
o
Q
0
o
t 7
Q
Q
Q
4)
4)
4>
4)
4>
4>
4)
4>
4>
i»
4)
4>
4)
4)
4)
4)
4)
4>
4)
4>
4>
4)
4)
4>
4>
4)
4)
4)
4)
4)
4)
4)
4)
4)
4)
4)
4)
4>
4>
4)
4>
4)
4)
4)
4)
PRIH.
SLDO
100 < 4)
100 < 4)
0
100
too
100
100
100
too
100
100
too
100
47
63
63
100
63
too
0
too
33
100
100
17
0
100
33
100
o
o
4)
83
too
0
too
100
too
47
100
too
0
too
100
47
4)
4)
4)
4)
4)
4)
4)
4)
4)
4>
4)
4>
4)
4)
4)
4)
4)
4>
4)
4)
4)
4)
4)
4)
4)
4)
4)
4>
4>
4)
4)
4)
4)
4)
4)
4)
4)
4)
4)
4)
4)
4)
4)
SEC.
SI DO
0 <
83 (
0 <
100 (
40 <
too <
100 <
100 (
too <
17 (
too (
too <
33 <
0 (
33 (
too <
too <
33 (
too (
0 <
too <
SO (
0 <
47 <
33 (
0 (
0 <
0 <
0 <
0 <
0 <
0 <
83 <
30 (
17 (
0 I
0 (
0 (
0 (
0 (
0 (
0 (
too <
too <
0 (
4)
4)
4)
4)
S>
4)
4)
4)
4)
4)
4)
4)
4>
4)
4)
4)
4>
4)
4)
4)
4>
4)
4)
4)
4)
4)
4>
4)
4)
4)
4)
4)
4)
4)
4)
4)
4>
4)
4)
4)
4)
4>
4>
4)
4)
TAP
UATER
0 ( 1)
100 < 1)
100
0
0
0
100
Q
Q
0
Q
100
0
too
0
0
|00
o
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1 )
1 )
1)
1)
1)
)
1)
1)
1)
1)
1)
1 )
1 )
t)
1 )
1)
1)
1)
1)
1 )
1)
1)
1>
1)
I)
1 )
1 )
1 )
1 >
1>
>
1
1 )
1 )
I II! I MIAMI S Hill tltilLb UEKE HUI 1'MLCIEb AT ANY brtHI-l E FOINI
LJIVl OHI IKHLU ttbllCll/ES UEKL AL,MII1t|j NO! I'tltt.llu
NlinbEMi IN t AKLNTHEUEb AKE THE NimbtK lit SAIUIES IAMN
IKM1HINARY bATA UNI r 10 lit VIKIMtl'
-------
SUMMARY OF ANALYTICAL DATA
PLAN! 19
.FRACTION
CONV.
"NON-CONV.
PARAMETER
0>
BUD
TOTAL SUSP. SOL I OS
CUD
OIL C GREASE
TOTAL PHENOLS
TOTAL SOLIDS
TOTAL DISS. SOLIDS
SETTLEABLE SOLIDS
TOTAL VOLATILt SOLIDS
VOLATILE 01SS. SOLIUS
TOTAL VOL. SUS. SOLIDS
AMMONIA NITROGEN
TOC
VOLAT1LES BENZENE
CHLQRCOENIENE
1,2-DlCHLORUETHANE
1,1,1-TRICHLOROETHANE
1,1-DICHLOROETHANE
I,1,2,2-TETSACHLJRUtlHANE
CHLOROFORM
1,2-TRANS-DICHLORUETHYLENE
1,2-D1CHLOROPROPANE
ETHYLBENZENE
HETHYLENE CHLORIDE
METHYL CHLORIDE
METHYL BRUHlOt
TRICHLOKOFLUOhOMETHAWE
OICHLURODIFLUOROMETIIANt
TETKACHLORUETHYLENE
TOLUENE
TRICHLORUETHYLENE
VINYL CHLORIDE
ACIDS. 2,4,6-TRICHLOROPHENOL
2-CHLOROPHENOL
2i4-DICHLOROPHENOL
2,4-OIMETHYLPHENOL
PENTACIILUROPHENOL
PHENOL
POLLUTANTS NOT LISTED MERE NEVER OEUCUO
L-LESS THANI N-D NOT DETECTED;
PRELIMINARY DATA ONLY TO BE VEKIFIEL
UNITS INFLUENT
MG/L
HG/L
MC/L
MG/L
UG/L
HG/L
HG/L
ML/L
HG/L
HG/L
MG/L
MG/L
HG/L
UG/L
UG/l
UG/L
UG/L
UG/L
UG/L
UG/L
UG/L
UG/L
UG/L
UG/L
UG/L
UG/L
UG/L
UG/L
UG/L
UG/L
UG/L
UG/L
UG/L
UG/L
UG/L
UG/L
UG/L
UG/L
379
IB7
7t 3
• 112
258
1061
745
t
3tO
9'..
134
34
211
4
3
1
49
0
L 1
It
5
2
21
93
32
I 20
0
167
15
60
32
IS
L 2
2
L 2
2
I 5
130
L
t
I
L
t
L
L
L
L
L
L
SECONDARY PCMT
EFFLUENT REH.
37
22
141
15
35
762
722
1
12B
109
13
19
17
1
I
1
30
0
1
16
I
I
4
66
340
36
1
20
18
3
18
20
2
1
1
1
5
0
90
88
DO
87
86
28
3
UB
66
90
44
68
75
6T
39
11
80
50
81
27
88
95
44
50
50
100
PRIMARY
EFFLUENT
325
132
698
37
271
1007
671
1
336
79
77
20
187
3
2
1
31
1
0
14
2
1
20
66
574
110
0
130
22
61
25
72
0
3
0
1
I 5
57
L
L
L
L
I
L
L
I
L
I
I
PRE CL PRIMARY
EFFLUENT SLUDGE
45
29
146
16
48
756
674
I
120
82
21
25
73
1
4
3
61
375
42
|
20
18
2
17
20
2
1
1
3
5
0
1-9693
79583
9-4400
7920
684
58303
NOI RUN
1000
40131
NOT RUN
47550
97
981
15
N-0
N-D
115
10
657
29
7
N-D
336
32
N-D
N-0
M-D
N-0
H-0
980
376
N-0
5
28
12
N-0
20
501
SECONDARY
SLUDGE
8989
22500
21734
512
205
18044
NOT
984
RUN
13354
NOT
RUN
13667
52
675
2
N-D
N-D
67
19
1
19
341
N-D
14
29
N-0
N-D
N-D
N-0
N-D
32
28
N^D
N-D
N-D
N-D
N-0
M-0
118
-------
SUMMARY OF ANALYTICAL DATA
PLANT
Co ^
A
tkAUIUH PARAMLIEK
bASE-NEUT. 1,2,4-rRlCMLORUbENJENE
1,2-OICMLOROBLNZENE
1 .3-01CHLOKOJEMENE
I .S-OICHLOROatNZENE
FLUURANIIIENE
NAPHItULtNE
B1SI2-ETHYLH£XYL) PHTHALAlf
bUKL BEU2YL PHTHALAIE
UI-N-BUTYL PillMALAIt
DI-N-OCIYL PHIHALATE
DIEIIIYL PIITHALATE
ANTHRACINt
PHENANTHRENt
PYHENE
PESTICIDES 4,4'-UOE
4,'i<-L)l)0
HEPIACHLUR
CAHHA-bHC
MLIALS ANIIHUNY
AKSLNIC
CAOHIUH
CIIKOHIUH
COPPER
CYANIDE
LEAD
MEKCURY
NICKEL
SELENIUM
SILVER
I INC
N-C MEIALS ALUMINUM
bARIUM
CALCIUM
IRON
MAGNESIUM
MANGANESE
iUIIIUM
UN 11 i
UC/L
UG/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
NC/L
NG/L
NC/L
NC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
NC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
MC/L
UC/L
MC/L
UC/L
MC/L
II.HUtM
L
I
L
I
I
L
t
L
I
I
L
5
7
5
2
4
3
Jj
19
I
S
3
5
S
*
200
Ub
35
105
SO
50
9
107
9b
714
47
too
54
50
1C
224
3i54
120
2b
2035
16
10
150
L
L
L
L
L
L
L
L
L
L
L
L
L
L
L
L
L
L
L
L
SCCUN'DAhV PCNT
EFFLULIH REM.
5
5
5
2
4
3
20
3
4
5
b
S
5
4
200
300
100
57
50
50
2
2t
16
337
50
03
44
50
5
38
337
16
25
643
16
111
152
29
39
64
46
70
76
64
53
66
19
50
63
91
65
11
59
22
L
L
L
L
L
L
L
L
I
I
L
L
L
PRIMARY
tFFLUENT
5
6
5
1
4
4
36
12
4
2
3
5
5
4
200
300
100
120
50
50
6
63
64
509
10
6t»3
58
50
10
249
298tt
IOJ
27
2257
16
125
148
L
L
L
L
L
I
L
L
L
L
L
L
L
L
L
L
L
I
L
PRE CL PRIMARY
EFFLUENT SLUOCL
5
3
5
1
4
3
20
3
4
5
5
5
5
4
200
300
100
26
50
50
2
23
15
247
50
100
45
25
5
43
325
18
25
656
16
109
149
479
911
300
519
114
471
5038
3428
377
19
N-U
229
229
32
H-0
N-0
N-0
N-0
150
265
917
5350
12363
166000
12363
219000
2042
147
650
26363
NOT KUN
NOT RUN
NOT KUN
NOT RUN
NOT RUN
NO! RUN
NOT f>UN
SECONDARY
SLUDGE
64
112
41
70
32
2
1914
N-0
21
6
N-0
N-0
N-0
11
,1667
N-0
N-D
N-0
82
131
2727
1343
2917
33917
5100
79167
346
17
410
16963
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
fllllUUNli NUI L1STLO UE.U NtVth UClLCIU)
I-IESS THAN! N-D NUI DtTECItUi
PKLLIMINAKY JAli UNLY II) Ut VEMMLL
-------
MASS BALANCE IN LBB. PER PAY
PLANT 19
FRACTION
CONVENTIONALS
NON-CONVENTIONALS
VOLATILE*
PARAMETER
BOD
TOTAL SUSP. SOLIDS
COD
OIL t GREASE
TOTAL PHENOLS
TOTAL SOLIDS
TOTAL DISS. SOLIDS
TOTAL VOLATILE SOLIDS
VOLATILE DISS. SOLIDS
TOTAL VOL. BUS. SOLIDS
AMMONIA NITROGEN
TOC
BENZENE
CHLOROBENZENE
1>2-DICHLOROETHANE
1>1>1-TRICHLOROETHANE
1,1-DICHLOROETHANE
1.1r2.2-TETRACHLOROETHANE
CHLOROFORM
I>2-TRANS-DICHLOROETHVLENE
1,2-DICHLOROPROPANE
ETHYLBENZENE
HETHYLENE CHLORIDE
METHYL CHLORIDE
HETHYL BROMIDE
TRICHLOROFLUOROHETHANE
DICHLORODIFLUOROHETHANE
TETRACHLOROETHYLENE
TOLUENE
TRICHLOROETHYLENE
VINYL CHLORIDE
2r4r6-TRICHLOROPHENOL
2-CHLOROPHENOL
2r4-DICHLOROPH£NOL
2r4-DIMETHYLPHENOL
PEHTACHLOROPHENOL
PHENOL
lr2r4-TRICHLOROBENZENE
lr2-DICHLOROBENZENE
lr3-DICHLOROBENZENE
lr4-DICHLOROBENZENE
FLUORANTHENE
NAPHTHALENE
BIB<2-ETHYLHEXYL> PHTHALATE
BUTYL BENZYL PHTHALATE
DI-N-BUTYL PHTHALATE
DI-N-OCTYL PHTHALATE
DIETHYL PHTHALATE
POLLUTANTS NOT LISTED WERE NOT DETECTED
L-LE59 THANI N-D NOT DETECTEDI
PRELIMINARY DATA ONLY TO BE VERIFIED
ACID EXTRACT
BASE-NEUTRALS
INFLUENT
21404?
10S330
408143
43394
H4
597225
420348
214614
53842
75848
19202
I1BB83
2.1
1.7
.7
27.5
.2
H-»
10.4
2.9
.8
12.0
52. 4
is.i
N-D
.2
74.1
8.6
34.0
17.9
10.9
N-D
1.2
N-D
1.0
N-D
73,4
N-D
4.0
N-D
1.3
N-D
1.4
IB. 4
10.5
.7
N-D
1.7
TOTAL OUT
138702
383547
48228S
32374
22.8
714432
-
274824
-
230811
11273
45452
L 0.1
N-D
.8
17.8
.2
1.6
9.4
2.4
.4
3.3
38.9
192
21.4
N-D
N-D
10.4
4.1
11.2
N-D
L 0.1
L 0.1
.6
,4
L 0.1
2.3
1.7
5.7
1.0
2,6
.5
1.2
38.3
8.4
I.I
L 0.1
N-D
SECONDARY
EFFLUENT
20803
12237
7V82I
8440
19,5
430452
407841
72197
61540
7248
10637
38028
N-D
N-D
.8
17.0
I 0.1
N-D
9.2
N-D
.4
2.4
38.4
192
21.4
N-D
N-D
10.4
I.S
10.1
N-D
N-D
N-D
.6
.4
N-D
L 0.1
N-D
2.5
N-D
.0
N-D
N-D
11.0
N-D
N-D
N-D
N-D
PRIMARY
SLUDGE
49212
198879
235904
19792
1 .7
145698
NOT RUN
100287
NOT RUN
118827
241
2451
I 0.1
N-D
N-D
.3
t 0.1
1.6
L 0.1
L 0.1
N-D
.8
L 0.1
N-D
N-D
N-D
N-D
N-D
2.4
.9
N-D
L 0.1
L 0.1
L 0.1
N-D
I 0.1
1.3
1.2
2.3
.7
1.3
.3
1.2
12.6
8.6
.9
L 0.1
N-D
SECONDARY
SLUDOE
68887
172431
144558
3924
1.6
138282
NOT RUN
102340
NOT RUN
104734
395
5173
L 0.1
N-D
N-D
.5
.1
L 0.1
.1
2.6
N-D
.1
.2
N-D
N-D
N-D
N-D
N-D
.2
.2
N-D
H-D
N-D
N-D
N-D
N-D
.9
.5
.9
.3
.5
.2
L 0.1
14.7
N-D
.2
L 0.1
N-D
-------
MASS BALANCE IN L6S. PER DAT
PLANT 19
m AC u UN
BASE-NEUTRALS
PESTICIOEfi
METALS
NOM-CONU. METALS
A £
PARAMETER
ANTHRACENE
PHENANTHREME
PYRENE
1.4'-DDE
4.4'-DDD
HEPTACHLOR
OAMHA-BHC
ANTIMONY
ARSENIC
CADMIUM
CHROMIUM
COPPER
CYANIDE
LEAD
MERCURY
NICKEL
SELENIUM
SILVER
ZINC
ALUMINUM
BARIUM
CALCIUM
IRON
MAGNESIUM
MANGANESE
SODIUM
INFLUENT
N-D
N-D
N-D
N-B
L O.I
L O.|
L O.t
N-D
N-D
4.9
40.3
SS.I
403
24.5
.3
30.4
N-0
5. 6
124
200?
67.7
15429
114V
9131
80.9
84904
TOTAL OUT
.4
.4
.2
L 0.1
N-D
N-D
L O.|
1.0
1.7
23.2
38.4
42.1
920
70.0
1. 1
32.6
.3
3.2
217
-
-
-
-
-
-
-
SECONDARY
EFFLUENT
N-D
N-D
N-D
N-D
N-D
M-D
L O.I
N-0
N-D
N-0
14.7
a. a
190
N-0
L 0.1
23.0
N-D
N-D
21.2
190
9.9
14308
474
9131
42.4
85437
PRIMARY
SLUDGE
.4
.4
I 0.1
N-D
N-D
N-D
N-D
.4
.7
2.3
13.4
30.9
470
30.9
.3
3.1
.4
2.1
43.9
NOT RUM
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
SECONDARY
SLUDOE
N-D
N-D
L 0.1
L 0.1
«-D
N-D
«-»
.4
1.0
20.9
10.3
22.4
240
39.1
.4
2.7
,1
I.I
130
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT LISTED WERE NOT DETECTED
I ILS6 MIAN* N-0 NOT DETECTED!
I'M! IMINAKY DATA ONLY TO BE VERIFIED
-------
PERCENT OCCURRENCE OF POLLUTANT PARAMETERS
PLANT 1?
PARAMETER
BENZENE
1.1r1-TRICHLOROETHANE
CHLOROFORM
ETHYLBENZENE
HETHYLENE CHLORIDE
TETRACHLOROETHYLENE
TOLUENE
TR1CMLOROETHYLENE
PHENOL
BUTYL BENZYL PHTHALATE
CHROMIUM
COPPER
CYANIDE
MERCURY
NICKEL
ZINC
CHLOROBENZENE
1,2-TRANB-DICHLOROETHYLENE
If 2-DICIILOROPROPANE
B1S<2-ETHYLHEXYL> PHTHALATE
CAOHIUH
SILVER
2-CHLOROPHENOL
NAPHTHALENE
OAMHA-BHC
LEAD
2.4-DIHETHYLPHEHOL
DIETHYL PHTHALATE
1•2-D1CHLOROETHANE
1,1-PICHLOROETHANE
METHYL CHLORIDE
VINYL CHLORIDE
1.2-DICHLOROBENZENE
1r 4-DICHLOROBENZENE
TRICHLOROFLUOROHETHANE
DICHLORODIFLUOROHETHANE
DI-N-BUTYL PHTHALATE
4r4'-DDD
HEPTACHLOR
1r1r2*2-TETRACHLOROETHANE
METHYL BROMIDE
2>4>6-TRICHLOROPHENOL
2.4-DICHLOROPHENOL
PENTACHLOROPHENOL
1,2,4-TRICHLOROBENZENE
1>3-DICHLOROBENZENE
FLUORANTHENE
'DI-N-OCTYL PHTHALATE
ANTHRACENE
PIIENANTHREHE
PYRENE
POLLUTANTS NOT LISTED HERE NOT DETECTED
UNCONFIRMED PESTICIDES HERE ASSUMED NOT
NUMBERS IN PARENTHESES ARE THE NUMBER OF
PRELIMINARY DATA OHLY-TO BE VERIFIED
INFL- PRIM. PRE CL. SEC. PRIM. SEC. Trtf
UENT EFFL. EFFL EFFL. SLUG SLOG WATER
100
100
too
100 '
100
100
ioo
100
100
too
100
loo
100
100
too
too
63
83
B3
B3
03
83
67
47
47
67
SO
50
33
33
33
33
33
33
17
17
17
17
17
0
0
0
0
0
0
0
0
0
0
0
6> 100
4) 100
«) 100
6) 100
6) 100
4) 100
6) 100
6) 100
6) 100
4) S3
4) 100
4) 100
6> 100
4) 100
41 100
4) 100
6) 03
6) 03
4) SO
4> 03
4> 100
6) 100
6) 03
4) 03
At 67
4) 17
6) 50
4) 30
6) 33
4) 33
4) iOO
4) 33
6) SO
6) 17
6) 17
6) 17
4) 0
4) 0
4) 0
6) 17
6> 17
6) 17
6) 17
6) 0
6) 0
6) 0
6) 0
6> 17
6) 0
4> 0
0 < 6) 0
4) 0
4) 100
4) 100
4) 100
4> 100
4) 100
4) 100
6) 03
6) 17
6) 0
4) 03
6) 100
6) 100
6) 33
4> 100
6) 83
4) 0
4) 0
4) 83
4> 100
6) 0
4> 0
6) 0
6) 0
6) 33
4) 0
6> 67
6) 0
6) 33
6) 33
6> 100
4) 0
4) 33
6) 17
4) 0
4) 0
4) 0
6) 0
4) 0
4) 0
4) 33
4) 0
4) 33
4) 0
4) 0
4) 0
4> 0
4) 0
4) 0
4> 0
6) 0
6) 0
4> 100
4) 100
6) 63
4) 100
4) 100
4) 03
6) 100
4) 17
4> 0
4) IOO
6) 100
6 ) IOO
6) 33
6> 100
4) 03
4) 0
4) 0
4) 67
6) 100
6) 0
6) 0
6) 0
6) 0
6) SO
6) 0
4) 17
6) 0
6) 33
6) 17
6) 03
4) 0
6) SO
6) 17
6) 0
6) 0
6) 0
4) 0
4) 0
4) 0
4) 33
4) 0
6) 33
6) 0
6) 0
6) 0
4> 0
6) 0
4) 0
4) 0
4> 0
4) 47
6) 100
4) 100
4) 100
4) 100
4> 0
4) 100
4) 100
6) 100
4) 100
6) IOO
4) 100
4) 100
4) 100
4> 100
6) tOO
6) 0
6) 17
4) 0
6) 100
4) 100
4) 100
6) 03
6> IOO
6> 0
4) 100
6) 0
6) 0
6) 0
6) 33
6) 0
6) 0
4) 100
6) 100
4) 0
6) 0
6) 100
6) 0
4) 0
6) 100
4) 0
6) 33
4) 50
4) 33
4) IOO
4) 100
4) 100
4> 17
4) 100
4) 47
4) 100
4> 100
4) 03
4) 100
4) 0
4) 100
4) 47
4) 03
4) 0
4) 100
4) 100
6> 100
6) IOO
4) IOO
4) 100
4) 0
4) 100
4) 0
4) 100
4) 100
4) 100
4) 0
4> 17
6) 0
6) 100
6) 0
6) 0
6) 0
4) 100
4) 0
4) 0
4) 100
4) 100
4) 0
4) 0
4) 33
4) 0
4) 0
4) 33
4) 0
4) 0
6) 0
4) 0
6) 03
4) 67
6) 100
6) 17
4) 0
4) 100 < 4) 0
4) IOO ( 6) 47
4> 0 < 1)
4) 0(1)
4) 100 ( M
4) 0(1)
4) IOO ( 1)
6) 0 < l>
4) 0
4) 0
6) 0
4) 0
4) O
6> 100
4) 100
6) 0
4) 0
4) IOO
6) 0
4> 0
4) 0
6) 0
6> 0
4) 0
4) 0
6) 0
1)
1 >
1)
l>
1 >
1>
1)
1)
1)
1)
1)
1)
1)
1)
1)
1)
1>
1 )
4) 0 < 1)
6) 0(1)
6) 0 < 1)
6) 0
6) 0
4) 0
6) 0
6) 0
4) 0
6) 0
6) 0
6) 0
6) 0
6) 0
6) 0
6) 0
6) 0
4) 0
4) 0
4) 0
4) 0
4) 0
4) 0
4) 0
4) 0
1)
1)
l>
1>
1)
1)
1)
1)
1)
1>
1)
1)
1)
1)
1>
1)
1)
1)
1)
1)
1)
1)
4) 0(1)
6> 0 ( 1)
CTED AT ANY SAMPLE POINT
NOT DETECTED
ER OF SAMPLES TAKI l|
-------
PERCENT OCCUKkENCE OF POLLUTANT PARAMETERS
PLANT 1»
fAKAMCILK
4.<'-DDE
AHTIHONV
AHSENIC
SELENIUH
INFL-
UENT
0
0
0
0
( 4)
( 4)
( 4)
PRIH.
EFFL.
0
0
0
0
( 4)
( 4)
< 6)
PRE CL.
EFFL
0
0
0
17
( 4)
< 4)
SEC.
EFFL.
0 I
0 I
0
0
( 6)
( 4)
PRIH.
SLDG
0
100
100
63
*>
SEC.
SLI'G
17 <
100 <
100 (
17 <
TAP
UATElt
0
0
0
0
( 1)
( 1)
MIIIIIIAHIS HOI LISItU ULKt NUT Iitlttltd AT ANr 6AHHLE POINl
Ml/I ONI H.HLLP PISIICIOtS UtKL ASSUMEb HU [ IiEltCltii
HllMbihS IN PARENTHESES ARE THE NUMbEfc OF SAMPLES
tktllHIHAKr DATA UNIV-IO bt I'tKIKItti
-------
SUMMARY OF ANALYTICAL DATA
PLANT 20
.FRACTION
CONV.
NON-CONV.
PARAMETER
VOLATILES
•vl
ro
00
A
AC1U5.
BOD
TOTAL SUSP. SOLIDS
COO '
OIL C CREASE
TOTAL PHENOLS
TOTAL SOLIDS
TOTAL OISS. SOLIDS
SETTLEABLE SOLIDS
TOTAL VOLATILE SOLIUS
VOLATILE OISS. SOLIDS
TOTAL VOL. SUS. SOLIDS
AMMONIA N1TROCEN
TOC
BENZENE
CARBON TtTRACHLURIDE
l.ltl-TRICHLOROETHANE
1,1-OICHLOROETHANE
CHLOROFORM
1,2-TRANS-OICHLUROETHYLENE
EIHYLBENZENE
HETHYLENE CHLORIDE
METHYL CHLORIDE
METHYL BROMIDE
BROMOFORM
DICHLOROBRUMOMETHANE
DICHLOROUIFLUOROMETHANE
CHLORODIBROMOMETHANE
TETRACHLOROETHYLENE
TOLUENE
TRICHLOROETHYLENE
VINYL CHLORIDE
2»4»6-TRKHLOROPHENUL
2,4-DICHLOROPHENOL
2,4-DIMETHYLPHENOL
PHENOL
BASE-NEUT. I,2,4-TRICHLOROBENZENE
1,2-DlCHLORUBEN/ENE
POLLUTANTS NOT LISTED HERE NEVER DETECTED
L-LESS THAN! N-0 NOT DETECTED!
PRELIMINARY DATA UMLY---TO OE VERIFIED
UNITS
HG/L
HG/L
MG/L
MG/L
UG/L
HG/L
HG/L
HL/L
MG/L
MG/L
MG/L
HC/L
MG/L
UG/L
UG/L
UG/L
UG/L
UG/L
UG/L
UG/L
UG/L
UG/L
UG/L
UG/L I
UG/L I
UG/L
UG/L
UC/L
UG/L
UG/L
UG/L
UG/L
UG/L
UG/L
UG/L
UG/L
UG/L L
INFLUENT
2*7
421
750
32
85
Ilb3
798
21
415
eo
256
Ib
90
2
1
32
3
5
2
5
51
5
37
1
1
40
0
15
23
31
13
1
0
0
9
It
5
I
I
I
L
L
I
L
L
L
L
L
L
L
L
SECONDARY
EFFLUtMT
21
13
41
12
50
757
741
1
100
92
7
13
16
1
1
1
1
2
1
1
14
25
20
1
1
19
1
1
1
0
20
1
0
1
0
5
5
PCNT
REM.
91
97
95
63
41
36
7
96
76
97
2»
84
50
97
67
60
50
80
73
46
52
93
96
100
100
6*
L
L
L
L
L
L
L
L
L
L
L
L
I
I
I
I
L
L
L
TERI1ARY
EFFLUENT'
8
5
40
e
21
612
794
1
119
101
2
1
14
1
1
1
1
24
1
1
2
25
20
2
19
17
14
1
1
1
20
1
1
1
1
5
5
PRIMARY
SLUDGE
15833
67833
41067
5337
194
58947
NOT RUN
998
35750
NUT RUN
43750
70
1304
II
N-D
N-D
N-D
N-0
507
61
N-D
N-D
N-D
N-D
N-D
N-0
N-D
N-0
197
309
N-0
N-D
N-D
N-D
53
3oa
88
SECONDARY
SLUDGE
7543
16986
9613
1623
127
B827
NUT RUN
983
(Oil
NO I RUN
10208
27
583
K-0
N-D
N-D
N-D
N-D
N-0
N-D
N-D
N-D
N-D
N-0
N-0
N-0
N-0
N-0
53
N-D
N-0
N-D
N-0
N-0
60
7
N-0
NIIRIMCA1IUM
SLUDGE
8350
25084
9960
270
118
8499
NOT RUN
870
6089
NOT RUN
16167
a
335
N-D
N-0
N-D
N-D
N-D
N-D
H-0
N-0
N-D
N-D
N-D
N-0
N-0
N-D
N-D
125
N-0
N-0
N-D
N-0
N-D
23
N-D
N-0
-------
SUMMARY Of ANALYTICAL OAIA
PLANI 20
IKiCIlUN PAKAHtlbK
ftASE-NtUI. FLUORANIHENE
____ . _ _ ISOPIIORONE
NAPHIHALLNE
blSIJ-EItlYLIIEXYL ) PlIIHJLAlt
BUHL BfN/YL PHIMALAU
OI-N-BUTYL PHTHALAIE
OIETHYL PIUIIALATE
1.2-bENlANIHRACENE
I 1,12-bENZQFLUORANIHENt
CHRY1.ENL
ACENAPHTHYLENE
ANTHRACENE
1.12-bENiOPERYLENE
FLUORENE
PHENANTHRENE
PYRENE
PESTICIDES 4.4--UUO
HEPTACHLUR tPOXlOE
ALPHA -BMC
CAHHA-UhC
htlM-S ANTIHUNY
ARSENIC
CADMIUM
CHRQHIUH
CUPPER
CYANIDE
LtAU
NEHCURY
NICKEL
SELENIUH
SILVER
l(Ht
N-L HEIALS ALUMINUM
OARIUH
CALCIUM
I RUN
HACMLSIUH
UNITS
UC/L
UC/L
UG/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
NC/L
NC/L
NC/L
NC/L
UC/L
UC/L
UG/L
UC/L
UC/L
UC/L
UC/L
NC/L
UC/L
UC/L
UC/L
UC/L
UC/L
UC/L
HC/L
UC/L
MC/L
UC/L
1M-LUCNI
I
I
I
L
L
L
L
L
L
L
L
L
I
t
I
4
6
3
24
b
3
3
5
5
5
10
5
25
5
5
4
52
38
50
113
50
9
2
39
its
f,}
26
761
63
50
7
370
27*0
125
40
2925
2i>
61
L
L
L
L
L
I
L
L
L
L
I
L
I
L
L
I
1
I
I
I
I
I
L
I
I
SECONUAkY PCNT
EFFLUENT REH.
4
10
3
6
3
*
S
5
5
5
10
5
2i
15
5
4
3CO
100
50
72
50
50
2
1
9
i7
bO
200
21
50
5
36
91
44
43
96
24
60
75
63
56
97
95
64
74
67
29
90
97
65
10
97
a
26
L
L
L
L
L
I
L
L
L
L
L
L
L
L
L
L
L
L
I
I
L
I
I
L
L
TERTIARY PRIMARY
EFFLUENT SLUOCE
4
10
3
9
3
4
5
5
5
5
10
5
25
5
5
4
600
200
22
125
50
50
2
5
10
1565
5o
200
14
50
5
3d
31
39
43
19
2*
4
10
N-0
H-0
2357
U27
200
12
N-0
N-0
N-0
N-0
37
N-0
N-0
37
10
N-0
N-0
N-0
N-0
186
258
86
3433
14433
30050
6467
127b52
3200
134 L
773
27617
NUT RUN
NOT kUN
NOT RUN
NO! RUN
NOT RUN
ttU I KUN
SECONDARY NITRIFICATION
SLUOCE SLUDCt
N-0
N-0
N-0
671
N-0
N-0
8
N-0
N-0
N-0
N-0
3
N-0
N-0
3
N-0
N-0
N-0
N-0
h-0
10
76
46
V98
3500
2917
1420
24167
632
100
247
8750
KOI RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
365
N-0
170
425
N-0
N-0
54
70
20
70
305
700
65
250
700
310
N-C
N-0
N-0
N-0
L 50
115
16
1010
2450
1650
1600
19500
775
I 100
165
5950
NUT
NOT
NOT
NOT
NUT
NUI
RUN
RUN
RUN
RUN
RUN
RUN
PULLUIAHIS NUI LISILO MlKt NLVtK JtllCILU
l-IESS IHANI N-D NOT OLTECTEUi
r«lllHlNAKY (JAIA QNLY --- 10 UE VERlFILb
-------
SUMMARY OF ANALYTICAL DATA
PLANT iO
SECONDARY PCNT TERTIARY PRIMARY SECONDARY NMRIFICATIIIN
FRACTION PAKAMETEK UNITS INFLUENT EFFLUtM KEM. EFFLUENT SLUDGE SLUDGE SLUDGE
N-C HETALS SODIUM HG/L 13,! U5 139 NOT RUN NOT RUN NOT RUN
Co
o
POLLUTANTS NUT LISTED HERE NEVER DETECTED
L-LESS THAN» N-0 NUT DETECTEDI
PRELIMINARY DATA ONLY- — TO BE VERIFIED
-------
MASS BALANCE IN LSS. PER DAT
PLANT 20
tHACTION
CONVENTIOMAL8
NUN-CONVENTIONAL 8
VOLATILE8
ui
ACID tXIKACI
UASE-NLUIKALB
I Llil ICll'tS
PARAMETER
BOD
TOTAL SUSP. SOLIDS
COD
OIL 1 GREASE
TOTAL PHENOLS
TOTAL SOLIDS
10TAL DISS. SOLIDS
TOTAL VOLATILE SOLIDS
VOLATILE DISS. SOLIDS
TOTAL VOL. SUS. SOLIDS
AMMONIA NITROGEN
TOC
BENZENE
CARBON TETKACHLORIbE
1 i 1 . 1-TRICHLOROETHANE
1.1-OICHLOROETHANE
CHLOROFORM
1. 2-TfcANS-DICHLOftOETHYLENE
ETHYLBENZENE
NETIIYLENE CHLORIDE
HEIMYL CHLORIDE
METHYL BROMIDE
DICHLOROBROMOMETHANE
DICHLOROblFLUOROHETHANE
CHLORODIBROMOMETHAME
TETRACHLOROETHYLENE
TOLUENE
TRICHLOK'OETHYLENE
VINYL CHLORIDE
2i4»6-TftlCHLOROPHENOL
2.4-D1CHLOROPHENOL
2.4-DIMETHYLPHENOL
PHENOL
i.2.4-IKICMLUkObtNZEME
I.2-OICULOKOHEN2ENE
FLUORANIHENE
ISOPHORONE
DIS(2-EIIIYI lltXYL > PHIHALATE
bUIH btNZVL PHTIIAIAIE
DI N Kimi tit THAI AIE
Ditrim tiiiiKHAit
AHIIIfiACt-Ht
PHtHAHl MHEHt
PYKtNt
4.4' -Pl'b
HLPIACm lift tt 0X1 Lit.
OAHMA-bllC
INFLUENT
245441
417680
745327
31435
84. 3
1173960
792862
411917
87286
234219
18033
96892
2.0
1.3
31.6
3.0
4.6
2.0
4.8
30.7
4.6
36.8
N-0
39.9
.2
13.2
22.9
30.3
13.3
.7
.2
,2
8.9
13.?
N-0
N-b
3.8
23.9
8. 1
2. 7
2. 7
N-0
NO
N-l)
I 0.1
I 0,1
.2
TOTAL OUT
229951
625427
402375
69218
\
52.9
1175027
-
367708
-
388033
13234
3IBB4
L 0.1
N-0
. 7
N-0
2.2
2.2
.3
13.7
N-0
N-II
1.2
19.2
.7
1.2
1.9
J.7
N-D
.3
.2
N-D
1 .3
1 .3
.4
L O.I
N-0
28.4
3.4
.9
. 3
1
. 2
L O.I
H b
N b
I O.I
SECONDARY
EFFLUENT
21200
13230
40413
12091
49.7
752283
736217
9921 1
91392
6936
12422
13403
N-D
N-0
.7
N-D
2.2
N-D
N-D
13.7
N-D
N-0
1 .2
19.2
.7
1.2
N-D
.3
N-0
.3
.2
H-D
.2
N-D
N-0
N-D
N-D
3.6
N-0
N D
N-D
N-0
N-0
N-0
N-b
N-b
L O.I
PRIMARY
SLUOOE
69899
299477
181303
23561
.9
260243
NOT RUN
137833
NOT RUN
193152
309
3736
t O.I
N-0
N-D
N-D
N-D
2.2
.3
N-D
N-D
N-D
N-D
N-D
N-D
N-D
.9
1 .4
N-D
N-D
H-D
N-0
.2
1 .4
.4
L O.I
N-D
10.4
3.6
.9
L O.I
.2
.2
L 0.1
N-0
N-l)
N-D
SECONDARY
8LUDOE
138832
312700
180637
33566
2.3
162499
NOT RUN
110664
NOT RUN
187925
303
10723
N-D
N-D
N-D
N-D
N-D
N-D
N-D
N-D
N-D
N-D
N-D
N-D
N-D
N-D
1.0
N-D
N-D
N-D
N-D
N-D
1.1
.1
N-D
N-D
N-D
12.4
N-D
N-D
.2
L O.I
L 0.1
N-b
N-U
N-D
N-D
MHIUIANIb NUI L IS I til UtNt NO I 1'CUCIED
I I I l,b 1HANI N D NUI I'lltLltlJI
CKIIIMINAkY DATA ONI Y 10 fc£ VEKUU'D
-------
FRACTION
METALS
MASS BALANCE IN LBB. PER DAY
PLANT 20
HOH-COMW. HETALS
PARAMETER
ANTIMONY
ARSENIC
CADMIUM
CHROMIUM
COPPER
CYANIDE
LEAD
MERCURY
NICKEL
SELENIUM
SILVER
ZINC
ALUMINUM
BARIUM
CALCIUN
IRON
MAGNESIUM
MANGANESE
SODIUM
INFLUENT
N-D
7.3
N-0
38. 4
184
241
26,2
,0
62. i
N-D
7.0
349
272J
124
47370
2707
25472
80.3
130844
TOTAL OUT
1 .0
2.5
1.2
34,9
137
308
54,4
1.0
49.9
.4
7.9
319
^
-
-
-
-
-
-
SECONDARY
EFFLUENT
N-D
N-D
N-D
1.3
9.3
84.3
N-D
N-D
20.5
N-D
N-0
33. A
70.4
43.4
42235
77.2
23517
40.0
134324
PRIMARY
SLUDGE
.8
1 .1
,4
15.2
43.7
148
28.3
.4
14.1
.6
3.4
122
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
SECONDARY
SLUDGE
.2
1.4
.8
IB. 4
44.4
53.7
24.1
,4
15.3
N-D
4.5
141
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
en
POLLUTANTS NOT LISTED WERE NOT DETECTED
L-LESS THAN* N-D NOT DETECTED*
PRELIMINARY DATA ONLY TO BE VERIFIED
-------
HASS BALANCE IN IBS. PER OAT
TERIARY TREATMENT SYSTEM
PLANT 20
FHACIION
CONVENIIONALB
NQN-CONVENT10NAL8
VOLAIILE8
ACID EXTRACT
DASE-NEUIRALB
ft til 1C I DEB
ML IAI b
PARAMETER
BOD
TOTAL 6USP. SOLIDS
COD
OIL | GREASE
TOTAL PHENOLS
TOTAL SOLIDS
TOTAL DISS. SOLIDS
TOIAL VOLATILE SOLIDS
VOLATILE DISS. SOLIDS
TOIAL VOL. SUS. SOLIDS
AHHONIA NITROGEN
TOC
I • I . I-TRICHLOROETHANE
CHLOROFORM
METHYLENE CHLORIDE
BROHOFORH
DICHLOROBROHOHETHANE
DICHLORODIFLUORONE THANE
CHLORODIBROHOHETHANE
TETRACHLOROETHVLENE
TOLUENE
IRICHLOROETHYLENE
2 . 4 • 4 - TR I CHLOROPHENOL
2.4-DICHLOROPHENOL
PHENOL
FLUORANTHENE
NAPHTHALENE
BIB(2-ETHYLHEXYL> PHTHALATE
DIETHYL PHTHALATE
I.2-0ENZANTHRACENE
1 I . I 2-BENZOFLUORANTHENE
CHRY6ENE
ACENAPHTHYLENE
ANTHRACENE
I. 12-BENZOPERYLENE
FLUORENE
PHENANTHRENE
PYRENE
ALPHA -t>HC
UAHHA-BHC
AKtitNIC
I ADHIUM
Cm f'EK
CYANII'L
SECONDARY
EFFLUENT
20383
12739
38855
11425
47.8
723274
707830
95384
86041
4488
11941
HBO*
.4
2.1
13.2
N-D
1.1
18.9
.4
1.1
N-D
.3
.3
.2
.2
N-D
N-D
3.4
N-0
N-D
N-0
N-D
N-D
N-D
N-D
H-D
N-D
N-D
N-D
L O.I
N-D
N D
1 .1
e.y
£13. 0
TOTAL OUT
2310S
50246
S4471
7820
19 .9
791242
-
12453*
-
31339
493
13513
N-P
22. B
2.2
1 .4
17. 0
14.4
13.3
N-D
.2
N-0
N-D
N-D
I O.I
.7
.3
e. »
I 0. 1
.1
L O.I
.1
.4
1.3
. 1
.3
1 .1
.4
L O.I
. 1
.2
L O.I
1 .»
11,1
MVU
TERTIARY
EFFLUENT
7803
4300
38218
7323
19.7
775447
738310
113380
94440
1911
478
12899
N-D
22.6
2.2
1.4
17. B
14.4
13.9
N-D
N-D
N-D
N-0
N-D
N-D
N-0
N-D
8.1
N-0
N-D
N-D
N-D
N-D
N-D
N-D
N-D
N-D
N-D
L O.I
.1
N-D
N-D
N D
9.4
1495
NITRIFICATION
SLUDOE
13302
4S94B
18253
495
.2
1SS7S
NOT RUN
11139
NOT RUN
29428
14.7
414
N-D
N-D
N-D
N-D
N-D
N-D
N-0
N-D
.2
N-D
N-D
N-D
I 0.1
.7
.3
lfl
L oil
.1
L 0. 1
.1
.4
1 .3
.1
.3
I .3
.4
N-D
N-D
.2
I 0.1
1 .9
4 .5
3.0
IIIIIUIANIb N01 IISUli UtKE NO I I'tHlILD
I llSb IHAMJ NO NOT DEItCUKI
IhlllMINARY DATA ONI Y 10 BE VERIFIED
I
-------
MASS BALANCE IN LBS. PER DAY
TERIARY TREATMENT SYSTEM
PLANT 20
FRACTION
METALS
NON-CONV. METALS
PARAMETER
LEAD
MERCURY
NICKEL
SILVER
ZINC
ALUMINUM
BARIUM
CALCIUM
IRON
MAGNESIUM
HANOANEBE
SODIUM
SECONDARY
EFFLUENT
TOTAL OUT
TERTIARY
EFFLUENT
NITRIFICATION
SI.UPOE
N-D
N-D
IV. 7
N-D
34,2
2.?
I 0,1
14. e
.3
47.5
N-D
N-D
13.4
N-D
34.4
2.9
L 0.1
1 .4
,3
10.9
84.9
41,7
40407
V3.3
22412
57.6
129143
29. 8
37,1
40925
18.3
23090
3.8
13,2808
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
NOT RUN
POLLUTANTS NOT LISTED MERE NOT DETECTED
L-LESS THANI N-D NOT DETECTEDI
PRELIMINARY DATA ONLY TO BE VERIFIED
-------
PERCENT OCCURRENCE OF POLLUTANT PARAMETERS
PLANT 20
01
A
<£>
PARAMETER
CHLOROFORM
MtlimENE CIILORIbE
COPPER
CYANIDE
ZINC
H I LIU OROBROMOHE THANE
TETRACHLOROETIIYLENE
NICKEL
CHLORODIHROHOHE THANE
HI6<2 ETIirLHEXYL) PIITHALATE
OAHHA-BIIC
2.4.4-TR1CHLOROPHENOL
1,1. 1-TftICHLOROETHANE
DICHLORODIFLUOROMETHANE
1MCHLORGETHYLENE
2.4-DICHLOROPHENOL
PHENOL
CHROMIUM
BENZENE
CARBON TETRACHLORIDE
ti I-DICHLOROETHAME
1 . 2-IRAM8-DICIUOROETHYLENE
EIHYLbLNZENE
METHYL CHLORIDE
HETIIYL bROHIbE
DROMOFORH
TOI UENE
VINYL CHLORIDE
2t V DIMLTHY! PHENOL
1 ,2.4-TRlCHLORObENZENE
1 . 2 DItHI OKOBENZENE
FLUORANTHENE
1GOFHQRONE
NAPHTHALENE
BUTYL KENZYL PIITHALATE
01 N bUTYL PIITHALATE
UILTHYL PIITHALATE
1.2 l L H I C
FOIIUIANIb NOT LISILli ULKt NO I I'tlLCIELi
IIHLONI IhHLU tESTICIUES WERE ASSUMED NUT
NIIHl.tKb IN PARENTHESES ARC THE NUHUER OF
II.LLIHINARY ('ATA ONLY-10 6E VERIFIED
INFL-
UENT
100
100
too
100
100
83
83
83
67
47
47
SO
33
33
33
17
17
17
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
tCTED
li NOT
UER OF
( 4)
( 4)
< 4)
( 4)
< 4>
( 4>
( 4)
( 4)
< 4)
( 4)
( 4)
( 6k
( 4)
( 4)
< 6)
< 4)
< 4k
( 4k
< 4)
( 4k
< 4k
< 4k
4 4k
4 4k
< 4k
4 4k
( 4k
( 4k
4 4k
4 4)
4 4k
4 4k
4 4k
4 4k
4 4)
4 4k
4 4)
4 4)
4 4)
( 4k
4k
4>
4k
4)
4k
4)
4)
4)
4)
4)
4)
AT ANY
PRE CL.
INFL.
100 4
100 4
100 4
100 4
100 4
0 4
100 (
100 4
17 4
100 4
tOO 4
47 4
100 4
47 4
100 4
17 4
47 <
100 4
47 4
33 4
63 4
83 4
100 4
17 4
33 4
0 4
100 4
17 4
17 4
47 4
0 4
0 4
33 4
0 4
63 4
SO 4
30 4
0 4
0 4
0 4
0 4
0 1
0 4
0 4
0 4
0 (
17 <
1 / 4
0 I
0 <
1 > (
SAMPLE
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4)
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
41
4k
4k
4k
4)
4k
4)
4)
POINT
TERT.
EFFL.
100
100
100
too
100
100
0
47
63
63
63
0
0
33
0
0
0
0
0
0
0
0
0
0
0
47
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
17
0
0
4)
4k
6)
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
1 4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
Sk
4k
4)
6k
4)
4k
4)
4k
4)
4k
4k
4k
6)
6)
4)
6)
6)
PRIM
SLDO
0
0
100
100
100
0
0
100
0
100
0
0
0
0
33
0
33
too
63
O
0
63
too
0
0
0
too
0
0
SO
33
17
0
0
100
100
17
0
0
0
0
33
0
0
33
17
0
0
0
too
100
4 4k
4 4k
4 4k
4 4k
4 4k
4 4k
4 4k
4 4k
4 4k
4 4k
4 4k
< 4)
4 4k
4 4k
4 4k
< 4k
4 4k
4 4k
4 4k
4 4k
4 4k
4 4k
4 6k
4 4k
4 4k
4 4k
4 4k
4 4k
4 4k
4 4k
4 4k
4 4k
4 4k
4 4k
4 4k
4 4k
4 4k
4 4k
4 4)
4 4k
4 4k
4 4)
4 4)
4 4k
4 4)
4 4k
( 4)
( 4)
( 4)
( S >
< 6)
SEC.
SLDO
0 4 4k
0 4 6k
100 4 4k
100 < 4k
100 4 4k
0 4 4k
0 < 4k
100 4 4k
0 4 4k
100 4 6k
0 1 4k
0 4 6k
0 4 4k
0 4 4k
0 4 4)
0 4 4k
33 4 4k
100 4 4k
0 4 4k
0 4 4k
0 ( 4k
0 4 4k
0 4 4k
0 4 4k
0 4 6k
0 4 4k
100 4 6k
0 4 6k
0 4 6k
17
0
0
0
0
0
0
t7
0
0
0
0
17
0
0
17
0
0
0
0
20
100
6k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4k
4)
4)
4k
5>
4k
NIT.
SLbO
0
0
100
too
100
0
0
100
0
100
0
0
0
0
0
0
so
100
0
0
0
0
0
0
0
0
100
0
0
0
0
so
0
so
0
0
so
so
so
so
so
so
so
so
so
so
0
0
0
0
100
4 2k
4 2k
4 2k
( 2k
4 2k
1 2k
4 2k
4 2k
4 2>
4 2k
4 2k
4 2k
4 2k
4 2k
4 2k
4 2k
4 2k
4 2k
4 2k
4 2k
4 2k
4 2k
4 2k
4 2k
4 2k
4 2k
4 2k
4 2k
4 2k
4 2k
4 2k
4 2k
4 2k
4 2k
4 2k
4 2k
4 2k
4 2k
4 2k
4 2k
4 2k
4 2k
4 2k
4 2)
4 2k
4 2k
4 2k
4 2)
4 2k
4 1 )
4 21
DETECTED
SAMPLES TAKEN
-------
PERCENT OCCURRENCE OF POLLUTANT PARAMETERS
PLANT 20
PARAMETER
CADMIUM
LEAD
MERCURY
SELENIUM
SILVER
INFL
UENT
0
0
0
0
0
-
( 4)
< A)
( 6)
( 4)
< 6)
PRE C
INFL.
0
33
100
0
67
L.
( 61
( A)
< A)
( A)
< A)
TERT
EFFL
0
0
0
0
0
t
•
( A)
( A>
( 4)
( 41
( «)
PRIM
SLl'O
100
100
100
100
100
,
( 4)
( A)
( «>
( 3)
< 4>
SEC.
SI. PO
JOO <
100 <
100 <
0 (
100 <
A)
A)
A)
5)
A)
NIT.
SI I'D
100
100
too
0
100
•
< 2)
< 2»
< 2)
< 1)
( 2)
Co 5
en =>
A
i
2
s
POLLUTANTS NOT LISTED MERE NOT DETECTED AT ANY SAMPLE POINT
UNCONFIRMED PESTICIDES WERE ASSUMED NOT DETECTED
NUMBERS IN PARENTHESES ARE THE MUMPER OF SAMPLES TAKEN
PRELIMINARY DATA ONLY-TO BE VERIFItD
-------
SECTICW n
-------
1.0 METHOD FOR PURGEABLE ORGANICS
1.1 Scope and Application
1.1.1 Scope
This method is used for the determination of purgeable (volatile)
organics. The complete list of compounds is provided in Table 1.1.
The method is complementary to liquid/liquid extraction techniques
for extractable organics.
1.1.2 Application
The method is applicable to the measurement of purgeafala orsanics
in municipal wastewater sludges. It can be used for screening sam-
ples of sludges for purgeable priority organics in surveys of mu-
nicipal wastewater treatment plants. The method uses GC/MS systems
for qualitative and semi-quantitative determination of these com-
pounds .
1.2 Siirmary
Sludge samples are diluted to 0.52 total solids content with organic-free
water. The diluted sample is then purged at room temperature (^ 22°C)
with an inert gas for 12 min. U'ater insoluble compounds boiling below
200°C are transferred from the aqueous phase to the gaseous phase. The
gaseous phase is passed through a sorbent trap where the organic compounds
-------
are concentrated. The contents of the trap are then injected into the
GC/MS by heating and backflushing the trap. As variations in recover}*
efficiencies for the individual purgeable organics can be affected by ;he
sample matrices, extensive quality control is required for accurate mea-
surements. The total analysis time including extraction is less than 1
hr. This method is recommended for use only by analysts experienced in
the analysis of purgeable organics at the trace levels or by experienced
technicians under the close supervision of a qualified analyst.
1.3 Apparatus and Reagents
1.3.1 For Sample Preparation
1.3.1.1 Purse and trap svstej: Assemble the system as depicted
in Jigures 1.1 and 1.2. A commercial version, such as
the Teksar Liquid Sample Concentrator Model LSC-1, or
its equivalent, may also be used. The purging device is
constructed or modified as shown in Figure 1.3. All saa-
ple contacting surfaces must i either glass or Teflon.
Th<=". trap is packed according to Figure 1.4. In order to
function properly, the trap uiust be packed in the follow-
ing order: Place the glass wool plug in the inlet end of
the trap, follow with the OV-1. Tenax, - ilica gal,. char_-
coal, and finally, the second glass wool plug. Reversing
the packing order, i.e., placing the charcoal in the trap
first will cause the silica gel and Tenax layers to be-
come contaminated with -har:?al dust causing poor cessrption
-------
efficiencies. Install the trap so that the effluent
from the purging device enters the Tenax end of the trap.
1.3.1.2 Glassware
a. Screw-cap vials - 40 ml with Teflon-lined caps
b. 10 al» 50 ml, and 100 nil volumetric flasks
1.3.1.3 Analytical balance
1.3.1.4 Roller aill and 1/4 in. stainless steel ball bearings
1.3.1.5 Catalytic gas purifier
1.3.1.6 Purging gas - He or N2, water compressed, high-purity
grade
1.3.1.7 Syringes - 10 ul, 100 1, 1 ml and 5 ml gas-tight.for
quality control spiking. A large bore 10-ml syringe is
used for saaple handling. A 20-ml gas-tight syringe is
used for preparing standards of neat gaseous compounds.
1.3.1.8 Purgeable - organics-free water. See Section 1.5
a. Activated Carbon-Calgon ?iltrasorb-200 or equivalent
1.3.1.9 Trap Packing Materials
a. 37. 07-1 on Chromosorb-W 100/110 mesh
b. Tenax-CC®- 60/80 mesh
c. Silica gel - Davison Grade 15 35/60 mesh or equivalent
d. Coconut charcoal - 26 mesh Barhaby Chaney No. CA-580-
26, Lot No. M-2649 or equivalent, as used in NIOSH
charcoal adsorption tubes, available through Supelco,
Inc. (Cat. No. 2-0267).
3
-------
1.3.1.10 Glass wool - Cleaned by thorough rinsing with hexine,
dried in a 110eC oven, and scored in a hexane-rinsad
glass jar with TIT -lined cap.
1.3.2 ~or Ouantitacion and Identification
1.3.2.1 Gas Chromatograph-mass spectrometer dtta system. Finrigan
• 4000 or equivalent - The GC/MS interface she-Id be a glass
jet separator. The computer system should allow acquisition
and storage of repetitive sc?r data thr ughout the GC/MS
runs. Computer software should be available to allow
searching of GC/MS data for display of extracted icn cur-
romt profiles (EIC?) and integration of the peaks. The
GC/MS should be fitted with a stainless steel or glass
column packed with 0.2" Carbowax 1500 or Carbopack^C.
Typical column dimensions are 8 ft x 1/3 in. OD stainless
steel or 6 ft :: 2 ma ID glass.
1.3.2.2 Reference naterials - Assayed quantity of compounds of
interest, and/or diluted standard solutions of compounds
of interest and internal standard compounds in nethanol.
1.3.2.3 Mass spectrometer calibration uoapouwd - p_-fluorobroao-
benzene.
1.4 Sampling and Tresarvation
1'. 4.1 Sampling
Samples must be collected in 40-al screw-cap vials with :ero head
space and sealed with Teflon-lined taps. 3ef:re using, wash all
4
24 i<
-------
sample bottles and TFi seals in detergent, rinse with tap water
and finally with distilled water. Allow the bottles .and seals to
air dry at rood temperature, heat in a 105°C oven for 1 hr, then
allow to cool in an area known to be free of organics. NOTZ:
Do not heat the TFS seals for extended periods of time (nore than
1 hr) because the silicone layer slowly degrades at 105°C.
1.4.2 Preservation
As a general guideline, ice samples immediately after collection,
refrigerate at 4eC> and purge within 10 days. Desorb "the trap
and complete the analyses immediately after purging.
1.4.3 Solids Determination
The total solids content of the sample is determined in duplicate
by weighing two ^ 1 ml aliquots of the extractable sludge sample
before and after drying overnight at 110*C. The general procedure
outlined in Standard Methods f.or the Examination of Water and Waste-
water, 14th ed. > for the determination of Total Dried Residue (Part
208A) at 103 to 105°C is applicable.
1.5 Preparation of Purgeable -Organic-Pree Water
Organic-free water is generated by passing tap water through a carbon
filter bed containing about 1 Ib of activated carbon and purged with pre-
purified N2, preferably overnight. A Millipore Super-Q Water System or
its equivalent may be used to generate organic-free deionized water.
Organic-free water can also be prepared by boiling distilled water for
15 min and transferring, while still hot, to a glass-stoppered bottle.
5
-------
Cool to room temperature. Continuous purging of che organic-free water
with pre-purified ^2 =isy be used during storage to r.ini=.iie contamination
with volatile organic compounds. Test organic-free water daily by analyz-
ing according to this method (see Section 1.9).
1.6 Preparation of Standards
1.6.1 Analytical Standards
Although this protocol assumes the preparation of standard solu-
tions from assayed reference materials, cocaercia.ily prepared stock
solutions, such as Supelco, Inc., Purgeable Seacards, nay be used
for analytical and fortification standards with appropriate dilution.
1.6.1.1 Preparation from neat compounds - 7rom individual assayed
reference materials prepare standard stock solutions (at
approximately 2 ug/ul) by adding, from a lOC-ul syringe,
1 to 2 drops of the 99+" pure reference standard tc meth-
anol (9.8 ml) contained in a tared 10-al volumetric flask
(weighed to the nearest 0.1 ag). Add the component so
that the two drops fall into the alcohol and do not con-
tact the neck of the flask. (Prepare gaseous standards,
i.e., vinyl chloride) in a similar asr-er using a 20-al
syringe (20 ml) with the gaseous compound. Weight the 13-
ml volumetric flask containing 9.3 til cf aethyl alcohol to
0.1 ag. Lower the syringe needle to aocut 5 m aocve t.-.e
aethvl alcohol meniscus and si owl'.- inject tna st^ncarc
-------
into the flask. The gas rapidly dissolves in the methyl
alcohol. Reweigh the flask, and use the weight gain to
calculate the concentration of the standard. Dilute to
volume, mix, and store in the sealed flask. Gas stock
standards are generally stable for at least 1 week when
maintained at less than 0"C. With the exception of 2-
chloroethylvinylether, stock standards of compounds that
boil above room temperature are generally stable for at
least 4 weeks when stored at 4°C. (Safety Caution: Be-
cause of the toxicity of most organohalides, dilutions
should be made in a glove box suitable for handling car-
cinogens. It is advisable to use an approved respirator
when high concentrations of -such materials must be- handled
in a fume hood).
From the primary stock solutions, prepare a multicomponent
secondary dilution mixture in methyl alcohol at'a concen-
tration of 1 ug/ml containing each of the compounds to be
determined. Assuming storage at 4CC, prepare a fresh mul-
ticomponent secondary dilution mixture on a weekly basis.
Daily prepare 10 ml of a 50 ng/ml standard from the 1 yg/
ml multicomponent standard by dosing 500 yl into -v 9 ml of
organic-free water, and adjusting the volume to 10.0 ml.
Analyze 1 ml and 5 ol aliquots of the aqueous standard
-------
Stock, solutions, as received are stored in a freezer vhea
not in use. To prepare a working standard, '25 ul of both
Purgeable Standard A and Purgeable Standard B are added
to •v 99 ml of organic-free water. Subsequently, 100 ul
of Purgeable Standard C and 50 ul of the acrolein/acrylo-
nitrile standard are added and the final volume adjusted
to 100 ml. Final concentrations for Purgeable A and B
compounds are 50 ng/ml. Final concentrations of Purgeable
C compounds are 200 ng/ml, and acrolein/acrylonitrila are
present at 500 ng/nl in the standard. Analyses of 1 r^l and
5 ml of this mixed standard (after volume adjustments to
10 ml with orgaaic-free water), will produce responses
nominally corresponding to 50 ug/liter and 250 ug/liter,
or 50 ng and 250 ng, respectively.
Prepare a fresh aqueous working standard on a dailv basis.
1.6.2 Internal Standard Spiking Solution
Although this protocol assumes the preparation of the standard so-
lutions from neat authentic compounds, appropriate reliable commer-
cial preparations may be used as suitable substitutes.
1.6.2.1 Preparation from neat compounds - From stock standard -
solutions prepared as above, add a volume of standard to
give 1,000 ug each of bromochiorccethane, 2-bromo-l-
chloropropane, and 1,4-dichlorobutane to «; ml of organic-
free water (blank water) contained in a 50-ml vcl-jmatric
Q
-------
flask, mix and dilute to volume. Dose 9.0 ul of this
internal standard spiking solution into every sample and
reference standard analyzed. Prepare a fresh method re-
covery spiking solution on a weekly basis. Prepare the
stock standard solutions monthly, or sooner if deteriora-
tion is indicated.
1.6.2.2 Preparation from commercial mixed stock solution - As an
alternate to preparation of the mixed internal standard
solution from neat compounds, a commercially prepared
stock mixture may be employed. The method outlined be-
low is specifically designed for use with the Supelco,
Inc., mixed stock internal standard solution which con-
tains 20 mg/nl of each compound.
1.7 Sample Preparation and Purging
1.7.1 Sample Compositing
VOA samples are collected at discrete time intervals by grab sam-
pling. When VOA results for relatively long time intervals, such
as 24 hr, are necessary or desirable, compositing of several VOA
grab samples must be performed. To do this, normally six VOA grab
samples (i.e., one 40-ml grab sample collected every 4 hr over a
24-hr period) will be composited. After storage, sample disrup-
tion with a. glass stirring rod may be necessary to remove the san-
ple from the VOA vial adequately. Care must be taken to avoid
10
246^
-------
displacement losses when the stirring roc -'s used. The chilled
samples are mixed with gentle swirling in 3. 250-ml round-bet torn
flask. Vigorous mixing must be avoided to prevent analyte losses.
Analysis should be performed immediately after compositing. In
cases where this is impossible or when sarnie material is to be
retained for future reference, aliquots of the composited VOA sam-
ples are returned to VCU vials with rero headspace and refrigerated
at 4"C. Normally, only four full VOA vials of composized material
can be prepared from six individual grab samples.
1.7.2 Sample Preparation and Purging
Condition the trap at 200°C with a flow of nitrogen or helium.
Turn off gas flow to the purging device.
Transfer that amount of sludge which contains greater than 50 ng
dry solids (i.e., 1 ml for a 5% sludge) to the syringe body. As-
semble the syringe body and plunger. Adjust the sludge aliquot
to a volume containing 50 mg dry solids. Add internal standard
to the adjusted sample aliquot through the syringe outlet. Trans-
fer the sample to the purging device. Rinse the syringe with
organic-free water and add to the purging device. Bring the level
in the purging device to the 10-ml mark with organic-free water.
Prior to purging, place c. glass wool plug in the top of the purge
tube to dispense excessive foam. Seal the purging device, and turn
on the gas flow to the purging device and adjust to a flow rate of
approximately 40 ml/min.
11
247<
-------
Purge the sample for 12 ^-fn while maintaining the sample and trap
at room temperature.
1.8 Analysis of the Sample ?urge
Analyze the sample purge by GC/MS using the 0.2% Carbowax 1500 on 80/100
mesh Carbopack C column described ia Section 1.3.2.1 operated with a He
carrier gas flow of 30 ml/min. Heat the trap to ISO to 200*C. Sackflush
it for 3 min into the gas chromatograph with the oven at 40°C. Hold the
oven temperature at 40°C for 3 min during the desorption stage. Immedi-
ately after desorption initiate .temperature programming. For 8-ft stain-
less steel columns a programming rate of 10°C/min to 170*C should be used.
For 6-ft glass columns a program rate of 6°C/min to 170°C is effective.
Hold at this temperature until all compounds of interest have eluted. The
purging device must be removed from the instrument and thoroughly rinsed
with copious volumes of volatile organic-free water between each sample
(nominally three rinses of *v 30 ml volume per rinse). Thoroughly•clean
the purging device according to procedures in Section 1.4.1 between par-
ticularly dirty samples. The trap must be conditioned at 180°C with flow
for 5 to 7 min between each sample. The MS should be repetitively scanned
ovejt the range m/e 20 to 275 at 3 to 5 sec/scan.
1.9 Purgeable Organies Analytical Quality Assurance
In addition to the instrumental quality assurance procedures specified in
Sections 1.9.1 and 1.9.2, analyses of replicate and fortified samples and
blanks ara required to indicate the method precision and accuracy. Since
the method precision may be very dependent on the sample matrix, the
12
243^
-------
.9.4 Fortified and Duplicate Samples
1-9.4.1 Sample Selection
After the analysis of samples collected at the first sam-
pling time, spike and analyze duplicate sample aliquots
from the first samples. For example, for a survey program
sampling a POTW plant daily for 4 to 6 days, collect trip-
licate samples for the first day. After ccmplecing analyses
of one set of the 1st day samples, spike and analyze dupli-
cate 1st day samples. Spike the 1st day samples using
procedures described in Section 1.9.4.2. The frequency
of selecting spiked duplicate samples for analysis for
sampling programs longer than 6 days should be date —ir.ed
from the detention times of the sludge types samples so
as to reflect possible changes in sample matrix.
1.9.4.2 Fortification Procedures
Add one or two stainless steel ball bearings (1/8 in.
diameter) to an empty vial and determine the tare --eight.
Fill the vi^l with sludge and reueigh; the weight differ-
ence determines the wet contents of the vial.
Fortify the sample with all of the compounds noted in "-able
1.1 to produce a final concentration two times the concen-
tration found in the unspiked sample, or 10 time3 the lower
limit of detection reported in Table A-l whichever is
14
-------
greater. Generally, blanket fortifications of analytes
can be accomplished using commercially available mixed
standards; however, for analytes present in unusually high
concentrations, supplemental fortification with an indi-
vidual solution may be required. -Seal the vial and place
on a roller mill in a 4°C cold room; roll the sample for
16 hr before analysis.
The fortified sample is handled as a regular sample during
analysis. The quantity of fortified sample analyzed aust
be equal the quantity of original unfortified sample ana-
lyzed.
1.10 Cata Handling
Using the characteristic retention times and ions listed in Tables 1.2
and 1.3, obtain extracted ion current profiles (EIC?s) of the character-
istic ions for each compound. Verify the presence of compounds of inter-
est based on the coincidences of peaks in the characteristic EICPs at
the appropriate retention times with intensities in the characteristic
ratios.
Calculate the concentrations of compounds identified by comparing Che
areas of the primary (highest abundance) ion peaks with the areas- o£ the-
corresponding standard peaks. If the sample matrix produces a significant
interference with the primary ion EIC?, a secondary ion plot may be used
for quantitation. Tor some analytes, such as toluene and ethylbenzene,
15
-------
it say be necessary to use ions of substantially lower intensity, e.g.,
n/e 93 or 107 for quantitative evaluation. Calculate the concentration
in the sample as follows:
\ /BIS\ /N\
— I — • ug/liter analyte in wet sludge
where: A » area of peak in sample
B » area of peak in standard
Aj£ * area of internal standard peak in sanple
BTS * area of internal standard peak in standard
N « nanograms in standard
V - volume of wet sludge analyzed (ml)
16
-------
Table 1.0. Stock VGA Standards Available ?rom Suoelco
Purgeable A
Purgeable 3
Purgeable C
Dichloroaethane
1,1-Dichloroethylene
1,1-Dichloroethane
Chloroform
Carbon tetrachloride
1,2-Dichloropropane
Trichloroethylene
1,1,2-Trichloroethan'e
Dibroaochloroaethane
Tetrachloroethvlene
Trifluoromethaae
tran'S-l,2-Dichloroethylene
1,2-Dichloroethane
1,1,1-Trichlofoethane
Broaodichlorcaiethane
trans-1,3-Dichloropropene
cis-l,3-DlchloropTopene
Benzene
Bronofora
1,1,2,2-Tetracnloroethane
Toluene
Zthylbenzene
Chloromethane
Dichlorodifluoromechane
Broiaamethane
Vinyl chloride
Colcroethane
17
-------
Table 1.1. Volatile Organics Detectable With the ?iiree-And-Trao Method
Comoound
Cotroound
F/Cl/Br/Methanes
Methylchloride (chloromethane)
Methylene chloride (dichloromethane)
Chlorofora (trichloronethane)
Carbon tetrachloride
(tetrachlorotnethane)
Methylbromide (bromomethane)
Bromoforra (tribromomethane)
Chlorodibromoinethane
Bronodichloromethane
Dichlorodifluoroaethane
Trichlorofluoronethane
Cl-Ethanes
Qiloroethane
1, 1-Dichlc roe thane
1,2-Dichloroethane
1,1, 1-Trichloroethane
1,1, 2-Trichloroethane
1,1,2, 2-Tetrachloroe thane
Cl-3enzenes
Benzene
Chlorobenzene
Toluene
Ethylbenzene
Cl-Zth-vlenes, Frooane
Vinylchloride (chloroethylene)
1,1-Dichloroethylene
(1,1-dichlcroethene)
Trans-1,2-dichloroethylene
(Trans--!., 2-dichloroethene)
Trichloroethylene (trichloroethene)
Tetrachloroethylene
(tetrachloroethene)
1,2-dichloropropane
1,2-dichloropropylene
Trans-1,3-dichloropropene
Cis-1,3-dichloropene
Alkenes
Acrolein (propenal)
Acrylonitrile (propene ^itril3)
Ethers
Bis-chloromethylether*
(sym. -dichlorodiaethylether)
2-Chloroethylvlnylether
(2-chloroethyl ethenylether)
Bis-(2-chloroethyl) ether
(3,3*-dichlorodiethylether)
Bis-(2-chloroisopropyl) ether
(S,S'-dichlorodisopropyl ether)
3is-Chloromethylether has a half-life of about 10 seconds in aqueous mixtures,
18
-------
Table 1.2. Elution Order of Volatile priority pollutants^'
C oapound
Chloroaethane 0.152
Dichlorodifluoromethane 0.172
BromcBethane 0.181
Vinyl Chloride • 0.186
Chloroethane 6.204
Methylene Chloride 0.292
Trichlorofluoromethane 0.372
1,1-Dichloroethylene 0.380
Br omochl or otne thane (IS) 0.457
1,1-Dichloroethane 0.469
Trans-1,2-dichldroethylene 0.493
Chloroform 0.557
1,2-Dichloroethane 0.600
1,1,1-Trichloroethane 0.672
Carbon Tetrachloride 0.684
Brosnodichloromethane 0.750
Bis-chloromethyl ether 0.760
1,2-Dichloropropane .- 0.818
Trans-1,3-dichloropropene 0.847
Trichloroethylene 0.867
Dibromochloromethane 0.931
Cis-l,3-dichloropropene 0.913
1,1,2-Trichloroethane 0.913
Benzene 0.937
2-Chloroethylvinyl ether 0.992
2-Bromo-l-chloropropane (IS) 1.000
Bromoform 1.115
1,1,2,2-Tetrachloroechene 1.262
1,1,2,2-Tetrachloroethane 1.281
1,4-Dichlorobutane (IS) 1.312
Toluene 1.341
Chjorofaenzene 1.489
EtHylbenzene 1.814
Acrolein Unknown
Acrylonitrile Unknown
£/ "These data were obtained under the following conditions: GC column -
stainless steel, 8-ft long x 0.1 in. I.D. packed with Carbopack C
(60/80 mesh), coated with 0.27. Carbowax 1500; carrier flow - 30 si/
Bin; oven cesperature - initial 60°C held for 3 min, programmed
8°C/min to 160°C and held until all conpounds eluted.
_b/ Retention times relative to 2-bromo-l-chloropropane with an absolute
retention tiae of 829 sec.
19
-------
CABZ1EX GAS R.OW CONTROL
PtESSUBE ZEGUIATC*
UOLBO INJECTION POUTS
PURGi GAS
COKT7.CL \
!3X MCUCUU8
aev? HUES
COLUMN OVEN
CONFIRMATORY COLUMN
COLUMN
HEATeS CONT7CL
NOT& ALL UNES
TIAf AND OC
SHOULTl !H H£ATH)
P«JIGING DEVK2 TO SO*C
Figure 1.1 - Schematic of Purge and Trap Device - Purge Mode
20
-------
CARRIES CAS aow CONTROL
UOUtO INJECTION POSTS
COLUMN OVEN
PRESSURE REGULATOR
V
PURGE GAS . .
FLOW CONTROL X|
ISX MOLfCULAR
OPTIONAL 4-?ORT COLUMN
SELECTION VALVE
TRAP INLET (TENAX END)
VALVE / RESISTANCE WTR£
HEATS CS
NOT& ALL LINES SETWEN
TRAP AND GC
SHOULD BE HEATS
TO 80-C
PURGING OEVJCE
Figure 1.2 - Schematic of Purge and Trap Device - Desorb Mode
21
-------
1/16" x 1/4"
Swage lock Reducing
Union, Bored Through
Wool
(Optional) for
Foaming Problems
to Trap
Sintered
Glass Frit,
4-8 Micron
1 .5 cm
1/4" O.D. Exit
O-Ring-
38 cm
Helium Purge Gcs
figure 1.3 - Sludge Purging Tube
-------
PACKING PROCEDURE
CONSIRUC1IOH
MUUIPURPOSf HAT
. *
GlASi WOOl 5MM
ACIIVAUO CHARCOAL 7.7CM
ORAOI IS
N> SIIICA Oil 7.7CM
LJ
%
8
*
n
UMAX 7.7CM
37. OV-I KM
GlAJi WOOt
JMM
•*" ^
^r
* •'/
\
^
^
i
L':.
'•'?;•
n,'/
;-o^
%'
>..'»
'/>/
M:
n
»&
s/s
7«/fOOI RCSISIANCf
WIRI WRAPI'IO SOIIU _f=.--~-'
(DOUBli lAVtRj
ISCM
~~-K
i /inni ofdifAtjrc
A-V/IUUI nijui^nv*
WIRt WHAPPll) $Olll>
(SINGH IAYIR)
8CM— *-
L
c
-^C
^-c
c
c
r
v^
C
c
c
^•^
C
c
c
" C
c
c
—
J-*-^ AND IIRRUIIS
P
?.
>
) ItlfRMOCOUPlE/CONIROUfft
__-^ — — — """" SINSOR
:' [ IUCIRONIC
" «v
)^^^ ^^_ IIMPIRAIURE
~) ^^^^^ CONIROl
J) •^'//^~ AflD
^ / PTHOMIUR
^> /
I
^ I
^ 1 IUBING JSCM O.IOS IN. ID
-* I OUS IN. O.O. SIAINIESS Slid
> /
^IS
•-
o
IHAP imil
Figure l.'i — Trap Packings and Conutrucl: ton
-------
Table 1.3. Characteristic Ions of Volatile Orzanics
Compound
El Ions
(Relative Intensity)
:n .sea to
Cuantifv
Chloromethane
Dichlorodifluoromethane
3rozoraethane
Vinyl chloride
Chloroethane
Methylene chloride
Trichlorof luoroniethane
1,1-Dichloroethylene
Brcaochloromethana (IS)
1,1-Dichloroethane
Trans-1,2-dichloroethylene
Chloroform
1,2-Dichloroethane
1,1,1,-Trichloroethane
Carbon tetrachloride
3roziodichlor one thane
3is-chloromethyl ether
1,2-Dichloropropane
Trans-1,3-Dichloropropens
Trichloroethylene
Dibro-mochloratoethane
cis-1,3-Dichloropropene
1,1,2-Trichloroethane
Benzene
2-Chloroethylvinyl ether
2-3romo-l-chloropropane (IS)
Broraofona
1,1,2,2-Tezrachloroethene
1,1,2,2-Tetrachloroethane
1,4-dichlorobutane (IS)
Toluene
Chlorobenzene
Ethylbenzene
Aero lain
AcTvionitrile
50(100); 52(33)
85(100); 87(33); 101(13); 103(9)
94(100); 96(94)
62(100); 64(33)
64(100); 66(33)
49(100); 51(33); 84(86); 86(55)
101(100); 103(66)
61(100); 96(80); 98(53)
49(100); 130(88); 128(70); 51(33)
63(100); 65(33); 83(13); 85(8); 98(7);
100(4)
64(100); 96(90); 98(57)
83(100); 85(66)
62(100); 64(33); 98(23); 100(15)
98(100); 99(66); 117(17); 119(16)
117(100); 119(96); 121(30)
83(100); 85(66); 127(13); 129(17)
79(100); 81(33)
63(100); 65(33); 112(4); 114(3)
75(100); 77(33)
95(100); 97(66); 130(90); 132(85)
129(100); 127(78); 208(13); 206(10)
75(100); 77(33)
83(95); 85(60); 97(100); 99(63);
132(9); 134(8)
78(100)
63(95); 65(32); 106(18)
77(100); 79(33); 156(5)
171(50); 173(100); 175(50); 250(4);
252(11); 254(11); 256(4)
129(64); 131(62); 164(78); 166(100)
83(100); 85(66); 131(7); 133(7);
166(5); 168(6)
55(100); 90(30); 92(.10)
91(100); 92(.78)
112(100); 114(33)
91(100); 106(33)
26(49); 27(100); 55(64); 56(83)
26(100); 51(32); 52(75); 53(99)
50
101
94
62
64
84
101
96
128
63
98
73
30
78
106
77
173
164
168
55
92
" i ?
106
-------
Table 1.4. a-Fluofobrcnotrszene Ions and Ion Abundance Criteria
Ion Abundance Criteria
50 20-40% of base peak
75 55-757. of base peak
95 base peak
174 75-987. of base peak
175 5-97. of m/e 174
176 75-987. of base peak and
93-997. of n/e 174
177 0-57. of m/e 176
25
-------
2.0 METHOD FOR SEMIVOLATTLZ C5.GANICS
2.1 Scope and Application
2.1.1 Scope
This method applies to the determination of the base, neutral, and
acid-extractable organic compounds as described in Table 2.1.
2.1.2 Application
The method is for the measurement of these compounds in municipal
wastevater sludges. It can be used as a qualitative and semiquantita-
tive screening procedure for the analyses of priority toxic orjanics
in surveys of sludges from municipal wastevater treatment plants.
As a screening tool, the procedure requires the use of a GC/HS.
spectrometer as the final detector.
2.2.1 This method (Figure 2.1) uses wet sludge/solvent extraction aided
by a high-speed homogenizer. The extract is separated by centri-
fugation and removed with a pipette. Sludges are extracted at ?H
S 11 and again at pH £2 to extract base/neutral and acidic com-
pounds, respectively. Both extracts are cleaned by gel permeation
chromatography (G?C) and semivolatile organic priority pollutants
are determined in the cleaned extracts by GC/HS.
The method is recommended for use only by experienced organic
analysts or by competent personnel under the close supervision of
an experienced organic analyst. '>i_: 1 <-
A*O _*_^
26
-------
2.3 Apparatus
2.3.1 For sampling, extraction and extract cleanup.
2.3.1.1 Imulsifier-Tekaar Tissuenizer, or equivalent, high capacity,
2.3.1.2 Centrifuge.
2.3.1.3 Centrifuge tubes with in-lined screw caps, 250 ml or
.larger capacity.
2.3.1.4 Kuderaa-Danish (K-D) Glassware -
a.. Snyder Columns - 3 bulb, macro and micro
b. Evaporating flasks - 500 ml
c. Receiver Ampuls - 10 ml, graduated, with spring
attachment.
2.3.1.5 Water or steam bath for Kuderaa-Danish concentrations.
2.3.1.6 Chromatographic (.Drying) Co limn - Pyrex (400-mm by 20-ca
ID) without a fritted plate.
2.3.1.7 Separators funnels - 500 ml with teflon stopcock.
2.3.1.8 Syringe - 100 ml, Pyres, with long needle.
2.3.1.9 Graduated cylinder - 500 ml.
2.3.1.10 Vials - 1 dram (^ 4 ml) with TFZ-lined screw caps.
* 2.3.1.11 Sample bottles - 1,000 ml or 4,000 ml glass with in-lined
screw caps.
2.3.1.12 G?C - Analytical Biochemistry Labs, Inc. G?C Autoprep
1002 or equivalent with a 25 mm ID column containing 50 to
60 g of SioBeads SX-3.
2.3.1.13 Syringe filter holder - stainless steel and TFZ, Gelaan
4310, or equivalent.
27
-------
2.3.1.14 Bottles - 500 ml, brown glass.
2.3.2 For identification and quantitation.
2.3.2.1 Gas chromatograph/mass spectrometer with data systam -
Finnigan 4000 or equivalent. The GC/MS interface should
be a glass jet separator. The computer system should ailcw
acquisition and storage of repetitive scan data throughout
the GC/MS runs. Computer software should be available to
allow searching of GC/MS data for display of estracted ion
current profiles (EICPs) and integration of the peaks.
GC columns required are:
a. 1.8 m x 2 mm ID glass packed with 17. SP-2250 on 100/
120 mesh Supelcoport.
b. 0.9-1.8 m x 2 mm ID glass packed with 1% SP-1240-DA
on 100/120 mesh Supelcoport.
2.3.2.2 Gas chromatograph/flaae ionization detection with the
same GC columns as for the GC/MS system.
2.3.2.3 Syringes, 10 and 100 ul.
2.3.2.4 Internal standard solution - D-10-anthracene, 2 yg/ul
in dichloromethane.
2.4 Reagents
2.4.1 For extraction and Extract Cleanup
2.4.1.1 Dichloromethane - Burdick and Jackson "Distill ir. Glass"
or equivalent, stored in original containers and used as
received.
28
-------
2.4.1.2 Hydrochloric acid (HC1) - 6 H.
2.4.1.3 Sodium, hydroxide (NaOH) - 6 IT.
2.4.1.4 Sodium sulfate (^SO^.) - Anhydrous, granular. Clean by
overnight Soxhlet extraction with dichloromethane, drying
in a 110° oven, and. then heating to 650"C for 2 hours.
;Store in 110°C oven-or in glass jar closed with TFI®-lined
screw cap.
2.4.1.5 Glass wool - Cleaned by thorough rinsing with hexane,
dried' in a IIO'C oven, and stored in a hexane-rinsed glass
jar with TF2®-lined cap.
2.4.1.6 Boiling chips - silica or .carborundum.
2.4.1.7 G?C calibration solutions:
a. Corn oil - 200 mg/ml in dichloromethane.
b. .bis(2-ethylhexylphthalate) and pentachlorophenol - 4.0
mg/ml in dichloromethane.
2.4.2 Identification and Quantitation
2.4.2.1 Reference Materials - Assayed quantity of compounds of
interest (Table 2.1) and/or dilute standard solutions of
- compounds of interest in appropriate solvents.
2.4.2.2 Calibration Standards - bis-(pentafluorophenyl)phenyl
phosphine and D-10-anthracene.
29
-------
2.5 Preparation of Standards
Primary standard solutions may be prepared from the pure compounds by
dissolving 10 mg quantities into 10.0 ml of dichlcroaethane. Mixed
analytical standards may be prepared by diluting the primary solutions.
Analytical standards for all semivolatile compounds should be prepared in
three solutions. The acids standard should contain each of the phenolic
compounds at concentrations in the range of 50 to 200 ng/ul. 3/N/? com-
pounds should be split between two solutions, both at concentrations in
the range of 20 to 100 ng/ul. One standard should contain the more un-
stable 3/N compounds listed in Table 2.2 and the second should contain -the
remaining 3/N/? compounds. Analytical standards nay also be obtained from
I?A Effluent Guidelines Division or be prepared' by dilution of stock stand-
ard solutions purchased from chromatographic materials suppliers such as
Supelco, Inc. All working standards must include D-10-anthracene at 20
ng/ul.
2. 6 Sampling and Preservation
2.6.1 Sampling
Samples must be collected in glass containers (1,000-4,000 all with
".. a TFE-lined cap. The container should be prewashed with acetone
and dried before use. Containers should be filled no more than tvo-
thirds full with sample to minimize breakage during freezing.
30 265-
-------
2.6.2 Preservation
Preferably, samples should "be iced or refrigerated at ^"C for not
more than 24 hours before extraction. Where extraction cannot be
performed within 24 hours, saaples should be frozen. Samples cay
be stored for up to 30 days at -20°C or indefinitely at -75'C. In
order to prevent breakage during storage, the containers should not
be slightly warmed and then recooled. The iced or defrosted sample
should be homogenized by nixing for 1 minute with a tissuemizar
before analysis.
2.7 Sample Sxtraetion
2.7.1 Preparation of Drying Column
Immediately prior to extracting a sample, prepare a drying tube
for the extract. Place a small glass wool plug in the bottom of
the column and add anhydrous sodium sulfate to a depth of 10 to
15 cm.
2.7.2 pH Adjustment
Thoroughly mix the sludge sample by homogenizing in the sample
bottle for 1 minute, 4 samples at a time, then quickly remove an
- 80 ml aliquot into a 100 ml graduated cylinder. Transfer the
aliquot into a 250 ml centrifuge tube. Basify the 80 ml portion-
to pH i 11 with 6 IT sodium hydroxide solution. Mix briefly with
the homogenizer to insure uniform sample pH.
(Mote: If copious precipitation of carbonates is observed when
sodium hydroxide is added, make the sample slightly acidic with
31
-------
6 !T hydrochloric acid and allow the carbon dioxide evolution to
caa.se before basifying the sample.)
2.7.3 Extraction
Add 80 ml of dichloromethane to the sample and homogenize
for 45 to 60 sec. Do not homogenize more than 60 sec to avoid
heating the sample. Centrifuge the samples and extracts at 3,000
rpm for 30 minutes. Repeat centrifugation if satisfactory phase
separation is not achieved. The mixture will separate into an
aqueous layer over the dichloromethane extract with a solids cake
at the water-dichloromethane interface. Withdraw the extract from
each centrifuge tube with a 100 ml pipette. Discharge the extracts
into a 500 ml separately funnel. Drain the dichloromethane through
the drying column into a Kuderna-Danish evaporator. Retain any
aqueous layer and return it in approximately equal volumes to each
of the four centrifuge tubes.
Extract the sample two more times (to achieve three-fold extraction)
according to procedures described in Sections 2.7.3 and 2.7.4. Wash
the drying column, with an additional 100 ml of dichloromethane and
combine the eluent with the extracts.
2.7.4 Extract Concentration
Add a. boiling chip to the extract in the Kuderna-Danish evaporator
and concentrate the extract to -v 8 ml using a 85°C water bath or a
steam bath. If the extract is only slightly colored and not viscous
32 f~*t^'~*a-
-------
concentrate it further to 5 ml. If the extract solidifies after
cooling, dilute it to '8 ml. Transfer the extract to a. 10 ml
volumetric flask (or 10 ml graduated tube) , dilute to the nark
and store at 48C rot GPC cleanup.
2.7.5 Acidic Extraction
Acidify the sludge sample portions to pH S 2 with 6 N hydrochloric
acid and extract the sample again by procedures described in
Sections 2.7.. 3 to 2.7.4. Discard the extracted sludge aliquots.
2.8 Extract Cleanup
2.8.1 G?C Setup, .and Calibration
2.8.1.1 Packing the column - Place 50 to 60 g of Bio Beads -SX-3
in a 400 ml beaker. Cover the beads with dichloromethane
and allow the beads to swell overnight (before packing the
columns) . Transfer the swelled beads to the colunn and
start pumping solvent through the column, from bottom to
to top, at 5.0 ml/min. After —1 hour, adjust the pressure
on the column to 7 to 10 psi and pump an additional 4
hours to remove air from the column. Adjust the column
pressure periodically as required to maintain 7 to 10 psi.
2.8.1.2 Calibration of the column - Load 5 ml of the corn oil
solution into sample loop No. 1 and 5 ml of the phthalate-
phenol solution into loop No. 2. Inject the com oil and
collect 10 ml fractions (i.e., change fraction at 2 ainuts
33
-------
intervals) for 36 minutes. Inject the phthalate-phenol
solution and collect 10 ml fractions for 60 minutes. De-
termine the com oil elution pattern by evaporation of
each fraction to dryness followed by a gravimetric determi-
nation of the residue. Analyze the phthalate-phenol
fractions by GC/FTD on the SP-2250 and SP-1240-DA coluoss.
Plot the concentration of each component in each fraction
versus total eluent volume (or time) from the injection
points. Choose a "dump time" which allows >85Z removal of
the corn oil and ^85Z recovery of the bis (2-et'nylheryl)i-
phthalate. Choose the "collect time" to extend at -least
10 minutes after the elution of pentachlorophenol. "Wash"
the column 20 minutes^ between samples. Typical parameters
selected are: dump time, 20 minutes (100 ml) , collect
time, 30 minutes (150 ml) , and wash time, 20 minutes
(100 nl) . The column can also be calibrated by the -use
of a 254 nm UV detector in place of gravimetric and GC
analyses of fractions. Measure the peak areas at various
elution times to determine appropriate fractions.
2.S.2 Operation
Prefilter or load all extracts via the filter holder to avoid
particulates that might cause flow stoppage. Load one 5.0 ml
aliquot for extracts of 10 ml volume. Purge the sample loading
34
-------
tubing thoroughly with solvent between extracts. After aspeciaj.lv
dirty extracts, run a. G?C blank .(i. e.,, dichloromethane) to check
for carry-over. Process the extracts using the dump, collect, sad
wash parameters determined from the calibration and collect the
cleaned extracts in 500 ail brown bottles. Concentrate the cleaned
extractsr combining collected fractions from multiple injections,
to •v 10 si using Kuderna-Danish evaporators and then to •v 3 al
using micro Snyder columns. Transfer the cleaned extracts to 10
ml graduated tubes and dilute to 5.0 ml with dichloromethane.
Store at 4"C for GC/MS analysis. Intensely colored extracts nay-
require a second GPC cleanup. ..
2.9 Sanole Extract Analysis J
2.9.1 Acid.Extracts
GC/MS analysis - Analyze acid extracts by GC/MS using
the SP-1240-DA column described in Section 2.3.2.1,-
operated under the following conditions:
. Column temperature - 85*C for 4 'minutes, 85 to 200.*C
at 10"C/min and 200°C until after
the elation time for 4-nitrophenol.
Injector temperature - 185°C
GC/MS interface temperature - 275°C
Carrier gas - Helium at 30 ml/min
Injection size - 2 ul
35 27CK
-------
The MS should be repetitively scanned over the range
n/e 40 to 475 at 3 sec/scan. Immediately prior to analysis,
spike each extract with 50.0 ul of the internal standard
solution of 2.0 ug/ul D-10-anthracene in cichloromethane.
2.9.2 Base/Neutral Pesticide Extracts
'GC/MS analysis - Analyze the 3/N/? extracts by GC/MS
using the SP-2250 column described in Section 2.3.2.1
operated under the following conditions:
Column temperature - 50°C for 4 minutes, 50 to 260°C
at 10°C/ain, and 260"C until after
the elution tiae for benz[£,h_,^]perylene.
Injector temperature - 225*C
GC/MS interface teaperature - 275*C
Carrier gas - Helium at 30 ml/min
Injection size - 2 ul
The MS should be repetitively scanned over the range u/e
40 to 475 at 3 sec/scan.
Immediately prior to analysis, spike each extract with
50.0 yl of the internal standard solution, which contains
2.0 ug/ul D-10-anthracene in dichloronethane.
36
-------
2.10 Zxtractable Orsanies Analytical Quality Assurance
In addition to the instrumental quality assurance procedures specified1 ia
Se-ctions 2.10.1 and 2.10.2, analyses of replicate and fortified sacples an
blanks are required to indicate the method precision and accuracy. Since
the method precision may be very 'dependent on the sample matrix, the fre-
quency and selection of replicate and fortified samples, method and field
blanks, and fortified blanks is designed to provide soiae precision and
accuracy data for each sample matrix encountered and is consistent with
the objectives and limitations of screening analyses.
2.10.1 Method Blanks
Analyze one -method blank (i.e., organic-free water) and one
method blank spiked with each of the representative semi-
volatile compounds at 10 times the detection limits for
every 15 samples analyzed or at least once each month
that analyses are being conducted. Method blanks and
spiked blanks are extracted and the extracts cleaned by
the same procedures used for samples. Analyze extracts
of. spiked blanks by the GC/ilS procedures described in
Section 2.0. Analyze extracts of blanks by' GC/TTD using
the same chromatographic columns and conditions. Analyze
all blank extracts by GC/MS that exhibit peaks more
intense than the D-10-anthracene internal standard.
37
-------
.10.2 r.-alvtical Standards
2.1C.2.1 Acidic Compounds
2.10.2.2 Analytical Quality Assurance
2.lQ.2.2.a. Analyze daily a GC/XS quality assurance solu-
tion containing 10 ng/vl decafluorotriphenyl-
phosphine (DFTPP), and 20 ng/ul of D-10-anthra-
cene and 50 ng/yl A-r.irrophenol. Detection of
4-nitrophenol and the acceptability of the
DFTPP spectrum quality, based on the ion
abundance standards outlined in Table 2.3, are
necessary criteria for proceeding with sample
extract analyses.
2.10.2.2.0 Analyze daily a standard solution containing
f
each of the acidic compounds listed in Table
2.1 in the concentration range of 50 to 200 ng/
ul plus D-10-anthracene at 20 ng/yl. Response
factor data obtained from these standards are
used to estimate the concentrations of compounds.
identified in sample extracts.
2.10.2.3 Base/Neutral and Pesticide Compounds
2.10.2.3.a Analyze daily a GC/MS quality assurance
solution containing 10 ng/yl DrT??, 20 ng/ul
D-10-anthracene, and 50 ng/ul benzicene.
Detection of benridene and the ac-=ttabili:v
33
21""*'}.—
«^O^
-------
of che DFTP? spectrum quality (see Table
2.3) are necessary criteria for proceeding
with sample extract analyses.
2.10.2.3.b Analyze daily standard solutions containing
the base/neutral and pesticide compounds
listed in Table 2.1 in the concentration
range of 20 to 100 ng/yl plus D-10-anthraceene
at 20 ng/ul. Response factor data obtained
from these standards are used to estimate
the concentrations of compounds identified
in sample extracts.
2.10.3 Field Blanks
Extract an 80 ml aliquot of each field blank by bech extraction
with 3 100 ml portions of dichloromethane in a 1,000 ml separator?
funnel. Dry the extract by passage through a short column .'of an-
hydrous Na2SO£ and concentrate to 1.0 ml in a Kudema-Danish
evaporator. Analyze field blank extracts by CC/FID using the
chromatographic columns and conditions described in Section. 2.0...
Analyze all blank extracts by GC/MS that exhibit peaks more in-
tense than the D-10-anthracene internal standard.
2.10.4 Fortified and Duplicate Samples
2.10.4.1 Sample Selection - After the analysis of samples collected
at the first sampling tiae, spike and analyze duplicate
sample aliquots from the first samples. For example,
39
-------
for a survey program sampling s. POTW plane daily for 4
to 6 days, collect triplicate samples for the first day.
After completing analyses of one set of the first day
samples, spike and analyze duplicate first cay sanples.
Spike the first day samples using procedures described
in Section 2.10.4.2. The frequency of selecting spiked
duplicate samples for analysis for sampling rrograms
longer than 6 days should be determined from the deten-
tion tines of the sludge types sampled so as to reflect
possible changes in sample matrix.
2.10.4.2 Fortification Procedures - Spike an 30 ml aliquot of
sludge vith all of the compounds identified in the sample
and the representative semivolatile compounds listed in
Table 3.2 to produce a final concentration that is tvo
times the observed concentration or 10 times the .lover
limit of detection reported in Table 2.9, whichever
is greater. The spike should be contained in two
acetone solutions. The first contains, acidic and
neutral compounds and the second contains basic con-
pounds. The concentrations of the spiking solutions
should be such that 1 to 5 ml of each solution are
added to the sludge sample. Homogenize the spiked
sample for 45 to 60 sec and store at -°C overnight
before extraction and analysis.
-------
2.11 Data Handling
Using the characteristic retention times and.ions listed in Tables 2.4
to 2.6, obtian ZICP's of the characteristic ions for each compound.
Verify the presence of the compounds of interest based on the coincidences
of peaks in the characteristic ZICPs at the appropriate retention tiaes
with intensities in the characteristic ratios. Calculate the concentra-
tions of compounds identified by comparing the areas of the primary
(highest abundance) ion EICP peaks"with the areas -of the corresponding
standard peaks. If the sample matrix produces a significant interference
with the primary ion ZIC?, a secondary ion EIC? may be used for quantisa-
tion. Calculate the concentration of compounds identified in the 'sample
as follows:
-L,
_ , , _ i i - I ug/liter of analyte in wet sludge -•
y7!/ \VS/ l F
where:
A » area of peak in sample extract
3 = area of peak in standard
A^j * area of internal standard peak in sample extract
B^j = area of internal standard peak in standard
Vj_ - volume of extract injected (ul)
VE = total volume of extract (ml)
N = nanograms in standard
Vg = volume of wet sludge extracted (1)
F = fraction of extract cleaned by GPC for analysis (e.g.,
20 ml - .8).
25 ml
-------
Table 2.1. Seiaivolatile Organic Prioritv Pollutants
ACIDS
i-Chioro-3-methylphen.ol
2-Chlorophenol
2,4-Dichlorophenol
2,4-Dimethylphenol
4,6-Dinitro~2-methylphenol
Benzidine
BASES
NEUT5ALS
?olycyclic Aromatic Hydrocarbons
Acenaphthene
Acenaph cylene
Anthracene
Benzo(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(g,h,i)perylene
Benzo(a)pyrene
?hthalates
3is(2-ethylhexyl) phthalate
Butylbenzyl phthalace
Diethyl phthalate
Chlorinated Hydrocarbons
2-Chloronaphthalene
1,2-Dichlorobenzene
1,3-Dcihlorobenzene
1,4-Dichlorobenzene
Eexachlorobenzene
Chloroalkvl Ethers
3is-(2-chloroethyl) ether
3is-(2-chloroechoxy)nethane
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
3,3'-Dichlorobenzidine
Chrysene
Dibenzo(a,g)anthracene
Fluoranthene
Fluorene
Indeno(1,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
Dimethyl phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Hexachloro-1,3-butadiene
Hexachloroethane
Hexachlorocyclopentadiene
1,2,5-Trichlorobenzene
3is-(2—chloroisopropyl) ethe:
2-Chloroethyl vinyl ether
42
277<
-------
Table 2.1 (Concluded)
NEUTRALS
Miscellaneous Neutrals
4-3romophenyl phenyl ether
4-Chlorophenyl phenyl ether
2,4-DiAitrotoluene
N-Nitrosodiethylamine
N-Nitrosodimethylaaine
S-Indosulfan
a-3HC
T-3HC
S-3HC
Aldrin
Heptachlor
Heptachlor epoxide
a-Endosulfan
-Dieldrin
4,4'-DDE
PESTICIDES
2,5-Dinltrotoluene
Isophorone
Nitrobenzene
N-Ni tr o s o diphenylanine
4,4'-DDD
4,4'-DDT
Endrin
Endosulfan sulfate
6-BHC
Chlordane
Toxaphene
.PC3-1242
PCB-1254
43
-------
Discard
Sludge
Sludge
(320ml.)
Adjust to pH> 11
with 6£J NoOH
Extract 3X with CH2Cl2
by Homogeni ration/
Centrifugation
Sludge
Adjust to pH< 2
with 6M HC1
Extract 3X wirh CH2CI2
by Homogenization/
Centrifugation
Dry with Na2$O4
Clean Up by GPC on
Bio Beads SX-3 Eluted
with CH2CI2
Determine Phenols
by GC/MS
on SP-1240-OA
txtract
Dry with
Clean Up by GPC on
Bio Beads SX-3 Eluted
with CH2CI2
Determine Base/Neutrcls
& Pesticides by GC/MS
on SP-2250
Analysis Scheme for Senivolatile Organics
-------
Table 2.2. Unstable 3/N Compounds
bis(2-Chloroiso?ropyl) ether
Nitrobenzene
N-Nitroso-di-h-propvlanine
bis(2-Chloroechoxy) methane
Isophorone
2,6-Dinitrotoluena
2,4-Dinitrotoluene
1,2-Diphenylhydrazine
Bensidine
3,3'-Dichlorobensidiae
N-Ni tr o sodimethylamina
Table, 2.3. DrTPP Kav Ions and Ion Abundance Criteria
Mass Ion Abundance Criteria
51 30-60Z of mass 198
68 less than 22 of aass 69
70 less than 27. of mass 69
127 40-60% of mass 198
197 less than 1% of mass 198
198 base peak, 100% relative
abundance
199 5-9% of mass 198
275 10-30% of mass 198
'365 1% of mass 198
441 _ less than mass 443
442 greater than 40% of mass 198
443 17-23% of mass 442
45 28CK
-------
Table 2.4. Acid Comoounds
Compound Name
RRT-/
D-10-Anthracene
Characteristic
El Ions (Rel. Int.)
2-Chlorophenol
2-Nitrophenol
Phenol
2,4-Dimethyl phenol
2 , 4-Dichlor opheriol
2,4, 6-Trichlorophenol
4-Chloro-m-cresol
2 , 4-Dinitrophenol
4 , 6-Dinitro-o-cresol
Pentachlorophenol
4-Nitrophenol
0.38
0.43
0.50
0.58
0.60
0.74
0.83
1.03
1.04
1.15
1.70
128(100), 64(54), 130(31)
139(100); 65(35), 109(8)
94(100), 65(17), 66(19)
122(100), 107(90), 121(55)
162(100), 164(50), 98(61)
196(100), 198(92), 200(26)
142(100), 107(80), 144(32)
184(100), 63(59), 154(53)
198(100), 182(35), 77(28)
266(100), 264(62), 268(63)
65(100), 139(45), 109(71)
a/ Column: 1.2 m x 2 mm ID glass; 1% SP-1240 DA on 100/120 Supelcoport;
He at 30 ml/min.
Program: 85°C for 4 min, then 10°C/iain to 200°C and hold for 15 ain.
46
2Si<
-------
Tab1e 2.5. Base-Neutral Compounds
Compound Nasne
1 , 3-Dichlorobenzene
1 , 4-Dichlorobenzene
Hexachloroethane
1 , 2-Dichlorobenzene
3is(2-chloroisopropyl) ether
Hexachlorobutadiene
1 , 2 , 4-Trichlorobenzene
Napthalene
3is(2-chloroethyl) ether
Hexachlo rocy clopentadiene
Nitrobenzene
3 is ( 2-chloroe thoxy) methane
2-Chloronaphthalene
Acenaphthylene
Acenaphthene
Lsophorone
Tluorene
2, 6-Dinitro toluene
1, 2-Diphenylhydra2ine^/
2, 4-Dinitro toluene
N-Nitrosodiphenylasine-^
Jexacj jprpbeazeme
4-3romophenyl phenyl ether
Phenanthrene
Anthracene
Diaethyl phthalate
Diethyl phthalate
Fluoranthene
Pyrene
Di-n-butyl phthalate
Benzidine'
Sutylbenzyl phthalate
Chrysene
Di-(2-ethylhexyl) phthalate
3enzo (a) anthracene
Di-n- octylphthalate
Benzo Cb) f luoranthene
3enzo (k) f luoranthene
3enzo(a)pyrene
Indeno (1,2, 3-cd) pyrene
RRT^
D-10-Anthracene
0.31
0.33
0.35
0.35
0.37
0.48
. 0.49
0.51
0.55
0.59
0.45
0.50
0.68
0.75
0.77
0.47
0.85
0.81
0.87
0.85
0.89
0.92
0.92
1.00
1.00
0.78
0.87
7.18
1.22
1.09
1.27
1.34
1.40
1.37
1.41
1.41
1.43
1.43
1.50
1.86
Characteristic
El Ions (Rel. Int.)
146(100), 148(64), 113(12)
146(100), 148(64), 113(11)
117(100), 199(61), 201(99)
146(100), 140(64), 113(11)
45(100), 77(19), 79(12)
225(100), 223(63), 227(65)
74(100), 109(80), 145(52)
128(100), 127(10), 129(11)
93(100), 63(99), 95(31)
237(100). 235(63), 272(12)
77(100). 123(50), 65(15)
93(100), 95(32), 123(21)
162(100), 164(32), 127(21)
152C100), 153(16), 151(17)
154(100), 153(95),' 152(53)
82(100), 95(14), 138(18)
166(100), 165(80), 167(14)
165(100). 63(72), 121(23)
77(100), 93(58), 10.5(28)
165<100.), 63(72), 121(23)
169(100), 168(71), 167(50)
284(100), 142(30), 249(24)
248(100), 250 (99), -141 (45)
178(100), 179(16), 176(15)
178(100), 179 (16), -176(15)
163(100), 164(10). 194(11)
149(100), 178(25), 150(10)
202(100), 101(23), 100(14)
202(100), 101(26), 100(17)
149(100), 150(27), 104(10)
184(100), 92(24), 185(13)
149(100), 91(50)
229(100), 229(19),' 226(23)
149(100), 167(31), 279(26)
228(100). 229(19), 226(19)
149(100), 167, 279
252(100), 253(23), 125(15)
252C100), 253 G3), 125(16)
252(100), 253(23), 125(21)
276C100), 138(23), 277(27)
47
-------
Table 2.5 (Concluded)
Compound Name
RRT
D-10-Anthracene
Characteristic
El Ions (Rel. Int.
3eazo(g,h,i)perylene
N'-Ni tr o s o dimethy lamina
N-Nitrosodi-n-propylamine
4-Chlorophenyl phenyl ether
3,3' -Dichlorobenzidine
2,3,7, 8-Tetrachlorodibenzo-p-dioxin
Bis (chloromethyl) ether
Deuterated anthracene (dlO)
1.98
0.15
0.42
0.85
1.45
1.33
—
1.00
276(100)
42,100),
130(22),
204(100)
252(100)
322(100)
45(100) ,
188(100)
, 138(37), 277(25)
74(88), 44(21)
42(64), 101(12)
, 206(34), 141(29)
, 254(66), 126(16)
, 320(90), 59(95)
49(14), 51(5)
, 94(19), 80(18)
a/ 1" SP-2250 on 100/120 mesh Supelcoport in a 1.8 m x 2 mm ID glass column;
He at 30 ml/min. Program: 50"C for 4 min, then 10eC/min to 260°C and
hold for 15 min.
b/ Elutes as azobenzene.
c/ Zlutas as diphenylaniine.
48
-------
Table 2.6. Pesticides
ConrDound Name
D-10- Anthracene
Characteristic
El Ions (Rel . Int . )
S-endosulfan
a-BHC
Y-BHC
S-BHC
Aldrin
Heptachlor
Heptachlor epoxide
c-Zndosulfan
Dieldrin
4,4' -DDE
4,4' -DDD
4,4' -DDT
Endrin
Endosulfan sulfate
0.47
0.94
1.00
1.03
1.05
1.06
1.13
1.14
1.18
1.20
1.22
1.27
1.30
1.30
201(100), 283(48), 278(30)
183(100), 109(86), 181(91)
183(100), 109(86), 181(91)
181(100), 183(93), 109(62)
66(100), 220(11), 263(73)
100(100), 272(60), 274(46)
355(100), 353(79), 351(60)
201(100), 283(48), 278(30)
79(100), 263(28), 279(22)
246(100), 248(64), 176(65)
235(100), 237(76), 165(93)
235(100), 237(72) , 165(59)
81(100), 82(61), 263(70) .
272(100), 387(75), 422(25)
o-BHC
Chlordane
Toxaphene
PC3-1242
PC3-1254
1.04
1.05-1.26
1.12-1.35
0.86-1.14
1.09-1.30
183(100), 109(86), 181(90)
373(19), 375(17), 377(10)-'
(231, 233, 235)£/
(224, 260, 294)£7
(294, 330, 362)-£7
a/ 1% SP-2250 on 100/120 mesh Supelcoport in a 1.8 ni x 2 sm ID glass
colimn; He at 30 ml/min. Program: 50° for 4 min, then 10*C/
min to 260° and hold for 15 min.
b/ These three ions are characteristic for the a and f forms of
chlordane. No stock should be set in these three for other
isomers.
c/ These ions are listed without relative intensities since the
mixtures they represent defy characterization by three masses.
49
-------
APPENDIX I
-------
Table A-2. Fortification Detection Liaits for Base, Neutral, Pesticide,
and Acid Zxtractable Organic Priority Pollutant Compounds
Detection Li=it "°
ng/uil CociDound
< 10 Naphthalene
Fluorene
Di-n-butylphthalate
Fluoranthene
Pyrene
Bis(2-ethylhexyl)phthalate
Ac enaph thy1ene
Diethylphthalate
Benzo(k)fluoranthene
Bis(2-chloroisopropyl)ether
1,2-diphenylhydrazine
Phenanthrene/anthracene
10 - 20 2-Chloronaphthalene
Acenaphthalene
2,6-Dinitrotoluene
Butylbenzylphthalate
Benzo[a]pyrene
1,2,4-Trichlorobenzene
Diaiethylphthalate
Di-n-octyl?hthalate
4-Chlorophenylphenylether
Hexachlorobenzene
Benzidine
3,3'-Dichlorobenzidine
4,4'-DDE
4,4'-DDT
Toxaphene
Chrysene/benzo[a]anthracene
20 - 30 m-Dichlorobenzene
> o-Dichlorobenzene
-------
Table A-2 (Concluded)
Detection Limit Range
ng/ml
Cotroound
30 - 40
40 - 50
50 - 100
230
240
200
630 - 600
Bis(2-chloroethyl)ether
a-BHC
T-3HC
Endrin
Heptachlor
2-Chlorophenol
2,4-Dinitrotoluene
N-Nitroso-di-n-propylamine
o-BHC
2,4-Dimethylphenol
2,4-Dichlorophenol
Nitrobenzene
Bis (2-chloroethoxy)aethane
Hexachlorocyclopentadiene
8-3HC
Heptachlor epoxide
Dieldrin
2-Nitrophenol
Trichlorophenol
p-Chloro-m-cresol
Pentachlorophenol
4,6-Dinitro-o-cresol
p-Nitrophenol
Isophorone
2,4-Dinitrophenol
SLJ Detection limit based on standard responses and a mininrua count of 1,000
for compound identification. Detection limits are for the original
analyte concentration in sludge and presumes use of this protocol.
54
-------
SECTION III
-------
made up to 10 ml volumes with organic-free water. The
resultant analyte concentrations are 5 ug/liter and 25
ug/liter (or 50 ng and 250 ng analyte weights, respec-
tively) .
Since reduced sensitivity is frequently observed for the
more volatile purgeabie compounds, including acrylonitrile,
bromomethane, chlorraethane, coloroethane, dichlorodifiuoro-
methane, and vinyl chloride, these compounds should be
present in the aulticcmponent standard at higher concen-
/
trations. A four-fold increas-e in the concentrations of
bromomethane, chloromethane, chloroethane, dichlorodiflu-
OTomethane, and vinyl chloride to produce 4 ug/nl final
concentrations of these compounds in the nulticomponent
secondary dilution will result in more reliable analyta
responses. Similarly, a five-fold increase in the- acryio-
nitrile concentration to 5 ug/ml in the multicomponent
standard is also desirable.
1.6.1.2 Preparation from commercial mixed stock solutions - As an
alternate to the preparation of standards from neat mate-
rials, high concentration stock mixtures of volatile or-
ganic priority pollutaats may be purchased commercially.
The method outlined below is specifically designed for
utilizing stock mixtures available from Supelco, Inc.
290-
-------
INTERIM REPORT
QUALITY ASSURANCE FOR LABORATORY ANALYSIS
OF
129 PRIORITY POLLUTANTS
PREPARED FOR:
ENVIRONMENTAL PROTECTION AGENCY
PbNiTORiNG & DATA SUPPORT DIVISION
OFFICE OF WATER PLANNING & STANDARDS
401 M STREET, S.W.
WASHINGTON, D,C. 20460
PREPARED BY:
VEESAR INC.
5621 ELECTRONIC DRIVE
SPRINGFIELD, VIRGINIA 22151
(703) 750-3000
CONTRACT No, 58-01-5908
TASK 1,4
FEBRUARY 4, 1980
-------
QUALITY ASSURANCE FOR. LABORATORY
ANALYSIS OF PRIORITY POLLLTCANTS
i Preface
ii List cf Tables
iii List:- of Figures
Acknowledgements
I ESiTKJCUCTION
II GENERAL QUALITY CONTROL CONSIDERATIONS AND ANALYTICAL
iMETHODDLCGIES
III PRIORITY POLLUTANT LABORATORY QUALITY CCNTJOL
IV PERFORMANCE CONTROL LIMITS FOR PRIORITY POLLUTANTS
-------
TABLE OF C3N7:NT3
Chapter
PREFACE .
ACKNOWLEDGMENTS
IMPORTANCE OF QUALITY CONTROL I-1
1.1 General - [
1.2 Quality Assurance Programs -1
1.3 Analytical Methods -2
1.4 Reference —
LABORATORY SERVICES :-[
2.! General . 2-!
i: Distilled Water M
2.3 Compressed Air 2-5
2.4 Vacuum . 2-5
2.5 Hood System 2-5
2.6 Electrical Services 2-5
2.7 References 2-5
INSTRUMENT SELECTION 3-1
3.1 Introduction 3-1
3.2 Analytical Balances 3-1
3.3 pH:Selective-Ion Meters 3-3
3.- Conductmry Meters 3-5
3.5 Turbidimeters (Nephelometers) 3-T
Spectrometers 3-3
Organic Carbon Analyzers 3-13
Gas Chromatographs 3-i-
Ri ferences 3 -1 -
GLASSWARE -i
-.! General —!
4.2 Types of Glassware — 2
4.3 Volumetric Analyses . . —3
~ - Federal Specifications :"cr Voiumecr.c Glassware —4
4.5 Cleaning of Glass and Porcelain ~-5
45 Special Cleaning Requirements 4-c
4." Disposable Glassware —"
4.3 Specialized Glassware —"
4.? F-::ed Ware —i
4 10 References ~-y
REAGENTS. SOLVENTS. AND GASES
5 . introduction
5.2 Reagent Quality -;
-------
5.3 Elimination of Determinate Errors
5.4 References
6 QUALITY CONTROL FOR ANALYTICAL PERFORMANCE . . . a- 1
5.1 Introduction ......... • • • • • . f-i
6.2. The Industrial Approach co QC ........... 6-1
6.3 Applying Control Chans in Environmental Laboratories ... 5-2
6 A Recommended Laboratory Quality Assurance Program . . . 6-9
5.5 Outline of a Comprehensive Quality Assurance Program . . . 5-iO
6.6 Related Topics ................. 6-13
6.7 References ........................ 6-! 3
7 DATA HANDLING AND REPORTING . .7-1
?. I Introduction ............ . ..... 7-i
7.2 The . Analytical. Value ..... •. ........ 7-1
7.3 Glossary of Statistical Terms ............... 7-3
7.4 Report Forms .... ............. ... . 7-5
7.5 References .......................... 7-11
8 SPECIAL REQUIREMENTS FOR TRACE ORGANIC ANALYSIS . . 3-1
8.1 'Introduction ..................... 8-1
8.2 Sampling and Sample Handling ............... 8-1
3.3 Extract Handling ................. 3-4
3.4 Supplies and Reagents . . . • ... . . . . .... 8-5
8.5 Quality Assurance .............. . . .8-7
8.6 References ............... ..... 8-10
9 SKILLS AND TRAINING" ...... ....... 9-1
9.1 General .................. 9-1
9.2 Skills ............... . . 9-2
9.3 Training ................... . . 9-4
10 " WATER AND WASTEWATER SAMPLING ....... 10- 1
10.1 Introduction .......... : ........ ... . 10-1
10.2 .Areas of Sampling ............... 10-2
10.3 References .................. 10-6
11 RADIOCHEMISTRY .................. !Ul
It. I Introduction ........ . . ... 11-1
11.2 Sample Collection . ... .11-1
11.3 Laboratory Practices . . . . 11-2
1 1.4 Quality Control . . ... 1 l-t
1 1.5 References . . . .
12 MICROBIOLOGY ........ ...
12.1 Background ........ .... .
12-2 Specific Needs in Microbiology . .
12.3 Intralaboratory Quality Control . 12-2
12.4 Interiaboratory Quality Control . . 12-2
1 2.5 Development of a Formal Quality Assurance Program 1 2-3
1 2.5 Documentation of a Quality Assurance Program 1 2-3
-------
12.7 Chain-of-Custody Procedures for Microbiological Samples ---3
12.8 References . 12-10
13 AQUATIC BIOLOGY . . .. :3-l
13.1 Summary of General Guidelines i 3-1
13.1 Discussion ... . 13-2
13.3 Rsferancs .... . 13-4
14 LABORATORY SAFETY . . L-M
14.1 Law and Authority for Safety and Health 14-1
14.2 EPA Policy on Laboratory Safety 1—5
14.3 Laboratory Safety Practices 14-7
14.4 Report of Unsafe or Unhealthful Condition 14-15
14.5 References . 14-15
Appendix A-Suggested Checklist for the Safety Evaluation of EPA Laboratory Areas A-1
v\i
-------
PREFACE
The following Quality Assurance Guide for laboratory Analysis of
Priority Pollutants vas produced at the request of the Monitoring
and Data Support Division of the Office of Water Planning and
Standards to support the National Urban Runoff Program surveillance
and analysis effort. The objective of this report is to reflect
EPA's best effort and understanding of what steps and actions are
required to define the meaningfulness of laboratory analysis.
-------
LIST OF TAHT.K
1. Priority Pollutant Fractions to be Analyzed
2. Purgeable Organic Fraction
3. Base/Neutral Fraction
4. Acid Fraction
5. Pesticide Fraction
6. Metals Fraction
7. Conventional Fraction
8. Priority Pollutant Batch Size Effect on Relative QC Effort
9. Standard C.C Format (example)
10. Surrogate Recovery Format (example)
11. Purgeable Fraction - Matrix Effect Spike
12. Purgeable Fraction - Surrogate Spike
13. Acid Fraction - Matrix Effect Spike
14. Acid and Base/Neutral Fraction - Surrogate Spike
15. Base/Neutral Fraction - Matrix Effect Spike
16. Pesticide Fraction - Matrix Effect Spike
17. Metals Fraction - Matrix Effect Spike
18. Conventional Fraction - Matrix Effect Spike
19. Possible Sources of Standards
20. Intra- Laboratory Comparison
21. Purgeable Organics
22. Acid Fraction
23. Base/Neutral Fraction
24. Pesticide Fraction
25. Metals, Cyanide and Phenolics
26. Priority Pollutant Surrogates
-------
LIST ..OF FIGOPES
1. Handbook for Analytical Quality Control
2. Surtnary of Required Samples and Audits for Priority Pollutant
Analysis
iii
-------
JONCWLEDGEMESTS
This document rests en the work and cones about throught the
efforts of numerous laboratories and scientists. Stable anoung
the contributors are R.D. Kleopfer and B.J. Fair less at Region VII,
Kansas City, Kansas; D. Ballanger and staff at EMSL, Cincinnati,
Ohio; and the Versar Inc. staff at Springfield, Va.
-------
This document defines those actions that must be taken to assure than
valid priority pollutant data is produced by analytical laboratories. The
general day-to-day procedures will be referred to as quality control (QC)
activities. The implementation coordination and supervision of these proce-
dures will be referred to as quality assurance (QA) activities. In this
broader sense, the program will cover the four major aspects of a quality
assurance program. Under the title of good laboratory practice will be
covered reference to all aspects of laboratory operation. The main areas of
procedures and methods will also be summarized. The major effort in this
program will be to develop a workable day-to-day QC model and, secondly, to
provide the detail control limits against which to measure a laboratory's
performance.
The methodologies and procedures, as well as associated good laboratory
practice, required to do the analysis will be defined primarily through
references. All references, to procedures and methods are based on EPA usual
practice. EPA concludes that these methodolcgies are adequate for priority
pollutant analysis. The adequacy of the data produced has been recently sum-
marized in an EPA report as follows:
"Vfe can be. confident that false positive analysis are
considerably less likely than false negative analysis
so that when a priority pollutant is detected in the
environment, we know the measured quantity is probably
smaller than the true value."
Two principal areas specific to priority pollutants are addressed in
this presentation. The first spells out those actions that must be taken to
assure that data produced will be of known quality. The second presents
criteria against which analytical data can be judged. Taken together, this
document will assure data that is statistically valid, defensible and of
known precision and accuracy.
For cost study work where the priority pollutants are really unknown,
where matrix effects are undefined and where sampling conditions are uncertain,
the procedures and QC practices specified here represent the most cost-effective
3CCK
-------
solution to a complex problen. As routine monitoring crograms cevelcc, a
relative reduction in the required quality control activities and, her.cs,
the cost is expected. Such considerations in cost reduction fall into a
broader management purview of quality assurance than this document addresses.
A comprehensive Laboratory Quality Control Program attempts to answer
the following sorts of questions:
(1) Are the field samples contaminated?
(2) Is the analytical instrument working?
(3) Are all matrix effects under control?
(4) Was each sample properly handled in the laboratory?
(5) Is the precision of the analysis in the acceptable range?
(£) Is the laboratory uncontaminated? "
Unless the answer to all of these questions is "yes," there is reasonable
doubt, for every sample batch, that valid data is being acquired. These
questions are answered by analyzing, along with the samples, solutions pre-
pared to address these concerns. A sample is defined as that portion of wacer
chosen to characterize a specific site. Any other solution is to be considered
as a quality control audit. This distinction can be made clear by considering
a duplicate sample taken in the field. One of the pair is a sample scluticr.
and the other a quality control audit solution. The comprehensive set cf CC
audit solutions to answer *11 of the above concerns include:
(1) A field blank
(2) A method standard
(3) A duplicate spiked with compounds of interest
(4) A duplicate analyzed
(5) A laboratory blank
The rain control objectives and many minor control objectives can be accom-
plished by running five quality control checks with each batch cf tr-venty
samples ccirrleted in one day. This -model will be expanded in detail considering
the entire pncri-y pollutant list cf organic and inorganic parameters in
Section "~.
-------
The 129 toxic and/or priority pollutants are giver.'in Tables 2-7. This
QA document addresses all of these except asbestos which is not within the
scope of this work. The toxics are grouped and named by their analytical
nethcdologies. The class names of the toxics and the number of class members
are defined in Table 1.
302<
-------
TABLE 1
PSJDRTTY POLLDTANT FRACTIONS
TO BE ANALYZED
General
Group
Organic
Parameters
Inorganic
Parameters
Class Name
Purgeables
Acids
Base/Neutrals
Pesticides
Metals
a. flame atonic
absorption
b. furnace atomic
absorption
c. cold vapor atomic
absorption
Ccraron
Abbreviation
VQA
A
B/N
P
AA
FAA
Mo. of Elements
or Compounds
31
11
46
25
10
2
1
Conventional, CN~ and
Phenol
Asbestos - not covered in this
document
Total
129
-------
TABLE 2
ORffiNICS FRACTION
(1) Acrolein (30) Trichlorofluoromethane
(2) Acryionitrile (31) Vinyl Chloride
(3) Benzene
(4) Brorodichloromethane
(5) BromofoCT
(6) Broncrrethane
(7) Carbon Tetrachloride
(8) Chlorcbenzene
(9) Chlorodibrortorethane
(10) Chloroethane
(11) 2-Chloro(ethyl vinyl) ether
(12) Chloroform
(13) Chloromethane
(14) Dichlorcdifluoromethane
(15) 1,1-Dichloroethane
(16) 1,2-Dichloroethane
(17) 1,1-Dichloroethylene
(18) Trans-1,2-Dichloroethylene
(19) Dichlororrethane
(20) 1,2-Oichloropropane
(21) Cis-l,3-Dichloropropene
(22) Trans-1,3-Diohloropropene
(23) Ethylbsnzene
(24) 1,1,2,2-Tetrachloroethane
(25) Tetrachloroethylene
(26) Toluene
(27) 1,1,1-Trichlcroethane
(23) l,i,2-Trichlorcethane
(29) Trichloroethylsne '
304<
-------
TABLE 3
BASE/NEUTFAL FSACTICN
(1) Acenaphthene (26)
(2) Acenapthylene (27)
(3) Anthracene (28)
(4) Benzidine (29)
(5) Benzo(a)anthracene (30)
(6) Benzo(b)fLuoranthene (31)
(7) Benzo(k)fluoranthene (32)
(8) Benzo(a) pyrene (33)
(9) Butyl Benzyl Phtha.late (34)
(10) Bis(2-chlorcethyl) Ether (35)
(11) Bis(2-chloroethoxy) Methane (36)
(12) Bis(2-chloroisopropyl) Ether (37)
(13) 3is(2-ethylhexyl) Phthalate (38)
(14) 4-Brorcphenyl Phenyl Ether (39)
(15) Butyl Benzyl Phthalate (40)
(16) 2-Chloronaphthalene (41).
(17) 4-Chlorophenyl Phenyl Ether (42)
(18) Chrysene (43)
(19) Dibenzo(a,h)anthracene (44)
(20) Di-n-butyl Phthalate (45)
(21) 1,2-Dichlorobenzene (46)
(22) 1,3-Dichlorcbenzene
(23) 1,4-Dichlorcbenzene
(24) 3,3'-Dichlorcbenzidine
(25) Diethyl Phthalate
Dimethyl Phthalata
2,4-Oinitrotoluene
2,6-Dini trotoluene
Di-n-octyl Phthalate
1,2-Oiphenylhydrazine
Fluoranthene
Fluorene
Hexachlorobenzene
Hexachlorobutadiene
Hexachlorocyclopentadiere
Hexachloroethane
Isophorone
Indeno(1,2,3-cd)pyrene
Naphthalene
Nitrobenzene
N-ni trosodime thy lar^ine
N-nitrosodiphenylamine
N-nitrosodi-n-propylamirjs
Phenanthrene
Pyrene
1,2,4-Trichlorobenzene
305
-------
TABLE 4
ACID FRACTION
(1) 2-Chlorophenol
(2) p-dloro-ov-cresol
(3) 2,4-Dichlorophenol
(4) 2,4-Oimethylphenol
(5) 4,6-Dinitro-o-cresol
(6) 2,4-Dinitrcphenol
(7) 2-Nitrophenol
(8) 4-Nitrophenol
(9) Pentachlorcphenol
(10) Phenol
(11) 2,4,6-Trichlorophenol
-------
TABLE 5
PESTICIDE FRACTION
(1) Aldrin
(2) alpha-BK:
(3) beta-BIE
(4) ganma-BKC
(5) delta-BHZ
(6) Chlordane
(7) 4,4'-ODD
(8) 4,4'-CDE
(9) 4,4'-DDT
(10) Dieldrin
(11) Endosulfan I
(12) Endosulfan II
(13) Endosulfan Sulfate
(14) Endrin
(15) Endrin Aldehyde
(16) Heptachlor
(17) Heptachlor Epoxide
(18-24) PCS (7 Aroclors)
(25) Toxaphene
307<
-------
TABLE 6
METALS FRACTION
(1) Antimony
(2) Arsenic
(3) Beryllium
(4) Cadmium.
(5) Chromium
(6) Copper
(7) Lead
(8) Mercury
(9) Nickel
(10) Selenium
(11) Silver
(12) Thallium
(13) Zinc
TABLE 7
CONVENTIONAL FRACTION
(1) Cyanides
(2) Total Phenols
308<
-------
13.
II GENERAL QUALITY CONTROL CONSI-EPATIGNS AND ANALYTICAL METHODOLOGIES
A. laboratory Good Practice
The Environmental Monitoring and Support Laboratory document (EPA-
600/4-79-019) contains all of the salient considerations which can fern the
general base for any Laboratory Quality Assurance Program. This document is
available in Icoseleaf form and should be used by all laboratories in these
programs. The abstract, and table of contents are included in this section
to show the scope of its concerns (Figure 1).
B. Priority Pollutant Methodologies
The methods required to do the 129 priority pollutants are found in
the following:
• "Sampling and Analysis Procedures for Screening of
Industrial Effluents for Priority Pollutants," U.S.
EPA, Environmental Monitoring and Support Laboratory,
Cincinnati, OH 45263, March 1977 (revised April 1977).
• "Handbook for Analytical Control in Water and Wastewater
Laboratories," U.S. EPA, Environmental Monitoring and
Support, Cincinnati, OH 45268, March 1979.
The documents are available from the Environmental Monitoring and
Support Laboratory (Cine.). In addition, various other aspects of the required
methods will be found in the following two references:
• "Procedure for Preliminary Evaluation of Analytical
Methods to be Used in the Verification Phase of the
Effluent Guidelines Division BAT Review," U.S. EPA,
Environmental Monitoring and Support Laboratory,
Cincinnati, OH 45263, March 1978
• "Addendum for Sampling and Analysis Procedures for
Screening of Industrial Effluents for Priority Pollu-
tants," U.S. EPA, Environmental Monitoring and Support
Laboratory, Cincinnati, OH 45268, April 1979.
And, lastly, the alternative methodologies recently proposed ara found' i-.:
• Federal Register, Volume 44, No. 233, December 3, 1979.
"Guidelines Establishing Test Procedures for the Analysis
cf Pollutants, Proposed regulations."
309<
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11.
FIGURE I
HANDBOOK FOR ANALYTICAL QUALITY CONTROL
IN WATER AND WASTEWATER LABORATORIES
Environmental Monitoring & Support Laboratory
(Cincinnati)
* Abstract
• Table of Contents
31CK
-------
ABSTRACT
One of the fundamental responsibilities of water and waste-water management is the
establishment of continuing programs to insure [he reliability and validity of analytical
laboratory and field data gathered in water treatment and wastewater pollution control
activities.
This handbook is addressed to laboratory directors, leaders of field investigations, and other
personnel who bear responsibility for water and wastewater data. Subject matter of the
handbook is concerned primarily with quality control (QO for chemical and biological :ests
and measurements. Chapters are also included on QC aspects of sampling, microbiology,
biology, radiochemistry. and safety as they relate Co water and wastswater pollution
control. Sufficient information is offered to allow the reader to inaugurate or reinforce
programs of analytical QC that emphasize early recognition, prevention, and correction of
factors leading co breakdowns in the validity of water and wastewater pollution control
data.
Lll
-------
Ill PSICSTTY PCIiLTANTS - LABORATORY QUALITY CONTROL
A. Introduction
This section is a summary of the efforts in several ZPA and contract
laboratories to develop a meaningful cost effective quality control model.
A listing of required samples and controls for priority pollutant analysis
can be seen in Figure 2. The general CC model will be discussed in the
following sections as it is applied to each fraction of the priority pollutant
list of 129. Five control solutions most be evaluated with each batch of
samples. The impact of the number of samples in each batch is shewn in
Table 8. The 25 percent controls required by this mcdel presupposes very
little or no experience- with the sample types and specific fractions under
consideration. As a data base develops, one can envision that only samples
spiked with surrogates would be used in the presence of sufficient data. For
most developmental study work, however, the 25 percent baseline- will have to
be maintained to assure the quality of the agency data base. Lastly, this
section will specify the quality control, documentation requirements necessary
to support this effort.
B. Basic Terms
1. Sample
A sample is a representative portion of an item from which
characteristics of the whole can, be extracted. In this program, a sample is
the volume of properly preserved water required to analyze for a specific
pollutant(s) of a given fraction. If duplicate field samples are taken, the
second one will be referred to as a QC control or a QC audit solution.
2. QA Audit Solution
A QC audit solution is the volume of water used to test seme
varible that it is desired to control. Examples of such solutions are spiked
solutions, blanks of various kinds and, generally, any material that is used to
ascertain the validity of the data.
-------
•7
3U-MAPY CF REQUIRED SAMPLES .--^ CCJ-.TPCLS
FOR
PRIORITY POLLUTANT ANALYSIS
Laboratory •
Sairinles Laboratorv
Method
Blank
I • 1
Spiked -vith Surrogate Solution
'— Spiked with Matrix Effect Solution
If, n = 20
Then, 25 saircles -.vould have to be analyzed
-------
13.
TABLE 8
PRIORITY POLLUTANT 3ATCH SIZE EFFECT ON
RELATIVE QC EFFORT
No. Sairoles in 1 Batch
No. QC Controls
% QC
1
2
5
10
15
20
5
5.
5
5
5
5
500
250
100
50
33
25
Batch sizes much greater than 20 are probably unrealistic.
-------
19.
The following subsections 3-15 are taken directly frcm a
Region '711 Document "Quality Assurance - Organic Parameters." Changes have
been made to make their suggestions relevant to this document and to r=rove
any responsibility for Region vn to provide either surrogate or matrix effect
spikes.
3. Volatiles
The laboratory shall run one duplicate (same sample run twice),
one field blank, one reagent blank (laboratory prepared "organic-free" water),
one method standard (standard addition to "organic-free" water), and one matrix
effect spike (standard addition to a sample) for each batch of samples processed.
The Laboratory shall calculate the percent recovery of the surro-
gates and the standards using the external standard quantitiation method. The
surrogate spikes will be added to every sample immediately before analysis
begins. The standard additions will be added and held for one hour prior to
the beginning of the analysis.
4. Extract"?bles - Acids and Base/Neutrals
The laboratory shall run one duplicate, one field blank, one
reagent blank, one method standard, and one matrix effect spike for each batch
(a group of samples from each plant studied) of samples processed. The pesti-
cides will be measured using the external standard method. The base/neutral
and acid fractions will be measured using the internal standard method.
5. Method Blank
The method blank is defined as an appropriate volume of "organic-
free" water which has been processed exactly as a sample (same glassware,
reagents, solvents, etc.). For the extractable parameters (3/N, A, P) , this
would recuire extraction of one liter of water. For the volatile fraction, 5
ml of "organic-free" water should be analyzed by the purge and trap methodology.
One method blank sample should be run with every batch of 20 or fewer samples.
Also, a r.ethoc blank should be run whenever a new source of reagent or solvent
is introduced into the analytical scheme. Reagents having background levels
315<
-------
that interfere with the compounds to be determined must be purified and shewn
to be free of known interferences or replaced with some that are acceptable.
6. Field Blank
It is the responsibility of the sampling team to provide the
appropriate field blanks to the analytical team. For the extractable para-
meters (B/N, A, P), the minimum requirement is to provide an appropriate volume
of blank water which has been processed through the sampling equipment in the
same manner as a sample. The field blank is then analyzed in the laboratory
as if it were a sample. When interferences occur, the analytical results must
be discarded or flagged so as not to result in the reporting of false positives
7. Replicates
To determine the precision of the method, a regular program of
analyses of replicate aliquots of environmental samples must be carried out.
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. For those parameters
where a sufficient number (15 sets) of positive results are accumulated over
a period of time, precision criteria should be developed as described below.
After 15 replicate results have been obtained, calculate the.
range (Rj_) of these results as follows:
\ ' Xil - Xi2 ' (1)
where Rj_ is the difference between the results of the pair (X^j_ and X^)
from sample i=l through n. The concentration of each sample is represented
by the mean:
lv j.. v \
I A. -, f A. -;
where Xj_ is the average of the results of the replicate pair. A preliminary
estimate of the critical difference (Hj.) between replicate analyses for any
specific concentration (C) can be calculated as:
n n _
RC = 3.27 (C E Ri)/(E XL) (3)
i=l i=l
316<
-------
Fran these data develop a table of such R 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 R_ to evaluate the accept .ability of R. If the R is greater than
Rj, the system precision is out of control and the source of this unusual
variability should be identified and resolved before continuing with routine
analyses. Record the results of all replicate analyses and periodically (after
25 to 30 additional pairs of replicate results are obtained), revise, update,
and improve the table of critical range values.
3. Matrix Effect Mditions to Samples
These are additions of known amounts of authentic standards to
the sample. The samples are then processed and analyzed in the same manner
as a sample. For the convenience of the analyst, a "reference" standard
addition should be provided. The "reference" standard should be prepared at
the same time that the samples are being spiked using the same piper and the
same standard solution or solutions. The volume of the "reference" should
then be adjusted by dilution, if necessary, to the same extract volume as will
be delivered for the spiked sample. The reference is extremely valuable in
determining accurate percent recovery because the same standard which was
added to the sample can be used for quantitation purposes. This eliminates
errors which might be introduced because of discrepancies between spiking
standards and quantitation standards.
Determine the recovery of the method for the analysis cf environ-
mental samples by adding a spike (Tj_, true value) sufficient to approximately
double the background concentration level (if known prior to extraction) of
the sample selected earlier for replicate analysis. If the original ccr.cer.tra-
ticn is higher than the midpoint of the standard curve (range cf the -ethod;,
then the 'Concentration of the spike should be approximately one-half the original
concentration, which assures that the final concentration is within the linear
ranee of the method. If the concentration cf the ori-ir.a_ Serbia was net
-------
22.
detectable, the concentration of the. spike should be 5 to 15 times the lewer
limit of detection. Generally, the concentration present in the sample will
be totally unknown prior to extraction; therefore, a spike which is 5 to 15
times above the lower detection limit is recommended. The volume of standard
added in aqueous solution should not dilute the sample by more than 10 percent.
The volume of standard added in an organic solvent solution should be kept
small (100 ul/1 or less)-
Analyze the sample, calculated the observed value (OjJ and the
solution concentration (Xj.), then calculate the recovery for the spike as
follows:
Pi = 100 (0L - Xi)/Ti (4)
where Pj_ is the percent recovery. If the sample was diluted due to the
addition of the-spike, adjust Xj_ accordingly.
After determining PI for at least 15 spike results, calculate
the mean percent recovery (?) and standard deviation (Sp) of the recovery as
follows:
_ n
P - (E P±)/n _ (5)
n
'-1 - (Z
(6)
where n = the number of percent recovery values available.
If the percent recovery of the spike is not within the interval
of ? - 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.
-------
22.
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. Matrix Effect additions to Blank Water (Method Standard)
These are additions of known amounts of authentic standards to
the water blank immediately before extraction. The samples are then processed
and analyzed in the same manner as a sample. The standards should be approxi-
mately equal to the concentration found in routine samples.
Analyze the standard and calculate Oj_ (the observed value) . The
percent recovery (Pj_) is then calculated as follows:
100 (0.)
Pi« T_ X (7)
where T.. = the true value.
After determining the Pi for approximately 15 check standards,
calculate the mean (P) and standard deviation (Sp) of the percentages as
follows:
(8)
n
and:
1 n n
L I P.2 - (I P) Vn (9)
n-1 " 'i
where n = the number of results available.
If the percent recovery for succeeding standard additions is r.ct
within the interval of ?~ - 2 Sp, the system should be checked for problems.
If crcblans ex^st, they must be resolved before continuing with routine analysis.
-------
24.
At least one blank water standard addition most be analyzed along
with each set of 20 samples or less that is analyzed at a given time. These
data must be obtained for each parameter of interest. Record the recovery of
all blank water standard additions and periodically revise, update, and improve
the accuracy criteria.
10. Surrogate Spikes
These are standards which are added to every sample prior to
analysis. The standards chosen should be chemically similar to compounds in
the fraction being analyzed. Also, the standards should be compounds which
would not likely be found in environmental samples. The purpose of the surro-
gate spike is to provide quality control on every sample by constantly moni-
toring the unusual matrix effects, gross sample processing errors, etc. The
surrogate spike should not be used as an internal standard for quantitation
purposes. Analyze the' spike extract and calculate Oj_ (the observed value) .
The percent recovery (Pj_) is then calculated as follows:
100 (0.)
Pi
where Tj_ = the true value.
After determining the Pj_ for approximately 15 spikes, calculate
the mean (P) and standard deviation (Sp) of the percentages as follows:
(12)
u
and
/ , |~n n
"5=rlz V - (E p)'/n
sp
where n = the number of results available.
(13)
-------
If tiie percent recovery for succeeding spikes is not within the
interval of P t 3 Sp, the system should be checked for problems. If prcbisrs
exist, they must be resolved before continuing with routine analysis. Peccrd
the recovery of all spikes and periodically revise, ocdate, and improve the
acceptance criteria as defined in section IV.
11. GC/MS cvM-ihi-ation Check
For the base/neutral fraction, run decafluro-criphenyLphcsphir.e
(DFTPP) daily according to EPA procedures. The requirement is for 20 nancgrams
of DETPP to meet the specifications..
For the volatile fraction and the acid fraction, run pentaflurc—
bronobenzene (PFBB) daily according to EPA procedures. The requirement is for
100 nanograms of PFBB to meet the specifica-cion.
12. GC Performance Check
For the base/neutral fraction, run benzidine daily either separately
or as a part of a standard mixture. The requirement is to be able to chrocatc-
graph the compound at the 100 nancgram level.
For the acid fraction, run pentachlorophencl daily either separately
or as part of a standard mixture. The requixarent is to be able to chraratc-
graph the compound at the 100 nancgram.. level.
For the pesticide fraction, run Aldrin daily either separately cr
as part of a standard mixture. An injection of 100 cicccrams should give a
recorder response of at least 50 percent full-scale deflection.
13. Inter-Laboratory Quality Control
In addition to establishing the precision and accuracy of the
method and routinely analyzing replicate and spiked samples, the laboratory zrust
also analyze a quality control (QC) check sample, at least once annually, for
parameters of interest as they are available from the Quality Assurance Branch,
Environmental Monitoring and Support Laboratory (Ci.-cirjiati} .
-------
14. Quantitation
External Standard Method
The external standard method is recommended for quantitation of
parameters frcm the pesticide fraction and the volatile fraction. Prepare
a master calibration curve using a minimum of three standard solutions of
each of the compounds that are to be measured. Plot concentrations versus
integrated areas or peak heights (selected characteristic ion for GC/MS or
electron capture response for GC/EC). One point, on each curve should approach
the method detection limit. Once the master set of instrument calibration
curves have been established, they should be verified dally by injecting at
least one standard solution. If significant drift has occurred, a new cali-
bration curve will have to be constructed. The concentration of the unknown
can be calculated from the slope and intercept of the curve. If the curve is
linear and the intercept is zero, the. unknown concentration can be determined
by the following equations:
For extractables:
Micrograms/liter
' _ ng standard
standard area
(A) (B) (Vt)
{Vi} (VS}
B *•' sample aliquot area
V. = volume of extract injected (yl)
V. = volume of total extract (ul)
V = volume of water extracted (ml)
For volatiles:
Micrcgrams/liter =
_ (A) (B)
(14)
(15)
V
Vo = volume of water purged (ml)
322*
-------
Internal Standard Method
The internal standard method is recotmended for quantitaricn cf
parameters from the base/neutral fraction and the acid fraction.
This method is preferred when the internal standard meets the
following conditions:
a. Does not interfere with other components
b. Elutes close to peaks of interest
c. Approximates concentration of unknown
d. Structurally similar to unknown
The utilization of the internal standard method requires the
periodic determination of response factors (R) which are defined as follcwsL
R = fs^LS. (16)
AIS Cg
Ag is the integrated area or peak height of the characteristic ion for the
priority pollutant standard.
integrated area or peak height of the characteristic ion for the
internal standard.
Cjs is the concentration of the priority pollutant standard.
By adding a known concentration of internal standard (Crg) to
every sample extract, one can then calculate the concentration of priority
pollutant (CcO in the extract using:
The concentration of priority pollutant in the origir>al sampl
is given by:
C- VTT
c0 - ^
whera '/r- is the volume of nhe extract and VQ is the volume of the crigiral
samcis.
-------
23.
The response factor (R) most be determined over ail concsntrad.cn
ranges of standard (Cs) which are being determined. (Generally, the amount
of internal standard •?iffif*3 to each extract is the same so that Cj£ ranains
constant.) This should be done by preparing a calibration chart where the
response factor (R) is plotted against the standard concentration (Cs) using
a minimum of three concentrations over the range of interest. Once this
calibration plot has been determined, it should be verified daily by injecting
at least one standard solution containing internal standard. If significant
drift has occurred, a. nevr calibration curve will have to be constructed.
To quantitate, add the internal standard to the concentrated
sample extract no more than a ferf minutes before the measurement to protect the
standard from losses due to evaporation, adsorption, or chemical reaction.
Calculate the concentration, if unknown, by using the previous equations with
the appropriate response factor taken from the calibration curve. (Ideally,
the response factor will hot change with concentration.)
15. Quality Assurance Documentation
Standard formats are to be utilized for reporting quality assurance
data. One form would summarize all relevant data concerning_blanks, standard
additions, and replicates for each parameter (see Table 9). A second form
would summarize surrogate recoveries for each fraction type (see Table 10)_^
Other forms would provide daily records of GC/MS calibration checks and GC
performance checks.
16. Combinations Used for Matrix Effect and Surrogate Spikes
A. Listing of Combinations and Concentrates
The following Tables 11 through 18 list the required materials
and range of spiking levels for matrix effect spikes and surrogate spike fcr
all fractions of the 129 priority pollutants. The following is a summary of
the requiranents.
324<
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Scike Tvce
1.
2.
3.
4.
5.
6.
Fraction
Purgeables
Adds
Base/Neutrals
Pesticides
Metals
CN~, Phenol
Matrix Effect
Table
Table
Table
Table
Table
Table
11
13
15 (Note: 4 mixes)
16 (Note: 5 mixes)
17
18
Surrogate
Table 12
Table 14
Table 14
None
None
None
B. Availability of Spiking Solutions
Either each laboratory must prepare all matrix effect and surrccazs
spikes or stock solutions are prepared at a central location and distributed
to each laboratory in a given program. In order to optimize data quality
at the minimum cost, the latter is the best approach. Region VIZ has provided
such a service in other programs and in the following section is preserving
the details of how they implemented such a program. If it is determined that
individual laboratories will prepare their own, see Table 19 for possible sources
of standards.
325 <
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30.
TABLE 9
STANDARD QC FORMAT (example)
Parameter Name - Matrix
Normal Detection Limit: 10 ppb
Date Sample £* Measured Value Amount Added Percent Recovery
10/11
10/11
10/11
10/11
10/11
10/11
1234
1234R
1234SS
1234SB
1234MB
1234FB ' "
40
60
75
45
<10
<10
0
0
50
50
0
0
— .
-
50
90
. -
-
Percent Recovery from Sample: P_ ± 3 Sp =
Percent Recovery from Blank: ,P.± 2 Sp =
Critical Differences betwe«=n Replicate Analyses:
*R = replicate; S3 = standard addition to- sample; SB = standard addition
to blank; MB = method blank,- FB = field blank
TABLE 10
RECOVERY FOEMAT (example)
Surrogate Name - Matrix
Normal Detection Limit:
Date Sample t Measured Value Amount Added Percent Recovery
10/11 1234 . 40 50 80
10/11 1235 '60 50 120
Percent Recovery from Samples: £ t 3
Percent Recovery from Blanks? P ± 2
-------
TABLE 11
FBACTION
MATRIX EFFECT SPIKE
Compound Approx. Cone, in Spike (cpb)
(1) Acrolein 240
(2) Acrylonitrile 110
(3) Benzene 20
(4) Brorcdichlorcmethana 20
(5) Bromoform 60
(6) Bronomethane 60
(7) Carbon Tetrachloride 20
(8) Chlorobenzene 20
(9 ) Chlorodibrcticraethane 20
(10) Chloroethane 60
(11) 2-Chloro (ethyl vinyl) ether 60
(12) Chloroform 20
(13) Chlorotiethane 60
(14) Dichlor Bifluorcmethane 60
( 15 } 1 , 1-Dichloroethane 20
(16) 1,2-Dichloroethane 20
(17) 1,1-Dichloroethylene 20
(18) Trans- 1,2-Dichloroethylene 20
(19) Dichloronethane 20
( 20 ) 1 , 2-Dichloropropane 2 0
(21) Cis-l,3-Dichloropropene 20
(22) Trans- 1,3-Dichlorcpropene 20
(23) Ethylbenzene 20
(24) 1,1,2,2-Tetrachloroethane ' SO
(25) Tetrachloroethylene 20
(26) Toluene 20
(21} 1,1, 1-Trichloroethane 20
(23) 1,1, 2-Trichlcrcethar.e 20
(29) Trichlcroe'chylene 20
(20) Tr^chlorofl'jornnerhane 20
(21) Vir.vl 'Chloride 60
-------
TABLE- 12
PUBGEftBLET FRACTION
SUBFCGATE SPIKE
Caiipjund Approx. Cone, in Spike (ppb)
cU benzene 30
o
cL toluene 30
o
dj.Q ethylbeizene 30
branochloranethane 20
1,4-dichlorofautane 20
l-chioro-2-bromopropane 20
-------
TABLE 13
ACID FPACTION
MATRIX EFFECT SQLCTICN
Ccnpound
(1) 2-Chlorophenol
(2) p-Chloro-nv-cresol
(3) 2,4-Qichlorophenol
(4) 2,4-DinethyIphenol
(5) 4,6-Dinitro-o-cresol
(6) 2,4-Dinitrophenol
(7) 2-Nitrophenol
(8) 4-Nitrophenol
(9) Pentachlorophenol
(10) Phenol
(11) 2,4,6-Trichlorophenol
Approx. Cone. Range of SpU
-------
24.
TABLE 14
ACED AND BASE/NEDTBAL
SURECGAIE SFIKE
Canaound Apprax. Cone, in Spike (ppb)
decafluorabiphenyl .50
pentafluorophenbl 100
4-fluoroaniline 100
330-
-------
TABLE 15
BASE/NEUTRAL
MKTKEX EFFECT SPI3E
Conpound
Mixture 1: 1,3-dichlorobenzene
1,2-dichlarobenzene
hexachlorobutadiene
napthalene
acenapthene
fluorene
2,4-dinitrotoluene
hexachlorobenzene
anthracene
diethylphthalate
pyrene
crysene
benzo(a)anthracene
Mixture 2: 1,4-dichlcrobenzene
bis(2-chloroiscpropyl)ether
bis(2-chloroethyl)ether
nitrobenzene
acenapthylene
2,6-dinitrotoluene
4-branophenyl-phenyl ether
diraethylphthalate
di-M-butylphthalate
bis(2-ethylhexyl)phthalate
3,3'-dichlorobenzidine
Mixture 3: ben?ndine
benzo(g,h,i) perylene
^nitroscdimethylamine
di-n-octylphthalate
Mixture 4: hexachloroethane
i^riitroso-di-isf-propylainine
1,2,4-trichlorobenzene
hexachlorocyclopentadiene
2-chloronapthylene
j_3cphorcne
1,2-diphenylhydraz±ne
M-nitroscdiphenylaraine
phenanthrene
flucranthene
cur'.• Ibenry 1 phthalate
Approx. Cone. Par.ee of Spike (ppb)
10 - 400
10 - 400
10 - 400
10 - 400
10 - 400
10 - 400
30 - 1200
10 - 400
10 - 400
20 - 800
10 - 400
20 - 800
20 - 800
10 - 400
20 - 800
10 - 400
10 - 400
10 - 400
30 - 1200
20 - 800
10 - 400
10 - 400
10 - 400
40 - 1600
40 - 1500
20 - 800
30 - 1200
20 - 300
10
30
10
20
10
40
20
20
10
10
20
400
1200
400
800
400
1500
800
800
400
400
300
331<
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36.
TABLE 16
PESTICIDE FRACTION
MATRIX £i'£'.ti.T SPIKE
Approx. Cone. Range of Spike (pcb)
Mixture 1: a-BEC
g-BHC
d-BHC
Heptachlor
Heptachlor epoxide
a-endosulfan
endrin
p,p'-DDD
Mixture 2: S-BHC
AMrin
p,p'-DDE
8 endosulf an
p,p'-DDT
Mixture 3: Tech grade chlordane
Mixture 4: Toxaphene
Mixture 5: PCS 1254
0.1 - 0.5
0.1 - 0.5
0
0
0
0
0
0
.2
.2
.2
.3
,3
.5
1
1
1
1.5
1.5
2.5
0.6 - 3.0
0.1 - 0.5
0.2 - 1.0
0.4 - 2
0.6 - 30
1 - 5
2 - 10
30 - 150
4 - 20
332<
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TABLE 17
METALS FRACTION
MKTBIC EFFECT SPIKE
Compound Approx. Cone. Range of ScLke (ppb)
Flame:* Beryllium 1-10
Cadmium 5-50
Chronium 5-50
Copper 5-50
Nickel 5-50
Silver 5-50
Zinc 5-50
Flameless:* Antimony 1-10
Arsenic 0.5-5
Lead 1-10
Selenium 1-10
Thallium 1-10
Cold Vapor: Mercury 0.2 - 2
*Either flame or flameless method may be used depending on concentraticns
of metals - typical distribution is given.
TABLE 18
CONVENTIONAL FRACTION
MATRIX EFFECT SPIKE
Material Approx. Cor.c. cf Spike (p?b)
or 10 - 100
Phenol 10 - 100
333<
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JS.
TABLE 19
POSSIBLE SOURCES OF STANDARDS
Aldrich Chemical Co., Milwaukee, Wise..
Analabs, Inc., North. Haven, Conn.
J.T. Baker Chemical Co., Phillipsburgh, N. J.
Chemical Procurement Laboratories, College Point, N.Y.
Columbia Organics Catalog A-*7, Columbia, S.C.
Eastman Kodak Co., Rochester, N.Y.
K&K Rare s Fine Chemicals, Plainview, N.Y.
Nanogens International, P.O. Box 487, Freedom, CA 95019
"analytical Reference Standards and. Supplemental Data for Pesticides and
Other Selected Organic Compounds," EPA-660/9-76H312 (May 1976'), Health Effects
Research Laboratory, Environmental Toxicology Division, Research Triangle Park,
N.C.
R.K. Chemical Co., 2135 Howard Street, Hartville, OH 44632
Tridom Chemical Inc., Hauttauge, N.T..
PCR Research Chemicals, Inc., Gainesville, Fla.
Supelco, Inc., Belief onte, PA.
Chem Service, West Chester, PA..
PolyscienCe, Warrenton, PA.
applied. Science Laboratories, State College, PA.
NOTEr These sources are not to be interpreted as being endorsed by the EPA.
334<
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19.
C. 3egicn '7H Stock Solution Supply Program
Summary
The contractor shall run one duplicate (same sample run twice), one
reagent blank (laboratory prepared distilled/deionized water), one
method standard (standard added to distilled/deionized water), and one
matrix effect spike (standard added to sample) for each batch of samples
collected at a given city. A field reagent blank will also be collected
and should be treated as a regular sample. Therefore, the laboratory
should receive 15 samples from the field for each city. Twelve of these
will be regular samples, one will be a field blank, one will be a duplicate
sample for the duplicate analyses and the remaining sample will be a
duplicate for the matrix effect spike.
Region VII will supply two types of quality control solutions to each
contractor- The first type of solution is called a surrogate stock
solution. These stock solutions contain non priority pollutant compounds
and are used to detect gross problems in sample work-up. The second
type of solution is called a standard stock solution. These solutions
contain most of the priority pollutantsand are used to estimate the
reliability of reported data. The quality control solutions provided will
be as follows:
Surrogate Solutions Standard Stock Solution
Volatiles 2 Volatiles 5
Extractables 1 Base Neutral 4
(acids, base & neutral) Acid 1
Pesticide 5
Metals 1
TOTAL 4 .TOTAL 16
Each day samples are started, the contractor should transfer an aliquote
(specific volume will be supplied with solution) from each surrogate
stock solution to a volumetric and dilute to volume. An aliquote of
this surrogate working solution is then added to each sample Just prior
to analyses.
The volatile standard additons are prepared by combining the 5 volatile
stocks, into one volumetric, diluting to volume, and spiking the resulting
solution into the blank water or into a sample. The 4 base/neutral stocks
and the 1 acid stock are combined in a similar manner. Of the 5 cesticide
stocks only 1 is used for spiking purposes at any one time. These should
be rotated so that all the pesticides eventually are included in the
quality assurance program. 'One metal solution will be provided which will
be adcec directly, without prior dilution, to the sample or blank water.
These procedures are explained in more details in the following^:a?es.
Please refer any questions to Dr. Robert Kleopfer (815-274-42S5).
-------
40.
INSTRUCTIONS FOK USE OF REGION VII SPIKING SOLUTIONS
Region VII has provided standard spiking solutions and surrogate spiking
solutions. These are to be used according to the following instructions
per each analytical group and the results are to be reported on the
attached quality assurance report sheet (one sheet per compound). Each
set of samples processed should include one method blank, one method
standard at one spiking level (spiked blank water - wait one hour),
and one matrix effect spike at one level (spiked sample - wait one hour),
and one field, duplicate. All samples are to be spiked with surrogate
solutions as instructed.
In order to eliminate errors caused by inconsistencies in true spiking
solution concentrations, we suggest that the Spiking solutions also be
used as. quantitation standards in determination of recovery values.
Ttiis can be done readily by preparing a reference standard at the same time
that a sample is spiked. For example, if 0.2ml of a spiking solution
is dosed into 1 liter of water sample, extracted and then concentrated
to 1 ml, then that same spiking solution should be used as the standard
by taking 0.2ntT and adjusting to 1 ml in volume.
336<
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Preparation of Base/Neutral Spiking Solutions for Matrix Effect
and Method Standard
I. General Comments
A. The contractor is provided with four 8/N mixes. The spikina
solution is prepared by mixing equal volumes of each of the four mixes
together.
B. Spiking levels for the B/N compounds are .2, .4, .6, 1, 2,
4, and 3 mis of the spiking solution.
II. B/N Mix I
A. Stock Solution
1. Mix I was made up in 10* benzene in methylene chloride.
2. Concentrations of components in stock:
Comoound Concentration
1,3 dichlorobenzene 200 ug/ml
1,2 dichlorobenzene 200 yg/ml
hexachlorobutadiene 200 yg/ml
napthalene 200 yg/ml
acenapthene 200 yg/ml
fluorene 200 yg/ml
2,4 dinitrotoluene 600 yg/ml
hexachlorobenzene 200 yg/ml
anthracene 200 yg/ml
diethylphthalate 400 yg/ml
pyrene 200 yg/ml
chrysene ' 400 yg/ml
benzo(a)anthracene 400 yg/ml
B. Spiking Solution
1. After diluting Mix I with equal volumes of the other
three compounds, the concentrations will then be 1/4 of the values just
reported.
III. B/N Mix II
A. Stock Solution
1. Mix II was made up in 101 benzene in methylene chloride.
2. Concentration of components in stock?"
337<
-------
42.
Compound Concentration,
1 ,4 dichlorobenzene 200
bis (2 chloroisopropyl) ether 400
bis (2-chloroethyl) ether 200 v9/ml
nitrobenzene 200 yg/ml
acenapthylene 200 yg/ml
2,6 dinitrotoluene 500 yg/ml
4-bromophenyl -phenyl ether 400 yg/ml
dime thylphthal ate 200 yg/ml
di-N-butylphthalate 200 yg/ml
bis (2-ethylhexyl) phthalate 200 yg/ml
3,3'dichlorobenridine 800
B. Spiking Solution
1.. All above concentrations will be quartered after spiking
solution is made up.
IV. B/N Mix III
A. Stock Solution
1. Mix III is made up in 10% benzene in methylene chlorids
2. Concentrations of components in stock!
Compounds Concentration
benzidine 800 ug/ml
benzo(g,h,i) perylene 400 yg/ml
N-nitrosodimethylamine 600 yg/ml
di-n-octylphthalate 400. yg/ral
B. Spiking Solution
K After diluting Mix M with equal volumes of the other
three mixes, the above concentrations will be quartered.
V. B/N Mix IV
A. Stock Solution
1.. Mix IV is made up in 102 benzene in methyl ene chloride.
2.V Concentrations of components in stock?
Compounds Concentration
hexachloroethane 200 yg/ml
H-nitroso-di-N-propylamine 600 yg/ml
1 ,2,4-trichlorobenzene 200 yg/ml
hexachlorocyclopentadiene 400 ug/ml
33S<
-------
Compounds Concentration
2-chloronapthylene - 200 uq/mT
isophorone 800 */ml
1,2 diphenylhydrazine 400 y|/ml
N-nitrosodiphenylamine 400 J/ml
phenanthrene 200 ug/ml
fluoranthene
butyl benzyl phthal ate
3. Spiking Solution
1. The above concentrations will be quartered.
339<
-------
44.
Preparation of Pesticide Spiking Solutions for Matrix Effect Spike
and Method Standard
I. General Comments
A. There are five pesticide stock solutions. When the spike
solutions are made up from these stocks, only one of the solutions
is spiked at a time. Otherwise pesticide peaks will overlap on a GC
run. So when a certain pesticide is suspected to be present in an
unknown, spike with the-mi* containing that pesticide.
B. All spiking levels for the pesticides are the same. 1, 2,
3, 4, or 5 mis of spiking solution should be pipetted into 1 liter
of sample (matrix effect spike) or. into 1 liter of organic free deion-
ized water (method standard).
II. Pesticide Mix I
A- Stock Solution
1. The contractor is provided with a 100X concentrated stock
solution. This stock solution is made up in hexane.
B. Spiking Solution
1. Preparation
-a. Make a 1/100 dilution on the stock solution into
either hexane or iso-octane. Be sure all solvents used are pesticide
quality.
2. Concentrations of compounds present in 1/100 dilution:
Compound Concentration
a-BHC TOO pg/ul
g-BHC TOO pg/ul
d-BHC 200 pg/ul
Heptachlor 200 pg/yl
Heptachlor epoxide 200 pg/uT
a-endosulfan 300 pg/ul
dieldrin 300 pg/ul
endrin 500 pg/ul
p,p' ODD 600 pg/ul
III. Pesticide Mix II
A. Stock Solution
1. Stock solution provided is 100X as concentrated as the
spiking solution to be used, and-is in hexane.
B. Spiking Solution
1. Preparation
340<
-------
45.
a. Make a 1/100 dilution of the stock provided into
either hexane or iso-octane. Be sure to use pesticide grade solvents,
2. Concentrations 'of compounds in spiking solution:
Compound Concentration
S-3HC TOO pg/ul
Aldrin 200 pg/ul
p.p1 DDE 400 pg/ul
3 endosulfan 600 pg/ul
p.p1 DDT 1 ng/ul
IV. Pesticide Mix III
A. Stock Solution
1. Stock solution provided to contractors is 10X as concen-
trated as spiking solution to be used.
B. Spiking Solution
1. Preparation
a. Make a 1/10 dilution of stock solution into hexane
or iso-octane.
2. Concentration in mix after 1/10 dilution:
Mixture Concentration
tech. grade chlordane- 2 n
V. Pesticide Mix IV
A. Stock Solution
1. Stock solution provided is 10X as concentrated as spiking
solution to be used and is in hexane.
B. Spiking Solution
1. Preparation
a. Make a 1/10 dilution of stock solution provided into
either hexane or iso-octane (pesticide, grade quality).
2. Concentration in spiking solution:
Mixture Concentration
toxaphene- 30 ng/ul
VI. Pesticide Mix V
A. Stock Solution
1. Contractors are provided with a 10X concentrated solution
in hexane.
-------
46.
B. Spiking Solution
1. Preparation
a. Make a 1/10 dilution of stock solution provided into
either hexane-or iso-octane (pesticide grade quality).
2. Concentration in spiking solution:
Mixture Concentration
PCS-1254 4 ng/ul
342-
-------
4".
8
Base/Neutral - Acid Surrogate Spiking Solution
I. Stock
A. The surrogate stock solution provided to the contractor contains
decafluorobiphenyl, pentafluorophenol, and 4-fluoroanil ine. It is made
up in 105 benzene in methylene chloride.
B. Concentrations of compounds in stock.
Comoound Concentration
decafluorobiphenyl .5 mg/ml
pentafluorophenol 1 mg/ml
4-fIuoroanil ine 1 mg/ml
II. Spiking Levels
A. The stock solution provided is also the spiking solution.
B. TOO ye of this stock or spiking solution is spiked into every
sample including quality control samples.
343<
-------
48.
Preparation of Acid Solution for Matrix Effect Spike
and Method Standard
I. Acid Mix
A. Stock
1. There is only one acid stock and it is in methylene chloride
2. The stock solution is 1QX as concentrated as the spiking
solution to be used.
B.' Spiking Solution
T. Preparation
a. Make a T/10 dilution of the stock in methylene chloride
2. Spiking Levels
a. 2, 4, 6, or 8 mis of the spiking solution is spiked
into 1 liter of sample (matrix effect spike) or 1 liter of organic free
D.I. H2Q (method spike).
3. Concentration of components in spiking solution.
Compound
2-nitrophenol
2-chlorophenol
2,4- dimethyl phenol
phenol
2,4,6 trichlorophenol
2,4 dichlorophenol
p-chloro-fl-cresol
pentachlorophenol
2,4 dinitrophenol
4-nitrophenol
4,5 dinitro-o-cresol
Concentration
20 yg/ml
10 yg/ml
15 jig/ml
10 vg/ml
17 yg/ml
12 yg/ml
18 yg/ml
55 yg/ml
800 yg/ml
250 vg/ml
450 yg/ml
344<
-------
10
Preparation of Surrogate Spike Solutions
to be Used for Volatile Organics
A. Reagents
1 . Dg benzene
2. D« toluene
3. "Dfo ethyl benzene
4. Supelco Mix - Catalog #4-8823 contains 20mg/m1 each in 1 mi
MeOH, contains broraothlorome thane , 1.4 dichlor-obutane and l-chloro-2-
bromopropene.
5. Reagent grade methanol
6. Organic free water
B. Apparatus
1. Volumetric flasks, clean and baked out at 180°C and cooled,
lOral and 25ml in size.
2. Hamilton syringe - gas tight, lOOul size.
C. Preparation of Deuterated Stock Solution
1. Into a clean 25ral volumetric flask carefully add about lEml
MeOH.
2. Add lOOul DS benzene.
3. Add IQOyl Dg toluene.
4. Add TOOul DIQ ethyl benzene.
5. Dilute to volume with MeOH.
6. Stopper, mix well, store in a protected atmosphere in a refrig-
erator.
Approximate concentrations of deuterated stock solutions:
Dg benzene » 3515 ppm
Dg toluene = 3468 ppm
ethyl benzene * 3469 ppra
D. Preparation of Working Surrogate Spike Solution
1. Into^ 10ml volumetric flask that contains 10ml organic free
water, -add 80yl deuterated stock solution.
2. Add lOyl Supelco surrogate spike solution.
3. Mix by inverting three times.
4. Add 5ul of surrogate spike solution to each '5ml sample being
analyzed by purge and trap followed by GC/MS.
5. Record total ion content for each spike and monitor spikes
throughout the day.
Concentration of spikes are approximate.
Dg benzene = 28 ppb
DS toluene = 28 ppb
D]o ethyl benzene =• 23 ppb
bromochloromethane = 20 ppb
1 .i dichlorobutane = 20 ppb
1 -cnl oro-2-bromopropene = 20 ppb
345<
-------
30.
11
Preparation of Volatile Organic Standards
Due to the nature (volatile organic compounds) and the number (31),
the standard reference mix for volatile organics is prepared by u'sing
the Supelco purgable mixes as stock solutions.
Stock Solutions:
A. Purgable A, catalog #4-8815, each constituent at 0.2 mg/ml
in methanol. From Supelco. Contains the following: Methyl ens chloride,
trichloroethylene, 1,1,-dichloroethylene, 1,1-dichlcroethane , 1,1,2-
trichloroethane, dibromochloromethane, 'chloroform, tetrachloroethylene,
carbon tetrachloride, chlorobenzene, 1,2-dichloropropQfe.
B. Purgable B, catalog. #4-8816, each constituent at 0.2 mg/ml
in methanol. Obtained from Supelco. Contains the following: Trichloro-
fluoromethane, cis-1,3-dichloroprop.ene, benzene, trans-1,2-dichloro-
ethylene, 1,2-dichloroethane, bromodichloromethane, toluene, trans-1,3-
dichloropropene, ethyl benzene.
C. Purgable C, catalog #4-8817, each constituent at 0.2 mg/ml
in methanol. Obtained from Supelco. Contains the following: Chloro-
methane, dichlorodifluoromethane, bromomethane, vinyl chloride, chloro-
ethane.
D. Acrolein stock, accurately weigh about SOOmg into a 100ml
volumetric flask which contains about 75ml MeOH. Dilute to volume
with methanol (cone. 6.O&.mg/ml-supplied).
E. AeryIonitrtle stock, accurately weigh about 1.6g into a 100ml
volumetric flask which contains about 75ml MeOH. Dilute to volume with
methanol (cone. 11.181 mg/ml supplied).
F. 2-Chi oroe thy! vinyl ether stock, "Iccura-tely weigh about lOOmg
into a 10ml volumetric flask containing MeOH. Dilute to volume with
methanol (conc» 11.6 mg/ml supplied).
Working Standard
Into a 2ml screw cap vial, which has been baked out at 180°C for one hour
and allowed to cool, add:
1. lOOul MeOH
2. 200yl Purgable A
3. 200yl MeOH
4. 200WT Purgable 3
5. 200U1 MeOH
6. SOOyl Purgable C
7- lOOyl MeOH
8. 20U1 Acrylonitrile stock
9. lOOyl MeOH
10. SOul Acrolein stock
11. lOOwl MeOH
346<
-------
12
12. lOyl 2-chloroethylvinyl ether stock
13. 90ul HeOH
Quickly add each. Do not let needle of syringe below the surface of "he
solvent. Touch sides of vial for draining. Label carefully. Stopper
tightly. Store in freszer under activated charcoal. Amounts may be halved
depending on need. Prepare workfng standard monthly.
5yl or working standard is spiked into Sral deionized water which is
then analyzed by purge and trap and GC/MS. This (5ul) represents a
spike having the following composition:
Compound Amount (ug/1 in gob)
Purgable A group 20
Punjabi e B group 20
Purgable C 60
Acrolein 243
Acrolynitrile 112
2-chloroethylvinyl ether 58
34'
-------
52.
T7 PESFOHfflNCE CKETSKIA
A. Introduction
The data generated for each fraction was compared at an EGD meetina
in Norfolk, Va. The data represent 10,000 points and were primarily qeneratsd
by the following laboratories:
1. AOL Inc., Cambridge, Ma.
2. Carborundum Co., Sacramento, Ca.
3. EPA-Begion VH, Kansas City, Kansas
4. Versar Inc., Springfield,- Va.
Smaller amounts of data were developed at three other laboratories
for a total of seven participants. The samples that were spiked with matrix
effect and surrogates range from, ground water to PCTW effluents and timber
and paper product waste.
The data can be used, to develop a set of control limits, both Upper
Control Limits (DCL) and Lower Control Limits (LCL) for priority pollutant
analysis. Sufficient data is presented to' evaluate both the operation of the
laboratory via method spikes and blanks and the impact of a particular matrix
via the duplicate spikes. The base data generated represent vastly varying
conditions and matrices and is quite useful. Most control limits would be
expected to decrease, i.e., improve, as methods are improved and laboratory
experience is gained.
B. Summary, of Control Limits for Matrix Effect Spikes
The data, and tables are directly from the Region VII presentation
and are to be used as control limit guides.
UCL = 2 Sp
LCL = 3 Sp
For example, consider the method spike for benzene (data fron Table 21).
348<
-------
In the Method Standard In the Matrix Spike
89 12 93 24
UCL 89 +• 3(12) =125 93 4- 3(24) = 165
LCL 89 - 3 (12) - 53 93 .- 3 (24) = 21
Therefore, within a given set of samples and control solutions, a recovery for
benzene in the method standard between 53% - 125% or in the matrix spike between
21% - 165% is said to be in control. Any data outside these limits need careful
examination and probable re-analysis. The Tables 20 through 25 give all data
relevant to matrix spike recovery.
C. Summary of Control Limits for Surrogate Spikes
The priority pollutant surrogates are presented in Table 26. The
data base upon which to make decisions is much smaller here than for the ra-crix
effect spike. In practice, the data generated by surrogates gives the analyst
a real-time instantaneous look at the operation of the overall analytical
systan in every sample. This instantaneous information is the most important
reason for the retention of the surrogates.
For the longer term record, the upper and lower control., limits are
calculated in the same way as for matrix effect spikes.
349<
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54.
TABLE 20. INTRALABORATORY COMPARISON
Priority
Pollutant
Fraction*5
Volatile
(MS)
Volatile
Sample Spike
Acid (MS)
Acid Sample
Blank
B/N-(MS)
B/N Sample
Spike
Pesticide
(MS)
Pesticide
Sample Spike
Metals (MS)
Metals
Sample Spike
Cyanide (MS)
Cyanide
Sample Spike
Phenol ics
(MS)
Phenol ics
Sample Spike
LAB
1
88+21
82+24
90 V]8
92+34
95+25
84+18
73+8
69+7
113+37
100+20
103+14
101+12
10+13"
93+15
LAS LAB
II III
95+5
101+9 .93+.! 3
89+5
72+10 62+1 Z
78+41
61+22 55+24
74+19
51+18 33+10
-
103+14
-
-
97+6
98+10
LAB LAB LAB
IV V VII
100+8 -
107+_9 -
57+.14 82+16 -
60+15 84+; 7 -
77+J 5 -
68+.16 - 63+J3
88+8
93+.S
103+8 -
92+7
103+8 -
93+J6 -
100+_7 -
97+_9
Averag
90+_13
92+_15
84+13
76+19
84+_25
68+_21
78+11
59+11
108+22
96+Jl
103+7
96+14
101+_8
96+_11
a) The values are in units of percent recovery (P) plus or minus (+J one
standard deviations (Sp).
b) MS refers to the method standard or the standard addition to blank water.
Sample spike refers to the standard addition to a sample.
c) P and Sp are weighted averages based on the number of data points
contributed by each laboratory.
35CK
-------
TABLE 21. PURGEA3LE ORGANICS
Comoound
Acrolein
Acrylonitrile
Benzene
Bromodi ch1oromethane
Bromofonn
Bromomethane
Carbon Tetrachlorfde
Chlorobenzene
Chlorodibromomethane
Chloroethane
Chloroform
Chioromethane
Oichlorodifluoromethane
1,1-Oichloroethane
1,2-Dichloroethane
1,1-Dichloroethylene
trans-1,2-Oichloroethylene
Dichloromethane
1 ,2-Oichloropropane
cis-1,3-Oichloropropene-
trans -1-3-Di'chloropropene
Ethyl benzene
Method13
Standard
774-30
96+.31
89+12
9 7 +11
94^14
90+16
91+23
94+23
86+12
67+JZ2
90+18
91+.22
108+11*
83^10
102^12
74+_24
90+25
82+46
94+_26
95+15
91+_13
109+19
Standard0
Spike
32*30
1 02+_28
93+_24
103+_31
88+12
78+15
91+_33
103+24
99+17
60+_23
91+26
64+_28
1144-8*
87+_21
103+27
80+32
85+35
66+66
99*30
98+20
93-16
106-28
351<
-------
56.
Continuation of Table 21
Method Sample
Compound Standard Spike
1,1,2,2-Tetrachloroethane 31+31 73+31
Tetrachloroethylene 97^13 99+25
Toluene 96+22 97+_25
1 ,.1,1 -Tri chl oroethane 92^21 94+_36
1,1,2-Trichloroethane 102_+14 103±19
Tri chloroethyl en* 106+14 110+22
Trichlorofluoromethane 59+23 67+_48
Vinyl Chloride 103+30 79+22
a) The values are in terms of P _+ Sp. Data from 2-4 laboratories have been
averaged except where noted with an (*) asterik. In general the concentration
added ranged from 10 to 1000 parts per billion.
b) Standard addition to blank water.
c) Standard addition to sample.
*0ata from only one lab were available.
-------
TABLE 22. ACID FRACTION3
COMPOUND
2-Chlorophenol
4-Chloro-3-methylphenol
2,4-Dichlorophenol
2,4-Dimethylphenol
4,6-Oinitro-o_-cresol
2,4-Oinitrophenol
2-Nitrophenol
4-Nitrophenol
Pentachlorphenol
Phenol
2,4,6-Trichlorphneol
METHOD13
STANDARD
80+_22
96*16
86+24
7U19
87+34
89+22
95+22
65+33
87+24
61+J1
91+22
SAMPLED
SPIKE
71+23
99*19
84^23
72+.16
102*23
92*_40
87+22
59+46
84*_22
54^24
30*24
a) The values are in terms of P _+ Sp. Data from 2-5 laboratories have
been averaged. In general the concentation added ranged from 20 to 2500
parts per bil1 ion.
b) Standard addition to blank water.
c) Standard addition to sample.
353<
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58.
TABLE 23. BASE/NEUTRAL FRACTION3-
Compound
Acenaphthene
Acanapthylene
Anthracened
Benzidine
Benzo(a)anthracenee
Benzo(b)fluoranthene^
Berizo(lc}fluoranthene^
Benzo(a)pyrene
Benzyl Butyl Phthalate
Bis(2-chloroethyl) Ether
Bis(2-chloroisopropyl) Ether
Bis(2-ethy1hexyl) PtithaUte
4-8romophenyl Phenyl Ether
2-Chioronaphthalene
Chrysene8
Dibenzo(a,h)anthracene
Di-n-butyl Phthalate
1,2-Oichlorobenzene
1,3-Oichlorobenzene
1,4-Oichlorobenzane
3,3'-Dichlorobenzidine
Method0
Standard
90+22
83+.2Z
98+20
44+27
105+33
96+68*
96+68
90+.22
49+39
98+48
15^136
70+33
80+25
88+20
105+33
80+42
80+32
65+24
67+_21
67+_22
71+85
Sampl ec
Spike
78+24
79+27
79+25
40+29
51+24
41+_21
47+27
43+21
49+22
30+_49
96+88
66+50
63+_25
79+21
77+_27'
36+_29
58+27
65+_27
62+_20
53+21
62+45
354<
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Continuation of Table 23
Compound
Diethyl Phthalate
Dimethyl Phthalate
2,4-Oi nitrotoluene
2,6-Oinitrotoluene
Di-n-octyl Phthalata
1,2-Oiphenylhydrazine
(and/or Azobenzene)
Fluoranthene
Fluorene
Hexachlorobenzene
Hexachlorobutadiene
Hexachlorocyclopentadiene
Hexachloroethane
Isophorone
Indeno(l,2,3-cd)pyrene
Naphthalene
Nitrobenzene
N-nitrosodipheylamine
(and/or Diphenylamine)
N-N i trosodi -_n_-propyl ami ne
Phenanthrene
Pyrene
1,2,4-Trichlorobenzene
Method0
Standard
71^37
43+_37
122+_55
115+41
84+_44
9.7+26
111+26
98+24
98+31
76+26
38+28
63+22
66+36
109+14
83+_24
106+_31
72+22
Samplec
S D i k e
65+37
66*43
94*_45
104*_35
38*32
91*_32
63+20
38+25
76+31
77*_45
27+_10
53+23
67^22
40+21
89*51
77^51
66+25
86+34
98+_20
142+_41
74+22
71^22
7920
59*24
a) The values are in terms of P + Sp. Data from 2-5 laboratories have been
averaged except where noted with an (*) asterik. In general the concentration
added ranged from 10 to 500 parts per billion.
b) Standard addition to blank water.
c) Standard addition to sample.
d.e,f) These isomers pairs are not separted by packed column GC. Also m^-ss
data are not sufficiently unique to allow differentiation, "
•Data from only one lap were available-
-------
50.
TABLE 24.. PESTICIDE FRACTION*
Compound
Aldrin
atpha-BHC
beta-BHC
gamma-BHC
deltaTBHC
Chlordane
4,4' -ODD
4,4' -ODE
4, 4 '-DDT
Dieldrin
Endosulfan I
Endosulfart II
Endosulfane Sulfate
Endrfn
Endrfn Aldehyde
Heptachlor
HeptachTor Epoxide
PCS
Toxapnene
Methodb
Standard
72+13
78+13.
79+21
78+; 4
82+J6
81+17*
82+; 4
76+14
85+17
71+14
65+14
67+19
74+^39*
82+25
64+76*
72+12
82+14
83 +11*
89+12*
Samplec
Spike
55+12
55+12
57+22
64+_1 1
61+16
39+_9*
62+; 6
57±1 8
76+26
62+16
61+13
66+14
84+_30*
68+18
34+_39*
49+12
65+11
42+13
-
a) The values are irt terms of P +_ Sp. Data from 2-4 laboratories have been
averaged except where noted with- an (*)asterik. In general the concentration
added ranged from. 0.1 to 100 parts per billion.
b) Standard addition to blank water.
c) Standard addition to sample.
*0ata from only one lab were available.
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51.
PARAMETER
TABLE 25. METALS, CYANIDE, AND PHENOLICSa
Antimony
Ars.enic
Beryllium
Cadm'i urn
Chromium
Copper
Lead
Mercury^
Nickel
Selenium
Silver
Tn a-11 i urn
Zinc
Cyanide
Total Phenols
METHOD^
STANDARD
61+47*
1 20+20
89+16
91+J8
99+30
136j+70
116+32
83+24
84+62
112+15
1 10+25
99+_33*
122+44
101+8
SAMPLEC
SPIKE
103+_24
97+25
94+_20
98+_23
106+25
99+24
93+_25
79+38
101+_26
93+_20
80+_25
95+23
106+^37
96+H
96+ II
a) The values are in terms of P _+ Sp. Data from 2-3 laboratories have been
averaged exept where noted with an (*) asterik. In genral the concentration
added ranged from 10 to 1000 parts per billion.
b) Standard addition to blank water.
c) Standard addition to sample.
d) Analyzed by the cold vapor technique.
*0ata from only one lab were available.
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62.
TABLE 26. PRIORITY POLLUTANT SURROGATES3
Compound LAB Illb
(Purgeable Orgnaics)
dg-Benzene
Bronochloromethane
d-Chloroform 139+_96
1,4-Dichlorobutane
d^-l,2-Oichloroethane 119.+29
dj-Oichloromethane 146+55
dig-£thylbenzene 102+25
f\ uorbenzene 96+20
dg-Toluene
d3-l,l,l-Tn'chloroethane 117^41
(Acids).
2-Fluorphenol 76+36
Pentafluorphenol 84+J30
d5-Phenol 55+20
Trifluoro-in-cresol 72+_42
(Base/Neutral)
Decaf 1 uorobi phenyl 39+_l 8
da-Nepthalene 76+22
2-fluornaphthelene 75+20
1-fTuronaphthelene 69+18
di2-benzo(a) anthracene 68+_16
2-flurobi phenyl 63+_5
ne 57+_36
358<
LAB
93+22
91+20
85+24
LAS VIII
94+18
92+18
50+22
101+39
41 + 29
46+13
-------
Continuation of Table 26
53.
Compound
LAB IIIb
LAS IV<=
LAB VI1
2-fluroaniline 74^39
dg-nitrobenzene 7(3+21
a) The values are in terms of P _* Sp. The concentration added ranged from
20 to 200 parts per billion.
b) The matrix for these surrogates included influent and effluent samples
from 12 different industrial categories.
c) The matrix for these surrogates included POTW, detergent, and chemical
disposal industries.
d) The matrix for these surrogates included POTW samples only.
353<
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SECTION IV
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PRIORITY POLLUTANT METHODOLOGY
QUALITY ASSURANCE REVIEW
Robert D. Kleopfer*
Jerry R. Dias and
Billy J. Fairless
United States Environmental Protection Agency
Region VII Laboratory
25 Funston Road
Kansas City, Kansas 66115
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c- ABSTRACT
t
e
Initial quality assurance statistics are presented for the priority
pollutants, the statistics are based on over 10,000 data points
contributed by seven laboratories. The average recovery of all the
organic prioirty pollutants from industrial effluents is 73 per cent
with a standard deviation of 26 per cent. Data are summarized for
metals* cyanides, phenolics, and the specific organic compounds which
are divided into four fractions. Recommended control limits are given
along with a summary of data for surrogate recoveries. The results
have permitted identification of the variables associated with EPA's
analytical protocol.
-------
INTRODUCTION
In compliance with a consent decree emanating from civil court actions
brought against the Environmental Protection Agency (EPA) by concerned
organizations, EPA has developed a list of 129 priority pollutants with
the goal of establishing industrial effluent limitations and guidelines.*
This paper will summarize the results of over 10,000 measurements collected
/
by seven laboratories on 104 of the 1U organic priority pollutants, all
the metals (13), and total phenol and cyanide. (Actually there are 130
priority pollutants if one differentiated 1,3-dichloropropene into cis
and trans isomers.) The seven different ArocVors are reported collectively
as PCB's while three base/neutral compounds, two volatile orgnaic compounds,
and asbestos are not included in this report. The data assembled herein
has permitted identification of probable problem areas and provides an initial
*"' estimate of the accuracy and precision of the EPA analytical methodology^ for
the priority pollutants.
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r
Analytical Methodology
The screening of wastewater for 114 organics is accomplished by analyses
of five different fractions.2 The fractions are pesticides (26 compounds),
base/neutrals (46 compounds), acids (11 phenols), purgeables (29 volatile
organics), and direct aqueous injection fraction (2 compounds).
The base/neutrals (B/N) include compounds such as 1,4-dichlorobenzene,
benzidine, and benzo(a)pyrene. These compounds are extracted from basic
aqueous solution with methylene chloride. The concentrated extracts, are
analyzed by GC/MS on a 1J SP-2250 column. Columns packed with 3% OV-17
and 3J SP-2250-DB have also been used effectively.
The acid fraction (A) consists of 11 phenols ranging from phenol itself
to pentachlorophenol. These are determined by extraction of acidic solution
with methylene chloride and analysis by GC/MS techniques. The preferred
column packing for this analysis is 1% SP-1240-DA.
The pesticide fraction (P) is prepared by extraction with 15% methylene
chloride in hexane. The pesticides are initially screened by gas chroma-
tography with electron capture detection.3 Any compounds which are tentatively
identified by that technique must be confirmed by GC/MS.
The purgeable organics, which include compounds ranging in volatility
from methyl chloride to ethyl benzene, are measured using a purge and
trap analytical technique. In this method, the volatile organics are swept
-------
from 5ml of sample with an Inert gas. The purged organlcs are retained
on a trap consisting of Tenax GC and Silica Gel. These organics are then
heat desorbed onto an analytical column consisting of 0.25 Carbowax 1500
on Carbopak C with a 3% Carbowax 1500 precolumn. Again, mass spectrometry
is used for the detection.
Finally, because of their high water solubility, acrolein and acrylonitrile
are determined by direct aqueous injection on Chromosorb 101 with mass
spectrometric detection. However, more recent work has shown that these
/
compounds can also be measured by the purge and trap technique.*
Identification is based on the appearance of mass chromatograms (extracted
ion current profiles) for three characteristic ions for each compounds.
As an example, for the three dichlorobenzene isomers, the molecular
ions at 146 and 148 and the fragment ion at 113 are used for identification
and quantification. The ions must appear at the correct retention time
with the correct relative responses in order to be considered a positive
identification. Quantisation is based on external standard methods for
the volatile organics and pesticide fractions and internal standard methods
for the base/neutral and acid fractions. The internal standard for these
fractions is fully deuterated anthracene which has a molecular ion occurring
at mass 188.
The metals are analyzed by flame!ess atomic absorption (AA) and cyanide
and total phenols are colorimetrically determined.5 Cyanide is measured
-------
f-~- colorimetrically by converting to cyanogen chloride with chloramine-T
which reacts with pyridine to give a product that forms a colored
complex with barbituric acid. Total phenol is colorimetrically determined
\
by oxidizing with potassium ferricyanide to give quinones that condense
with 4-aminoantipyn'ne to form colored complexes.
Quality Assurance Requirements
The original priority pollutant methodology document^ specified several
quality assurance (QA) requirements, but additional features were sub-
sequently added^t?. These requirements include the following:
1. Method Blank
The method blank is defined as an appropriate volume of "organic-free"
water which has been processed exactly as a sample (same glassware,
(£
^^ reagents, solvents, etc.). For the extractable parameters (B/N, A, P)
this would require extraction of one liter of water. For the volatile -
fraction, 5ml of "organic-free" water should be analyzed by the purge
and trap methodology. One method blank sample should be run with every
batch of 20 or fewer samples. Also, a method blank should be run whenever
a new source of reagent or solvent is introduced into the analytical scheme.
Reagents having background levels that interfer with the compounds to be
determined must be purified, and shown to be acceptable or replaced with
some that are acceptable.
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r
£" 2. Field Blank
It 1s the responsibility of the sampling team to provide the appropriate
field blanks to the analytical team. For the extractable parameters (B/N,
A, P) the minimum requirement 1s to provide an appropriate volume of blank
water which has been processed through the sampling equipment in the same
manner as a sample. The field blank is then analyzed in the laboratory '
as 1f 1t were a sample. When inteferences occur, the analytical results
must be discarded or flagged so as not to result in the reporting of false
positives. Field blanks for the volatiles consists of "organic-free" water
t
which has been sent from the laboratory to the sampling site and retained
with the samples. The purpose is to check on possible contamination of
the sample by permeation of volatiles through the septum seal. Sample
blanks should be protected with activated carbon during transit and during
storage in the laboratory.
3. Replicates
To determine the precision of the method, a regular program of analyses
of replicate aliquots of environmental samples must be carried out. At
least two replicate aliquots of a well mixed samples must be analyzed with
each set of 20 samples or less analyzed at a given time. For those parameters
where a sufficient number of positive results are accumulated over a period
of time, precision criteria should be developed. A minimum of 15
*
replicates at a particular concentration or concentration range where linearity
exists is required to start an on-going program for QA and subsequent estimates
367<:
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r
of precision.
4. Standard Additions to Samples
These are additions of known amounts of authentic standard to the sample.
The samples are then processed and analyzed in the same manner as a sample.
The percent recovery is then determined as described in reference 6. At
least one spiked sample is analyzed along with each set of 20 samples or
less. Spiked data are obtained for each parameter of interest.
5. Standard Addition to Blank Water (Method Standard)
" ' . *
These are additions of known amounts of authentic standards to the water
blank before extraction. The samples are then processed and analyzed in
the same manner as a sample. The standard should be approximately
equal to the concentration found in routine samples. The percent recovery
is determined as described in reference 6. At least one method standard
must be analyzed along with each set of 20 samples or less.
6. Surrogate Spikes
These are standards which are added to every sample prior to analysis.
The standards chosen should be chemically similar to compounds in the
fraction being analyzed. Also, the standards should be compounds which
would not likely be found in environmental samples. The purpose of the
surrogate spike is to provide quality control on every sample by -
*
constantly monitoring for unusual matrix effects, gross sample processing
error, etc. The surrogate spike should not be used as an internal standard
for quantisation purposes.
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8
fe
^ 7. GC/MS Calibration Check
For the base/neutral fraction, and add fraction decafluorotriphenyl-
phosphlne (DFTPP) 1s run dally according to EPA procedures. The require-
ment 1s for 50 nanograms of DFTPP to meet relative ion abundance criteria**.
For the volatile fraction pentaflurobromobenzene (PFBB) 1s run daily according
..-..•• >"
to EPA procedures. The requirement is for 100 nanograms of PFBB to meet the
relative ion abundance criteria?. More recently, p-fluorobromobenzene has
been recommended as a replacement for PFBB.9
8. GC Performance Check
For the base/neutral fraction, benzidine is run daily either separately or
as a part of a standard mixture. The requirement is to be able to chroma-
tograph the compound at the 100 nanogram level. For the acid fraction,
fr
^ pentachlorophenol is analyzed daily either separately or as part of a
standard mixture. The requirement is to be able to chromatograph the
compound at the 100 nanogram level while giving an acceptable tailing
factor7-10. For the pesticide fraction, Aldrin is run daily either
separately or as part of a standard mixture. An injection of 100 picograms
should give a recorder response of at least 501 full-scale deflection.
Results and Discussion
The results have been condensed and summarized in eight tables. In order
to maintain readability, information such as the number of data points
contributed by each lab for each parameter and the corresponding concen-
C
-------
tration range have not been Included. Also specific results from each
laboratory for each parameter are hot included. These data are, however,
available from the authors upon request*
Interlaboratory Comparison
All the data in this report was collected before June 1979, while the control-
ling protocol was published in April 1977. There are four primary laboratories
(cf. with acknowledgment) contributing almost 10,000 data points to this re-
view. Some of the data was statistically rejected. In Laboratory I, 3i of
the B/N and metal analytical data was rejected' using the statistical one-sided
test at the 2.5% significance level11. Similary, 0.3S of the data from
Laboratory II was also excluded. A total of 18* of the data from Laboratory
III was rejected for two reasons: 1) the spiking levels were not at least
two times above the background level (especially at low levels) and 2)
application of the one-sided test suggested to a 97.55 confidence that the
data removed were likely outliers.
The data are expressed in terms of percent recovery (P) plus or minus
(+) one standard deviation (Sp) where
Sp
-f £")>,)
, ^=1
'/.
-------
10
Table I summarizes the data for the various classes of priority pollutants.
The inter!aboratory comparison gives the average recovery of only the
compounds analyzed by all the contributing laboratories in the method standard
analysis. Once this comparison set had been determined, then the same set
of compounds was used as the basis for interlaboratory comparison for the .
matrix spike. This precaution minimized data variability between the
laboratories due to properties associated with the individual compounds like
volatility, reactivity, etc. (vide infra). Laboratory III had no method
standard analytical data and had analyzed fewe.r compounds. Note that Sp
in the interlaboratory comparison is the deviation of the recovery means
and not measurement deviation.
PURGEABLE ORGANIC COMPOUNDS. As part of the process of quality assurance
f& ^_—_——^—_———.^——
Labs I, II, III, and IV analyzed field blanks consisting of organic-free
water that was transported to the analytical laboratory along with the
samples. Invariably, dichloromethane (methylene chloride), the extraction
solvent, was observed in field blanks and laboratory blanks. Typical levels
for laboratory IV were 2 _+ 1 parts per billion. No data are reported for
2-chloroethyl vinyl ether and bis(chloromethyl) ether; the former appears
not to have been available and the latter is an alpha-chloromethyl ether
which is well known to undergo facile hydrolysis. In a ten month stability
study, Radian Corporation found that the initial concentration of both
C 371<
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n
these ethers in their methanolic standard was reduced to zero probably from
substitution reactions with methane!12. Also, the concentration of acrolein
was reduced to zero. Note that acrolein can undergo air oxidation, Michael
addition, and dimethyl acetal formation 1n methanol.
Tables I and II summarize the results obtained for the purgeables. The
difference in recoveries between the method standard analysis and matrix
spiked analysis should be indicative of sample matrix effects and in
this case there appears to be slight increase in recovery in going from
the method standard analysis (Interlab Comparison Average = 90_+ 13) to the
matrix Spiked analysis (Interlab Comparison Average = 92 +_ 15).
Volatility is a very important variable in the analysis of the purgeable
organic compounds (VOA). Labs I and III have omitted analysis of many
of the most volatile compounds, including bromomethane, chlormethane,
dichlorodifluoromethane, and vinyl chloride. Inspection of the individual
laboratory data show significant differences in going from the most
volatile group of compounds (bp < 75*C) to the least volatile compounds
(bp > 112eC) for Labs I and III only. Recoveries increase and relative
standard deviations decrease. Using the two-tailed statistical test for
significance of the sample differences between the most volatile group
and the intermediate and least volatile groups, assuming there is,no
difference between the population means from which these samples are drawn
it is established to a greater than 99.9S confidence that the observed
-C 372<
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T2
difference for these groups arise from volatility. Lab II cooled their
^ Tenax sorbent trap with liquid COg and Lab IV used a sorbent trap mix
containing Tenax, silica gel, and activated charcoal. In a separate
precision study (method standard analysis) by Lab IV involving five
measurements at each of four different concentration, standard deviations
of 11.2+3.4 and 10.0+2.4 were obtained for the most volatile group (11
compounds or 220 data points) and the intermediate and least volatile 7
groups (17 compounds or 340 data points), respectively. Thus, to a 95X
confidence it appears that even in analytical laboratories where volatility
is mainly under control, the more volatile compounds exhibit greater
<
measurement fluctuation.
Comparison of the recovery data of deuterated purgeable organic surrogates
in Table VII versus the recoveries of the corresponding nondeuterated
^y priority pollutant in Table II gives, respectively, 93_+22 and 93+_24 for
benzene, 139+_96 and 110+21 for chloroform, 146+55 and 88+24 for dichloro-
methane, 94+18 and 106+28 for ethylberizene, 92+18 from 97+25 for toluene,
119+29 and 103+_27 for 1,2-dichloroethane, and 117+41 and 94+36 for 1,1,1-
trichloroethane. The large scatter for the data would suggest that d-
chloroform and d2-dichloromethane are poor choices for surrogates.
PHENOLIC ACIDS
After the B/N compounds have been extracted from the alkaline sample
373<
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13
with methylene chloride (Figure 1), the aqueous phase is made acidic with
6H HC1 and again extracted with methylene chloride. This latter methylene
chloride extract is dried by passing through a column of anhydrous sodium
sulfate and the solvent concentrated by distillation in Kuderna-Danish
apparatus. Lab III investigated acid carryover in waste samples from the.-
leather tanning industry which tended to form emulsions and therefore were
extracted continously for 24 hours; they noted a pH change from greater than
11 to 8-9. In a separate study, Lab IV demonstrated that, in
the absence of emulsians, significant carryover of only the weakest acids,
2-4-dimethylphenol (50%) and 4-chloro-3-methylphenol (10%), occurred.
Lab V minimized emulsion problems by dilution of the creosote waste from the
wood preserving industry before commencing to analyze it.
A strong relationship exits between acid volatility and analytical recovery.
In all laboratories contributing to this report, acid recovery was. lower
for the more volatile phenols (bp < 211°C: 2-chlorphenol, phenol, 2,4-.
dichlorophenol, and 2,4-dimethylphenol), than for the less volatile ones
(bp >211°C: 2-nitrophenol, 4-chloro-3-methylphenol, 2,4,6-trichlorophenol,.,
and pentachlorphenol). In general, the relative standard deviation decreased
in going from the most volatile to least volatile group; the p-nitrophenols
were excluded from consideration in the volatility grouping because of their
propensity to thermally undergo /intramolecular oxidation to p-quinones which
may also explain why these phenols chromatograph poorly. Application of the
•c
374<
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14
two-tailed statistical test for significance of the overall difference in
recoveries for these two groups of acids results in a greater than 95% con-
fidence that the volatility hypothesis is valid.
Comparison of the recoveries of phenol (Table III, 54+24) and ds-phenol
(Table VII, 55+_20) suggests that ds-phenol is a good choice for a surrogate.
BASE/NEUTRALS COMPOUNDS
The simultaneous analysis of the 46 B/N compounds probably represents the
most difficult task in the analysis of the organic priority pollutants. This
- - - »
report summarizes the analytical results of 43 B/N compounds. No analytical
results for bis(2-chloroethoxy)methane, 4-chlorophenyl phenyl ether, or N-
^
nitrosodimethyl amine are contained in this report. Presumably, 4-chlorophenyl
phenyl ether and bis(2-chloroethoxy)methane are not readily acquired. Absence
of data for N-nitrosodimethylamine probably results because of its poor chromatc
graphic properties (GC gives a low broad peak). Also it is questionable
whether bis (2-chloroethoxy)methane is stable enough in the aqueous environ-
ment, particularly under basic conditions, to be analyzable per the specified
methodology. Dibutyl and bis(2-ethylhexyl) phthalates were invariably present
in the method and field blanks analyzed by Labs III and IV. Since the waste
samples from the leather tanning and timber industries were particularly
beset with emulsion problems, some carryover of B/N compounds into the
acid fraction was observed. The most significant carryover occurred in the
a
-------
15
lagoon influent samples taken from the timber industry, and these
samples invariably had a high background of the prioirty pollutant
being analyzed. Analysis for the basic compounds in the acid fraction
would probably be futile since they form hydrochloride salts that would
most likely remain in the aqueous phase even if they were carried into the
acid fraction. If the B/N compounds are separated into reactive and
nonreactive groups, then discernible recovery differences become evident
(Table VIII). The reactive group comprises of the alkyl amines and
chlorides, the phthalate esters, and isophorene (an enone); the nonreactive
group consists of all the other B/N compounds. It is well known that
alkyl amines and chlorides react with each other to produce alkylated
ammonium salts^4- Futhermore, alkyl chlorides can undergo elimination
and substitution reactions, like reaction with hydroxide ion to form alkene
and alcohols (aryl chlorides are inert to mucleophilic substituion and are
placed in the nonreactive group); perchlorocarbons can also form aldehydes,
ketones, and carboxylic acids by reaction with hydroxide ion. Esters are
saponified by base arid isophorone can undergo condensation and Michael
addition reaction14. Thus, greater analytical variability is to be expected
in the B/N reactive group. The data in Table VIII appears to verify this
anticipation since, in general, recovery decreases and relative standard
deviation increases in going from the nonreactive group to the reactive
group. Lab II and Lab IV have noted instability indications associated
376^
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16
with the standards for the B/N analysis. Radian Corporation did a ten
month storage stability study of their B/N standard in methylene chloride
and found significant changes in the concentrations of the chloroalkyl
ethers, N-nitrosoam1nes, hexachlorocyclopentadiene. dibenzo(a,h)anthracene,
and benzidine*2. Because of emulsion problems, Lab III used continuous
extractors in the analytical processing of the samples from the leather
tanning and timber industries. As noted earlier the pH was initially
adjusted to above 11, but after 24 hours of extraction the pH dropped to
8-9. Lab III performed analyses on sample matrices from a more complex and
diverse industrial cross section and have the lowest Interlab Comparison
recovery value (55^24) in Table I, .in spite of statistical refinement of
the data. Other problems in the GC/MS screening of the B/N compounds include
coelution of anthracene with phenanthrene, benzo(a)anthracene with chrysene,
and benzo(b)fluoranthrene with benzo(k)fluoranthrene coupled with the inability
to distinguish between these pairs by"mass spectrometry. Thermal decomposition
of 1,2-diphenylhydrazine to azobenzene and N-nitrosodiphenylamine to diphenyl
amine and tetraphenylhydrazine has been documented15.
Comparison of the respective recoveries for dg-naphthalene (76+22) and d£-
nitrobenzene (70+71) 1n Table VII versus naphthalene (89+51) and nitrobenzene
(77+51) in Table IV is favorable.
377
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17
PESTICIDES
The GC/EC analysis of the pesticides is the most straight-forward of
the organic priority pollutants^. Since found Chlordane, PCB, and
Toxaphene are indistinguishable due to interferences between the'many
compounds in the spike, that the pesticides are spiked in groups of
compounds known to be separable. Endrin aldehyde has a high standard
deviation in Table V probably because of partial air oxidation to a
carboxylic acid.
HETALS
For the most part, none of the laboratories had difficulty in the metals
analysis above concentration of approximately 25 ppb. The high standard
deviations present in the data of Lab I is no doubt due to the low spiking
level which is close to the detection limit of the method used by the
laboratory. ' In the flameless analysis of zinc, environmental contamination
problems were apparently experienced by Labs I and II. It is also possible
that in the method standard analysis of chromium, copper, and nickel, Lab
I was having contamination problems from copper and stainless steel plumbing.
i
CYANIDE AND TOTAL PHENOLS
Total phenols were colorimetrically determined by Labs II and IV via a
totally automated procedure^. Recovery data for the cyanide and total
phenols are presented in Table VI.
37?
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18
SUMMARY AND CONCLUSIONS
A summary of the overall recoveries of the priority pollutants is given
in Table I. In every case, except for the purgeable organic compounds,
the overall recovery decreases and the relative standard deviation
increases in going from the method standard to the matrix spiked analysis.
Of the organic priority pollutants, the analysis of the purgeable and acid
organic, compounds results in the highest recoveries with the smallest
of tK<. ^vxfneo\Ae Pfr*jaWt C^povi/rv^s t*4 tt\c dtifmse "•>
matrix effect. The increase in recovery for the phenolic acids in going
from unadulterated water to a matrix aqueous medium may be a salting-out
and salting-in effect, respectively, and needs to be studied. The two
major variables for these groups is volatility and carryover of phenolic
acids into the B/N fraction, the latter arising mainly from emulsion problems
since the data from Lab III suggest that no pka dependence was associated
^»,
with their observed acid carryover. The process of continuous extraction
itself may be responsible for carry over which needs to be experimentally
determined. Volatility can be controlled by close monitoring of the
analytical process. Ascertaining that the pH is greater than 11 and, in
the case of emulsion, performing an additional base wash of the B/N
methylene chloride extract will rectify carryover of the acids into the
B/N fraction. The question concerning the stability of methylene chloride
«
during long term (24 hour) contact with hydroxide solution under emulsion
conditions needs to be investigated.
-------
19
In part, the analysis of the base/neutral and pesticide compounds give-the
lowest recoveries because of their greater propensity to react among each
other or with hydroxide or water^*. Several laboratories have noted that
when the four different B/N methanolic standards are mixed in methylene
chloride that this solution becomes turbid and eventually changes to a
yellow color. Thus, the stability of the priority pollutants, benzidine / '
and 1,2-diphenylhydrazine in contact with methylene chloride needs to be
fully determined. Saponification of the phthalate esters has been observed
during the B/N analysis by several laboratories. Another major variable
in the analysis of the B/N compounds is carryove'r into the acid fraction
in the presence of emulsions; this appears to be particularly acute at high
background concentrations of the B/N component.
The VOA analysis per the EPA protocol has proved to be the most successful.
The acid and pesticide analyses have been moderately successful, and the B/N
analysis has been less successful on samples with severe matrix problems, as
from the leather tanning and timber industries. Nevertheless, the present
methodology is adequate and appears capable of improvement. We can be con-
fident that false positive analyses are considerably less likely than false
negative analyses so that when a priority pollutant is detected in the environ-
ment we know the measured quantity is probably smaller than the true value.
Table IX summarizes problems associated with the current priority pollutant
methodology.
C
380-=
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20
Initial recommended performance control limits can be computed by
adding (upper control limits, UCL) or subtracting (lower control limit
LCL) three times the standard deviation from the average percent
recovery values presented 1n Tables I to VI1116. Some of LCL's will no
doubt increase as the analytical methodology improves. Also, one should
note that these control limits are somewhat dependent upon the level of
standard addition, the degree of which has not been fully investigated.
-------
Acknowledgement
The major portion of the data in this summary came from EPA-Region VII
and EPA Quality Assurance Contract Reports from A.D. Little. Inc. Acorn
Park, Cambridge, HA 02140 (EPA contract #68-01-3857) Carborundum Co. 3401
LaGrande Blvd. Sacramento CA 95823 (EPA contract #68-01-4689) and Versar,
INC., 6621 Electronics Dr.-, Springfield, VA 22151 (EPA contract # 68-01-3852).
-------
Literature Cited
1. Environmental Science and Technology, February 1978, p. 154
2. "Sampling and Analysis Procedures for Screening of Industrial
Effluents for Priority Pollutants," US EPA, Environmental Monitoring
and Support Laboratory, Cincinnati, OH 45268, March 1976 (Revised April 1977)
3. Federal Register, 38(125), 17318(1973)
4. "Midwest Research Institute Final Letter Report on Evaluation of Test
Procedure for Acrolein and Acrylonitrile, "MRI Project NO. 4719-A,
US EPA Environmental Monitoring and Support Laboratory, Cincinnati,
OH 45268, June, 1979.
5. "Methods for Chemical Analysis of Water and Wastes," US EPA, Enviro-
mental Monitoring and Support Laboratory, Cincinnati, OH 45268, March,
1979.
6. "Procedure for Preliminary Evaluation of Analytical Methods to be
Used in the Verification Phase of the Effluent Guidelines Division BAT
Review," US EPA, Environmental Monitoring and Support Laboratory,
Cincinnati, OH 45268, March 1978.
7. "Addendum for Sampling and Analysis Procedures for Screening of
Industrial Effluents for Priority Pollutants," US EPA, Environmental
(~~* Monitoring and Support Laboratory, Cincinnati, OH 45268, April, 1979.
8. J.W. Eichelberger, L.E. Harris, and W.L. Budde, Anal. Chem. ,47, 995
9. Federal Register, Volume 44, NO. 233, December 3, 1979. "Guidelines
Establishing Test Procedures for the Analysis of Pollutants, Proposed
Regulations".
10. H.M. McNair and E.J. BonelH, "Basic Gas Chromatography." Consolidated
Printing, Berkeley, CA, 1969, p. 52.
11. American Society of Testing and Materials., D2777.
12. Private communications with Dr. L.H. Keith, Radian Corporation., Austin,
Texas.
13. M.R. Spiegel, "Statistics," (Schaum's Outline Series), McGraw-Hill Book
Co., San Francison, CA, 1961, -p. 170.
C
-------
14. R. Morrison and R. Boyd, "Organic Chemistry," 2nd Edition, Allyn and
Bacon Inc., Boston, HA, 1969
15. "Seminar on Analytical Methods For Priority Pollutants," Proceedings,
US EPA, Denver, Colorado, November, 1977.
16. "Handbook for Analytical Control in Water and Wastewater Laboratories,"
US EPA, Environmental Monitoring and Support Laboratory, Cincinnati, OH
45268, March, 1979.
384<
-------
TABLE I. IKTERLABORATORY COMPARISON8
Priority
Pollutant
Fraction"
Volatile
(MS)
Volatile
Sample Spike
Acid (MS)
Acid Sample
Blank
B/N-(MS)
B/N Sample
Spike
Pesticide
(MS)
Pesticide
Sample Spike
Metals (MS)
Metals
Sample Spike
Cyanide (MS)
Cyanide
Sample Spike
Phenol ics
(MS)
Phenolics
Sample Spike
LAB
I
88+21
82+24
90+18
92+34 ~
95+25
84+18
73+8
69+_7
113+_37
100+20
103+J4
10U12
10+13
93+.15
LAB LAB
II III
95+_5
101+9 93+J3
89+_5
72+10 62+J2
78+41
61+22 55+_24
74+J9 ' -
51+18 33+10
-
103+J4
-
-
97+6
t
98+J 0
LAB LAB LAB
IV V VII
100+8 -
107+_9 -
67+_14 82+.16 -
60+15 84+.17 -
77+_15 -
68_+16 - 63+_13
88+8
93+5
103+.8 -
92j+7
lOSjfS -
93+J6 -
100+_7 -
97+9
Averagec
90+_13
92+_15
84_+13
76+J9
84+_25
68+_21
78+_ll
59+_ll
108^22
96+_ll
103+_7
96^14
101 +_8
96+11
a) The values are in units of percent recovery (P) plus or minus (+) one
standard deviations (Sp).
b) MS refers to the method standard or the standard addition to blank water.
Sample spike refers to the standard addition to a sample.
c) P and Sp are weighted averages based on the number of data points
contributed by each laboratory.
-------
TABLE II. Purgeable Orgam'csa
Compound
Acrolein
Acrylonitrile
Benzene
Bromodichloromethane
Brcmoform
Bromomethane
Carbon Tetrachloride
Chlorobenzene
Chiorodibromomethane
Chloroethane
Chloroform
Chloromethane
Dichlorodifluoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethylene
trans-7,2-Dichloroethylene
Dichloromethane
1,2-Dichloropropane
cls-1,3-Dichloropropene
trans -1-3-D1chloropropene
Ethyl benzene
Hethodb
Standard
77+30
96+^31
89+12
97+11
94 +.14
90^16
91+23
94+^23
86+12
67+22
90^18
91+^22
108+11*
83j+10
102.+12
74+,24
90+^25
82^46
94+_26
95^15
91+13
109+19
Standard0
Spike
32+30
102^28
93+24
103+31
88+12
78+15
9H33
103+24
99+17
6CH23
91+26
64^28
- 114+8*
87+21
103^27
80+32
85+35
66^66
99^30
98+20
93^16
106+28
c
386<
-------
Continuation of Table.II
Method Sample
Compound Standard Spike
1,1,2,2-Tetrachloroethane 81+31 78+31
Tetrachloroethylene 97+13 99+25
To!uene 9S+22 97+_25
1,1,1-Trichloroethane 92+21 94^36
1,1,2-Trichloroethane 102^14 103^19
Trichloroethylene 10fr+14 110+22
Trichlorofluoromethane 59+^23 67^48
Vinyl Chloride 103+30 79+22
a) The values are in terms of P ± Sp. Data from 2-4 laboratories have been
averaged except where noted with an (*) asterisk. In general the concentration
added ranged from 10 to 1000 parts per billion.
b) Standard addition to blank water.
c) Standard addition to sample. :
*Data from only one lab were available.._.
C
387-:
-------
COMPOUND
2-Chlorophenol
4-Chloro-3-methylphenol
2,4-Dichlorophenol
2,4-Dimethylphenol
4 ,s--Di ni tro-£-cresol
2,4-D1n1trophenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophneol
TABLE III. ACID FRACTION3
HETHODb
STANDARD
96^16
86+24
71+19
87+_34
89+22
95+_22
65+_33
87+24
61+11
91+22
SAMPLEC
SPIKE
71+23
99^19
84+_23
72+_16
102^23
92+40
87+_22
59+46
84^22
54+_24
80+24
a) The values are In terms of P _+ Sp. Data from 2-5 laboratories have '
been averaged. In general the concentration added ranged from 20 to 2500
parts per billion.
b) Standard addition to blank water.
c) Standard addition to sample.
-r
388^
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TABLE IV BASE/NEUTRAL FRACTION*
C
Compound
Acenaphthene
Acenapthylene
Anthracene*^
Benzldine
Benzo(a)anthracenee
Benzo(b)fluoranthene^ -
Benzo(k)fluoranthene'f
8enzo(a)pyrene
Benzyl Butyl Phthalate
Bis(2-chloroethyl) Ether
Bis(2-chloroisopropyl) Ether
Bis(2-ethylhexyl) Phthalate
4-Bromophenyl Phenyl Ether
2-Chloronaphthalene
Chrysenee
Dibenzo(a,h)anthracene
Di-n-butyl Phthalate
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
3,3'-Dichlorobenzidine
Method^
Standard
90+_22
83+22
98+20
44+27
105+33
96+68*
^™ t
96+68
90+22
49+39
98+48
154+;! 36
70+33
80+25
88+20
105+J33
80+42
80+_32
6&+24
67+_21
67+_22
71+85
Sample0
Spike
78+_24
79+27
79+26
40+29
51+_24
41+_21
47+_27
43+21
49+_22
80+_49
96^88
66+50
63+25
79+_21
77+_27
36+_29
58+_27
65+27
62+20
63+_21
62+45
C
389<
-------
c
Method^
Standard
71+37
43+37
122+55
115+41
84+44
97+.2S
111+26
98+24
98+31
76^26
38+28
63+22
66+36
109.+14
83+24
106.+31
72^22
86+.S4
98+20
142^41
74+22
Sample0
Spike
65+37
66+43
94+45
104+35
88+32
91+32
63+20
88+25
76+31
77+45
27+JO
58+23
67+_22
40^21
89+51
77+51
66+25
7H22
79+20
63+_20
-69+24
C
Compound
Diethyl Phthalate
Dimethyl Phthalate
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di-n-octyl Phthalate
1,2-Diphenylhydrazine '
(and/or Azobenzene)
Fluoranthene
Fluorene
Hexachlorobenzene
Hexachlorobutadiene
Hexachlorocyclopentadiene
Hexachloroethane
Isophorone
Indeno(l,2,3-cd)pyrene
Naphthalene
Nitrobenzene
N-ni trosodi pheylamine
(and/or Diphenylamine)
N-Nitrosodi-^-propylamine
Phenanthrene
Pyrene
1,2,4-Trichlorobenzene _ _
i
a) The values are In terms of P _+ Sp. Data from 2-5 laboratories have been
averaged except where noted with an (*) asterisk. In general the concentration
added ranged from 10 to 500 parts per billion.
b) Standard addition to blank water.
c) Standard addition to sample.
d.e.f) These isomers pairs are not separted by packed column GC. Also mass
spectral data are not sufficiently unique to allow differentiation.
*0ata from only one lab were available.
39CK
-------
e
TABLE V. PESTICIDE FRACTION*
Methodb
Standard
72+13
78413
79+21
78+14
82_+16
8H17*
82^14
76^14
85+17
7H14
65+14
67±19
74^39*
82+_25
64+76*
72^12
82j+14
83f!l*
89+12*
Sample0
Spike
v 55+12
55^12
57+22
64+11
_61±16
39_+9*
62+16
57^1 8
76+26
62+16
61+J3
66jfl4
844.30*
68^18
34^39*
49^12
65+11
42^13
Compound
AldHn
alpha-BHC
beta-BHC
gamma-BHC
delta-BHC
Chlordane
4,4'-ODD
4,4'-DDE
4,4'-DDT
Dieldrin
Endosulfan I
Endosulfan II
Endosulfane Sulfate
Endrln
Endn'n Aldehyde
Heptachlor
Heptachlor Epoxide
PCB
Toxaphene
a) The values are in terms of P *_ Sp. Data from 2-4 laboratories have been
averaged except where noted with an (*)asterisk. In general the concentration
added ranged from 0.1 to 100 parts per billion.
b) Standard addition to blank water.
c) Standard addition to sample.
•data from only one lab were available.
r
391<
-------
TABLE VI. METALS, CYANDIE, AND PHENOLICS3
c
PARAMETER
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury^
Nickel
Selenium
Silver
Thai 1 ium
Zinc
Cyanide
Total Phenols
METHOD13
STANDARD
61+47*
120+20
89+16
9H18
99+30
136j+70
116+32
83+24
84^62
112+15
110+25-'
99+33*
122+44
103+7
101+8
SAMPLE2
SPIKE
103+24
SL ^*
97+_25
94+20
98+23
106+_25
99+24
93+_25
79+_38
101+_26
93+_20
80_+25
95+_23
106+_37
96_+14
96+11
a) The values are in terms of P _+ Sp. Data from 2-3 laboratories have been
averaged exept where noted with an (*) asterisk. In genral the concentration
added ranged from 10 to 1000 parts per billion.
b) Standard addition to blank water.
c) Standard addition to sample.
d) Analyzed by the cold vapor technique.
*Data from only one lab were available.
-r
332<
-------
TABLE VII. PRIORITY POLLUTANT SURROGATES*
Compound
(Purgeable Orgnalcs)
ds-Benzene
Bromochl oromethane
d-Chl orof onn
1 ,4-Dichlorobutane
d4-l ,2-Dichloroethane
d~Dichl oromethane
nzene
Fluorobenzene
dg-Tol uene
i ^3-1 ,1 ,1-Trichloroethane
1-chl oro-2-bromopropane
(Acids)
2-Fluorophenol
Pentafl uorophenol
LAB
LAB
LAB
139+_96
119+29
146+55
102+_25
96+20
117+41
Tri f 1 uoro-m-cresol
(Base/Neutral)
Decaf 1 uorobi phenyl
ds-Napthalene
2-f 1 uoronaphthal ene
1-fluoronaphthalene
2-fl uorobi phenyl
76+.36
84^30
55+_20
72+42
39+,! 8
76+_22'
75+^20
69+18
68+J6
63+5
95^10
98+11
96+10
97+12
95+10
93+11
50+22
41+29
101+39
46+13
-------
Table VII (cont'd)
ds-aniline 57+36
Compound LAB I lib ' LAB IVC LAB VII id
2-fluoroaniline 74+39
ds-nitrobenzene 70+21
a) The values are in terms of P _+ Sp. The concentration added ranged from
20 to 200 parts per billion. '
b) The matrix for these surrogates included influent and effluent samples
from 12 different industrial categories.
c) The matrix for these surrogates included POTW, detergent, and chemical
disposal industries.
d) The matrix for these surrogates included POTW samples only.
331+
-------
TABLE VIII. REACTIVITY GROUPS OF THE B/N PRIORITY POLLUTANTS
Method Standard Analysis
Matrix Spiked Analysis
Nonreactive Group Reactive Group Nonreactive Group Reactive Group
Laboratory
I
II
III
IV
VII
P+Sp
102+26 .
93+31
-
82f!0
_
P+Sp
.86+21
52+46
'
67^18
.
P+Sp
87+.18
60>21
.58+26
71 +.12
65+11
/
P+Sp
78+17
64+25
48+12
63+J8
57+17
Nonreactive B/N Compounds: Acenaphthene, Acenaphthylene, Anthracene, Benzo(a)anthra-
cene, Benzo(g,h,i)perylene, benzo(a)pyrene, 2-Chloronaphthalene, 1,2-,1,3-, and 1,4-Di
chlorobenzene, 2,6-Dinitrotoluene, Fluoranthene, Fluorene, Hexachlorobenzene, Naptha-
lene, Nitrobenzene, Pyrene, and 1,2,4-TrichlorobenzeTie.
Reactive B/N Compounds: Benzidine, Bis(2-chloroethyl) Ether, Bis(2-ethylhexyl),
Diethyl, and Dimethyl Phthalates, 1,2-Diphenylhydrazine, Hexachlorobutadiene,
Hexachloroethane, and Isophorone.
31*
-------
TABLE IX PROBLEM PRIORITY POLLUTANTS
COMPOUND
Dlchloromethane
bis-chloromethylether
N-nitrosodimethylamine
Di-n-butylphthalate
Bi s-(2-ethylhexyl)phthal ate
1,2-diphenylhydrazine
Benzidine
Hexachlorocyclopentadi ene
Endrin Aldehyde
Anthracene and Phenanthrene
Chrysene and benzo(a)-
Anthracene
benzo(b)fluoranthrene and
benzo(k)fluoranthrene
PROBLEM
Frequently found in"blanks and
samples because of In lab con-
tamination.
Readily hydrolyzed in water., '
Poor chromatographic properties.
Frequently found in blanks.
Frequently found in blanks.
Thermally decomposes to diphenyl
amine and tetraphenylhydrazine.
Poor chromatographic properties.
Subject to thermal and hydrolytic
decomposition.
Is readily oxidized.
Coelute on packed columns.
Coelute on packed columns.
Coelute on packed columns.
-------
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON. D.C. 20460
OFFICE OF
RESEARCH AND DEVELOPMENT
SUBJECT: Toxics Data System—Evaluation of Region VJZ Data Set
FROM: Chris Timm, Director /'pLs^'
Quality Assurance Management Staff£,
Office of Monitoring and Technical Support (RD-680)
TO: Edmund Notzon, Director
Monitoring and Data Support Division
Office of Water and Waste Management (WH-553)
In response to the request by Fred Leutner at the May Agency Quality Assurance Advisory
Committee meeting, the. QAMS agreed to review your evaluation of the four data sets.
prepared for the initiation of the Toxics Substances Data Systems. Subsequently, I met
with Paul Durand of your staff to review the files on your original assessment. As I
understand it, the initial assessment was developed solely by phone coversations between
your staff and the project officers or principal investigators with no further documentation
of the compliance with data evaluation criteria.
Consequently, I requested Bob Booth, Deputy Director, Environmental Monitoring Systems
Laboratory-Cincinnati, to evaluate the Region vn data set in order to verify their reported
status for each of the criteria being considered. Bob completed his evaluation during the
week of June 23-26, 1980, and a copy of his report is attached.
Based upon this report, we believe that the Region YE data set is of adequate quality
and documentation for input into the Toxics Substances Data System. We do recommend,
though, that some type of assessment of the data quality, such as the Quality Assurance
Criteria recommended earlier or preferably, a numerical assessment of precision and
accuracy be input along with the data in order to assure future credibility.
V.'e are proceeding with a review of the other three data sets, based upon the information
provided by your staff, and should have our evaluation reports to you before September
30, 1980.
Attachment
cc: Courtney Riorcsn (RD-680)
Richard Dov.-d (A-101)
Robert Booth (E.MSL-CI)
Thomas Stanley (RD-680)
sjrnov Verner '(RD-680)
"
39'
-------
X*0*"*,
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
CINCINNATI. OHIO 45263
DATE: July 24, 1980
SUBJECT: Toxics Data System; Evaluation of Region 7 Data
FROM: Robert L. Booth, Deputy Director /
Environmental Monitoring and Support
Laboratory - Cincinnati
TO: Christopher M.'Tiwm,.. Director
Quality Assurance Management Staff
Office of Monitoring and Technical Support
Per our discussions on- this Subject, I reviewed the Region 7 data sets
that are being considered as part of the pilot storage study for TOXET.
The following comments are made around the headings of the "check list
reference" table given in Ned Notion's draft of April 23, 1980. This
evaluation was made as part of our on-site evaluation of Region 7's
laboratory during the week of June 23-26, 1980.
1. STATION IDENTIFICATION
The data to be considered for the'pilot study will be that
generated from the POTW studies being done for O'FarreVs -
group in headquarters. The stations were apparently picked
by O'Farrel. Burns and Row, the prime contractor, is responsible
for the sampling. In my discussion with Charles Hensley and
Billy Fairless, it was recognized that there is probably not
an adequate station identification/description for STORET/TOXET
purposes at this time. Providing resources were made available
to the region, this information can be provided.
2. IN STORET FORMAT
The identification number is assigned by the prime contractor and
the sample is shipped to the regional laboratory. Once the
analysis has been completed and the results reviewed by Charles
Hensley the data are forwarded to O'FarreTl. Regional staff do
not believe the data are currently in EPA STORET format. Again,
the region does have the necsessary expertise to provide this
required input but additional resources would need to be.provided,
398<
-------
3. QUALITY ASSURANCE (QA) PLAN APPROVED
No formal plan was prepared for the study. In reviewing their
QA program I learned that the following protocol is being used.
»
a. In a set of 12-16 samples representing a single POTW site,
the region is provided with a field blank and at least
one duplicate sample by the contractor.
b. A spiked sample is prepared in the laboratory.
c. Once a set of approximately 15 duplicate and spiked
data points is available, i.e., from 15 different POTW
sources, a statistical summary is prepared.
d. Two standard deviations is used as a warning
limit and three standard deviations as a control
limit. These limits are generated by the lab
staff on the above mentioned samples. Their precision and
accuracy data are significantly better than the data
being provided by the other three contractors in the
POTW studies. In factf as a side issue, in my review
of the data, I would strongly recommend that at least
2 of the 3 contractors be fired and that their data
be purged from the system.
The regional QA plan is now available in draft form. As
you know, however, it does not provide the kind of detail
that is needed for a laboratory QA plan. This will probably
be forthcoming when the laboratory staff is required to
prepare standard operating procedures and QA project plans
as a part of the Agency's Mandatory QA Program.
4. QA AUDITS
The laboratory has actively participated in our performance
evaluation studies, and they routinely make use of our Quality
Control check samples. A review of their data shows that they
are within the Agency's acceptance limits 98% of the time for all
contaminants at varied concentration levels. Clearly, they rank
as one of the Agency's best laboratories in this category.
5. QUALITY CONTROL (QC)
It was apparent from our on-site lab evaluation and from the candid
conversations that I had with management, that region 7 has an
excellent on-going QC program. As is the case with a number of
programs, there is a need to document in some areas what is being
-------
done. Overall, the field collection, laboratory analysis, and
data management systems are being"quality-controlled in an
exemplary manner.
6. PRECISION AND ACCURACY
As indicated, precision and accuraricy data are available on real
world samples. More importantly, they have a strong data base from
previous studies to compare their current performance samples.
Their methods of calibration are well documented and they are
readily available. In this regard, it should be noted that Dr.
Jerry Dias, a consultant to their program, has done an outstanding
job in presenting their QA data in an easy to follow manner.
Perhaps even more noteworthy, he has had an opportunity to
review the data and make some interesting observations concerning
the fate of these organic contaminants in the environment.
7- METHODS
Approved methods are being used in the POTW studies. The organic
analysis is being done by use of GC/MS techniques and the toxic
metals are being done by ICP . Both methods are published in the
Federal Register and will be part of final rulemaking for section
304(h) methodology in the near future.
8. DATA REVIEW
ie following system is used for review of data:
a. Data are provided to a key puncher with an absolute mini-
mum number of transfers by staff.
b. Key puncher provides data cards which are verified by a
second party.
c. Roy Crossland, Data Coordinator for the region, does a
spot review of the data printout and makes certain
checks to verify validation of data.
d. Charles Hensley, Acting Chief, also reviews the printout
in a similar manner before approving its forwarding to
headquarters. Although a detailed line-by-line
review of the data is not being made, any major errors are
probably, being caught by this review process.
As we have discussed, a very important element that is not covered in the table
heading is that of sample conditions. This would include the type of
containers used, the preservative used, and the holding times that are required.
In reviewing these elements with the laboratory staff, it would appear that
4OCK
-------
there is a holding time problem for the organics. This is limited to the
holding time that the sample extraction may be held after the liquid liquid
extraction has been made on the aqueous sample. In some cases, due to
instrumental failure or an unusually large number of samples coming in at
one time, sample extractions are being held for longer than the currently
recognized holding times. They are already running two shifts to alleviate
this problem and have taken other actions to limit the instances in which
sample extracts are held too long.
All of the above information was provided to Paul Durand in a meeting held in
Alexandria, Virginia, on July 17. At his request, I provided him this detailed
information so that he would be properly perpared for a briefing he was to
have with Ned Notzon on July 25. As I noted to him, I believe that, overall,
the POTW data being generated by Region 7 can be used in this pilot study.
It is obvious, however, that certain elements need to be strengthened
before we can consciously say "yes" on the check list table.'
cc: Charles Hensley, Chief, Laboratory Branch, Surveillance and Analysis
Division, U.S. EPA, Region 7
Billy Fairless, Deputy Director, Surveillance and Analysis Division,
U.S. EPA, Region 7
-------