DETERMINATION OF PURGEABLE ORGANICS
IN SEDIMENT USING A MODIFIED
PURGE AND TRAP TECHNIQUE
David N. Speis
XW'r
-------
DETERMINATION OF PURGEABLE ORGANICS IN SEDIMENT
USING A MODIFIED PURGE AND TRAP TECHNIQUE
DAVID N. SPEIS
U.S. ENVIRONMENTAL PROTECTION AGENCY
REGION II
EDISON, NEW JERSEY 08817
OCTOBER 10, 1980.
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DETERMINATION OF PURGEABLE ORGANICS IN SEDIMENT
1. Scope and Application
1.1 Thi's method is desiqned to determine volatile organics
trapped in sediment that are capable of beinq thermally
desorbed from the sediments and deposited by a carrier
gas onto a porous polymer tran.
1.2 This method can be used to determine oriority pollutant
puraeables as listed in Table 1.
1.3 This purae and tran techniaue is preferably used with
gas chromatography/mass soectrometry but can be used with
electron capture gas chromatography.
2. Summary of Method
2.1 An aliauot of sediment is nlaced into a hyno vial and
sealed. The vial is attached to the thermal purge
modification of-a purge and trap apparatus. The volatile
organics are thermally desorbed from the sediment and
transferred to a porous polymer tran using an inert gas.
When thermal desorption is complete, and all volatile
organics have been transferred to the trap, the trap is
backflushed with the inert purge gas and rapidly heated,
desorbing the concentrated organics to the inlet of the
gas chromatograph. The mixed volatile organics are
chromatographically separated and analyzed using a mass
spectrometer or electron capture detector to provide
gualitative data and quantitative information.
3. Interferences
3.1 The analytical system must be demonstrated to be free from
interferences as demonstrated throuqh the analysis of an
orqanic free blank. Extremely contaminated samples may
contain compounds that chromatoaranhically mask compounds
of interest. This can be especially serious if the masking
compounds contain interferinq ions.
-------
3.2 Cross Contamination
3.2.1 Cross contamination can occur in the analytical
system when extremely contaminated samples are
analyzed. An organic free water blank should be
analyzed after the analysis of a contaminated
samnle to insure that cross contamination does not
occur.
3.2.2 Cross contamination can occur via diffusion during
transportation or storaae of contaminated samples.
A trio blank should accompany samnle vials throughout
the entire survey process. This blank should be
analyzed with the reaular samples to monitor possible
cross contamination.
4. Apparatus and Materials
4.1 Sampling Eauinment
4.1.1 Teflon-coated stainless steel spatula (methanol-
rinsed, oven-dried at 105 C).
4.1.2 40 ml screw cap vial (deterqent-washed and dried;
105° C oven).
4.1.3 Teflon-backed silicon septum (detergent-washed
and dried; 105 C oven)
4.2 Analytical Equipment
4.2.1 Purge and trap device capable of meeting specifi-
cations outlined in Federal Register Method 624,
(Sec. 4.2) with modification for sediment purging
consisting of a variably heated sand trap as
illustrated in Figure 1. This device consists of
a 250 ml sand-filled beaker wrapped with heating
tape. A 15 ml septum vial is connected in series,
using 1/16" I.D. stainless steel tubing with the
purge gas line and organic free water trap.
4.2.2 Gas chromatograph (capable of meeting Federal Register
Method 624 specifications (see Table 2).
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4.2.3 Mass spectrometer/Data System capable of meeting
Federal Register Method 624 specifications.
4.2.4 Stainless steel soatula.
4.2.5 10 ul syringe.
5. Reagents
5.1 Commercially available puraeable priority pollutant
standard solution consisting of compounds listed in Table 1.
5.2 Commercially available surroaate standards (pure) diluted
to a concentration capable of delivering 500 ng of standard
with a normal injection size.
5.3 "Oraanic Free" distilled water. "Oroanic Free" or "Reaaent
Free" water can be generatedpby passing distilled water
through a bed of Tenax G.C. ' and activated charcoal.
6. Sample Collection and-Preservation
6.1 Samples are collected in 40 ml sampling vials with teflon-
Backed silicon septa lining the vial caps. The vials
should be filled to capacity to minimize the amount of
headspace. A methanol-rinsed stainless steel spatula
is used for sample collection.
6.2 Samples should be.shipped and stored at wet ice temperature.
Samples must be analyzed within one week of collection.
7. Sample Extraction and Analysis
7.1 Weigh 2-3 qrams of a sediment sample into a Pierce (or
equivalent) 15 ml Hypo vial". Quickly seal the vial with
a teflon-backed silicon septum (a maximum of 6 grams of
sediment may be used if the sample is sandy and appears
to be uncontaminated.)
7.2 Inject 2 ul of three internal standards (to be used for
matrix affects monitoring). The compounds are bromo-
chloromethane, 2-bromo-l-chloropropane, and 1.4-dichloro-
butane at a level of 250 ng/ul. Inject the internal
standards directly into the sediment using a 10 microliter
syringe.
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7.3 Adjust the temperature of the sand bath to 110° C + 2.0 C.
NOTE: Sand bath temperatures above 110° C may cause excess
water vapor to enter the GC/MS system. This will be
immediately noticeable by monitoring the recovery
of bromochloromethane. Monitor the sand bath
temnerature after each analysis.
7.4 Fill the FLO trap with 5 ml of reaaent free H20. Attach
the 15 ml nyno vial to the purge and trap modification
as indicated in Figure l,.usina a sharpened piece of S.S.
tubing to pierce the septum of the sample vial. Immerse
the vial into the sand bath.
7.5 Purge and Tran
7.5.1 Heat the sample for 20 minutes while purging at
a rate of ^0 ml/min.
7.5.2 At minute 20 - turn filament on.
7.5.3 At minute 20 - begin 4 minute Tenax trap desorption.
7.5.4 At minute 21 - start data collection.
7.5.5 At minute 22 - begin temperature programming GC oven.
7.5.6 At the completion of the desorption phase, vent
the trap for a minimum of 10 minutes.
7.5.7 Drain the H~Q from the trap and rinse with reaaent
free H20.
7.6 Gas Chromatography
7.6.1 Use columns as indicated in Federal Register
Method 624, Table 2.
7.7 Additional Purge Parameters
Purge gas: Helium UHP
Trap Dimensions: 1/8 in O.D. x 25 on long
Trap Sorbent: Tenax G.C. 60/80 mesh-- (15 cm), type 15
silica gel 35/60 mesh - (8 cm).
-------
7.8 Mass Spectrometer - caoable of scanning from 20 to 260 amu
in 7 seconds or less at 70 electron volts (nominal), and
producing a mass spectrum which meets the criteria in
Table 4 from 50 nanograms of n-bromofluorobenzene (BFB)
when this material is introduced into the mass spectrometer
either by syrinae injection into the gas chromatograph or
throuah the purae and trao system. Alternatively, the
mass spectrometer must be capable of producing a mass
spectrum which meets the criteria in Table 3 from 50
nanoarams of decaf!uorotriphenyl phosohine (DFTPP, also
known as bis (perfluorophenyl) phenylphosphine) when this
material is introduced into the mass spectrometer by
syrinae injection into the gas chromatoaranh and using one
of the columns recommended in Method 625, Federal Register.
The criteria in Tables 3 and 4 are comoatible, and a
spectrometer meeting the criteria in Table 3 (DFTPP) will
also meet the criteria in Table A (PFB). The mass
spectrometer must be interfaced with a aas chromatograoh
designed for packed-column chromatography. It is recommended
that the interface between the end of the chromatoaraphic
column and the ion source of the mass spectrometer be
constructed with deactivated glass or glass-lined materials.
However, the GC/MS interface can use any-separator, transfer
line, or other interface part, orovided it is demonstrated
that the system gives acceptable and reproducible mass
spectra of all the compounds listed in Table 1 at the
specified limits of detection, and that all other performance
criteria included in this section are achieved.
7.8.1 If the system performance criteria are not met,
the instrument must be retuned and rechecked
until the criteria are met. No samples shall be
analyzed until the performance criteria are met.
8. Qualitative and Quantitative Determination
8.1 To identify a compound, obtain the background subtracted
mass spectrum of the compound of interest. The criteria
below must be met for an identification.
8.1.1 All of the ions that are present above 10% relative
abundance in the 70 ev (nominal) electron
ionization spectrum of an authenic sample of the
comnound (or library spectrum) must be present
in the experimental-spectrum with agreement to
plus or minus 10% of the base oeak abundance.
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8.1.2 If the reference ion's abundance is 30%, allowable
limits on the relative intensity of the samole's
ion would be 20-40%.
8.1.3 The unknown peak should be within +_ 30 seconds
and all references to scan numbers should be
deleted because variable times may be used for
a complete scan.
Structural isomers that have very similar mass
spectra can be explicitly identified only if the
resolution on the GC column between the isomers
in a standard mix is acceptable. Otherwise,
structural isomers are identified as isomeric
pairs.
Acceptable resolution is achieved if the depth
of the valley between the oeaks, measured from
the smallest peak, is 50% of the smaller peak
height.
8.2 Primary ions listed in Table 5 should be used for
quantisation. Primary ion interferences can be avoided
by using secondary ions for auantitation.
8.3 External Standard Calibration
Concentrations of identified ourgeable organics may be
calculated using a single point calibration. This
techniaue should be used after response vs. concentration
linearity has been proven for the compound to be
calculated. Use Eguation 1 for this calculation.
Equation 1. (A)(B)
A = Micrograms Standard
B = Area of the unknown
C = Area of Standard
D = Kilograms Sample
-------
Bibliography
1. Federal Register, Volume 44, No
December 3, 1979.
233, pg. 69532 - 69539.
2. Determination of Purgeable Organics in Sediments. D.N. Speis.
Hydrocarbons and Halogenated Hydrocarbons in the Aquatic
Environment, Plenum Press, New York, NY 1980,
3. Bellar, T.A., Lichtenberg, J.J., and Kroner, R.C. Deter-
mining Volatile Organics in Microgram per Liter levels by
Gas Chromatography. Journal American Water Works Association,
Volume 66, No. 12, December 1974.
4. Sediment Sampling for Volatile Organics. U.S. Environmental
Protection Agency, Environmental Monitoring and Support
Laboratory. Cincinnati, Ohio. August 2, 1977.
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TABLE 1
CHLOROMETHANE
BROMOMETHANE
VINYL CHLORIDE
CHLQROETHANE
DICHLOROMETHANE
TRICHLOROFLUOROMETHANE
1,1- DICHLOROETHYLENE
1,1- DICHLOROETHANE
TRANS L, 2 - DICHLORETHYLENE
CHLOROFORM
1,2- DICHLOROETHANE
1,1,1- TRICHLOROETHANE
CARBONTETRACHLORIDE
BROMODICHLOROMETHANE
1,2- DICHLOROPROPANE
1,3- DICHLOROPROPENE
TRICHLOROETHYLENE
BENZENE
DIBROMOCHLOROMETHENE
1,1,2- TRICHLOROETHANE
BROMOFORM
1, 1, 2, 2 - TETRACHLOROETHANE
TETRACHLOROETHYLENE
TOLUENE
CHLOROBENZENE
ETHYLBENZENE
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TABLE 2
GAS CHROMATOGRAPHY OF PURGEABLE ORGANICS
'RETENTION TIME (MIN) LIMIT OF DETECTION 3
COMPOUNDS :~~ (ug/kg)
Col . 1 ' Col . 2 2
CHLOROMETHANE-
BROMOMETHANE
VINYL CHLORIDE
CHLOROETHANE
METHYLENE CHLORIDE
TRICHLOROFLUOROMETHANE
1,1-DICHLOROETHYLENE
1,1-DICHLOROETHANE
TRANS-1 ,2-DICHLOROETHYLENE
CHLOROFORM
1,2-DICHLOROETHANE
1,1,1-TRICHLOROETHANE
CARBON TETRACHLORIDE
BROMODICHLOROMETHANE
1,2-OICHLOROPROPANE
1,3-DICHLOROPROPANE
TRICHLOROETHYLENE
DIBROMOCHLOROMETHANE
BENZENE
1,1,2-TRICHLOROETHANE
BROMOFORM
1,1,2 ,2-TETRACHLOROETHANE
TETRACHLOROETHYLENE
TOLUENE
CHLOROBENZENE
ETHYL BENZENE
BROMOCHLOROMETHANE 4
2-BROMO-l-CHLOROPROPANE 4
1,4-DICHLOROBUTANE 4
ACROLEIN
ACRYLONITRITE
1.50
2.17
2.67
3.83
5.25
7.18
7.92
9.30
10.08
10.68
11.40
12.60
13.02
13.65
14.92
15.22
15.80
16.48
16.30
16.52
19.23
21.62
21.67
24.79
24.18
29.03
8.48
-
17.50
9.10
9.65
1.43
1.87
2.30
2.60
3.37
4.43
4.80
5.43
5.93
6.20
6.77
7.60
-7.93
8.40
9.60
9.90
10.50
10.90
10.97
11.03
13.63
16.27
16.83
18.20
19.53
21.70
4.90
12.27
16.83
-
-
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
_
_
-
-
-
Eight ft. stainless steel column (1/8 in. OD x 0.1 in. ID) packed with 1%
SP-1000 coated on 60/80 mesh Carbopack B preceded by a 1 ft. stainless steel
column [1/8 in. OD x 0.1 in. ID) packed with 1% SP-1000 coated on 60/80 mesh
Chromosorb W. (A glass column (1/4 in. OD x 2 mm ID) may be substituted).
Carrier gas helium at 40 ml/min. Temperature program: 3 min isothermal at
45°C, then 8°/ min to 220°, hold at 220° for 15 minutes.
2
Eight ft. stainless steel column (1/8 in. OD x 0.1 in. ID) packed with 0.2%
Carbowax 1500 coated on 60/80 mesh Carbopack C preceded by a 1 ft. stainless
steel column (1/6 in. OD x 0.1 in ID) packed with 9% Carbowax 1500 coated on
60/80 mesh-Chromosorb W. A glass column (1/4 in. OD x 2 mm ID) may be substituted.
Carrier gas: helium at 40 ml/min. Temperature program: 8 min. isothermal at
6.0°C then 8°/min to 160°, hold at 160 until all compounds elute.
-------
3
This is a minimum level at which the entire system must give recognizable
. mass spectra and acceptable calibration points.
4
Internal Standard.
TABLE 3
DFTPP KEY IONS AND ION ABUNDANCE CRITERIA
MASS ION ABUNDANCE CRITERIA
51 30-60% of mass 198
68 less than 2% of mass 69
70 less than 2% 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 greater than 1% of mass 198
441 less than mass 443
442 greater than 40% of mass 198
443 17-23% of mass 442
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TABLE 4
p-BROMOFLUOROBENZENE KEY IONS AND ION ABUNDANCE CRITERIA
MASS ION ABUNDANCE CRITERIA
50 15-40% of the base peak
75 30-60% of the base peak
95 base peak, 100% relative abundance
96 5-9% of the b,ase peak
173 less than 1%'of the base peak
174 greater than 50% of the base peak
175 5-9% of mass 174
176 greater than 50% of the base peak
177 5-9% of mass 176
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TABLE 5
CHARACTERISTIC IONS OF VOLATILE ORGANICS
COMPOUNDS
El IONS
PRIMARY ION
CHLOROMETHANE-
BROMOMETHANE
VINYL CHLORIDE
CHLOROETHANE
DICHLOROMETHANE
TRICHLOROFLUOROMETHANE
1,1-OICHLOROETHYLENE
1,1-OICHLOROETHANE
TRANS-1,2-DICHLOROETHYLENE
CHLOROFORM
1,2-DICHLOROETHANE
1,1,1-TRICHLOROETHANE
CARBON TETRACHLORIDE
BROMODICHLOROMETHANE
1,2-OICHLOROPROPANE
1,3-OICHLOROPROPENE
TRICHLOROETHYLENE
BENZENE
DIBROMQCHLOROMETHANE
1,1,2-TRICHLOROETHANE
BROMOFORM
1,1,2,2-TETRACHLOROETHANE
TETRACHLOROETHYLENE
TOLUENE
CHLOROBENZENE
ETHYL BENZENE
BROMOCHLOROMETHANE
2-BROMO-l-CHLOROPROPANE
1,4-OICHLOROBUTANE *
50,52 50
94,96 94
62,54 62
64,66 64
49,51; 84,86 84
101,103 101
61,96,98 96
63,65; 83,85; 98,100 63
61,96,98 96
83,85 83
62,64; 98,100 62
97,99; 117,119 97
117,119,121 117
83,85; 127,129 83
63,65; 112,114 63
75,77 75
95,97; 130,132 130
78 78
127,129; 206,208 129
83,85; 97,99; 132,134 97
171,173,175; 250,252; 254,256 173
83,35; 131,133; 166,168 83
129,131; 164,166 164
91,92 91
112,114 112
91,106 91
49,51; 128,130 128
77,79,156 77
55,90,92 55
Internal Standard.
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F J G I! R F J.
PURGE GAS INLET WO ML/MIN)
15 ML SEPTUM SEALED VIAL
2-5 GMS WET SEDIMENT
HEATED SAND (110° C)
1/16" STAINLESS STEEL TUBING
PURGE EFFLUENT TO TENAX/SILICA GEL TRAP
15 ML SEPTUM SEALED CENTRIFUGE TUBE
5 ML REAGENT FREE WATER
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PREPARATION OF SPIKED SEDIMENT SAMPLES FOR ANALYSIS
A pre-selected sediment was heated to 600°C in a muffle furnace to remove any
volatile organic compounds. The muffling also activated the surface of the sediment
to produce a matrix that would bind organics.
Five grams of the sediment were weighed into a 15 ml hypo vial. A solution of
purgeable organics (Table 1) was prepared in water so that 2 ml of this solution
would deliver the desired quantity of each organic. Two ml of water was sufficient
to thoroughly wet the sediment sample without floating it. Five replicates of each
spike are prepared along with 2 unspiked sediment blanks. The samples are sealed
with aluminum seals and teflon-lined silicon septa. After sealing, the spiked
samples were placed in a 5°C refrigerator and equilibrated for 16 hours before
>.
analysis.
The levels of the spikes for the listed compounds were: 2ng; lOng; 20ng; 40ng;
80ng.
The attached table contains nanograms recovery, % recovery and standard deviation
(% recovery) for each compound in the 5 spike levels. Correlation coefficient has
been calculated for each compound over the spiking range.
Conclusions: Recoveries were linear and reproduceable over the concentration
range of 10-80 ng. Quantitative recoveries for amounts lower than lOngs are er-
ratic. Qualitative determinations are possible for some compounds at the 2ng level.
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The average recovery in the linear range was 75-80%.
The Internal Standard, bromochloromethane, is an excellent indicator of potential
trouble caused by excess water vapor carried into the GC/MS that has not condensed
in the reagent free water trap. When recoveries are less than 80%, the analyst
can expect a 20-60% reduction in the recovery of 1,2-dichloroethane, 1,1-dichloro-
ethane, chloroform, 1,1-dichloroethylene and 1,2-trans dichloroethylene. These
compounds elute under the broad chromatographic peak caused by water.
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1
SPIKED COMPOUNDS
"HLOROHETHANE
BROMOMETHANE
INYL CHLORIDE
HLOROETHANE
.ETHYLENE CHLORIDE
i R I CHLOROTR I FLUOROMETHANE
1 ,1-DICHLOROETHYLENE
i,l-DICHLOROETHANE
:RANS 1 ,2-DICHLOROETHYLENE
:HLOROFORM
i ,2-DICHLOROETHANE
1 ,1,1-TRICHLOROETHANE
JARBON TETRACHLORIDE
'.ROMODICHLOROMETHANE
' ,2-DICHLOROPROPANE
1 ,3-DICHLOROPROPENE
RICHLOROETHYLENE
jIBROMOCHLOROMETHANE
ENZENE
1,1,2-TRICHLOROETHANE,
iROMOFORM
,1,2,2-TETRACHLOROETHANE
HRACHLOROETHYLENE
ULUENE
ILOROBENZENE
HYLBENEZENE
INTERNAL STANDARDS
::-OMOCHLOROMETHANE
BROMO-1-CHLOROPROPANE
4-DICHLOROBUTANE
'
* NOT RECOVERED
** IN SCANS V 2. SEC.
2 NG 10 NG 20 NG 40 NQ 80 NG
**
R.T.
43
56
69
78
101 1
133
144
163
178
186
203
J28_
238
252
288
297
315
327
329
331
409
488
505
546
586
651
147
368'
505
.
NG
REC.
*
*
*
*
*
8.9
*
5.0
7.0
7.4
*
12
2.1
1.7
3.2
*
2.4
1.9
3.2
*
2.6
*
*
0.5
1.8
2.3
NOTE 1: EXCESS WATER JflftPOR IJNTERFE
NOTE 2: EXTERNAL CONT^INATIJON >
II 1
%-
REC.
448
250
350
327
602
106
86
161
121
98
162
128
26
89
[Ti2
122
104
83
RENCE
200%
"SD
W
no
18
61
62
47
12
15
_19_
12
25
33
86
18
8.1
10
20
9
25
_ ..__
NG
REC.
8.3
9.7
8.8
6.5
5.6
4.4
6.7
6.7
6.9
7.8
7,5.._
7.4
7.4
6.9
8.4
4.9
8.4
7.3
6.3
7.0
7.5
5.9
7.7
8.9
6.4
6.3
%
REC.
83
97
88
65
56
44
67
67
69
78
75
74
74
69
84
49
84
73
63
70
75
59
77
89
64
63
95
97
92
SD-
(X)
10
7.2
13
14
12
6.3
13
17
2.3
4.8
16 .._
8.9
7.7
10
_6.2. .
9.4
6.9
9.0
17
8.8
14
3.9
5.3
7.3
6.9
3.9
17
8.1
27
f
~N(T"
REC.
23.1
24.8
2
-------
SPIKED COMPOUNDS
CHLOROMETHANE
BROHOMETHANE
VINYL CHLORIDE
CMLOROETHA'NE
METHYLENE CHLORIDE
TR I CHLOROTR I FLUOROMETHANE
1,1-DICHLOROETHYLENE
1.1-DICHLOROETHANE
TRANS 1 ,2-DICHLOROETHYLENE
CHLOROFORM
1 ,2-DICHLOROETHANE
1,1,1-TRICHLOROETHANE
CARBON TETRACHLORIDE
BROMOD I CHLOROMETHANE
1 ,2-DICHLOROPROPANE
1,3-DICHLOROPROPENE
TRICHLOROETHYLENE
DIBROMOCHLOROMETHANE
BENZENE
1,1,2-TRICHLOROETHANE
BROMOFORM
,1,1,2,2-TETRACHLORQETHANE
TETRACHLOROETHYLENE
TOLUENE
CHLOROBENZENE
CTUVI ncwCTrNF
INTERNAL STANDARDS
3ROMOCHLOROMETHANE
2-BROMO-l -CHLOROPROPANE
M-TnaiLOROBUfANE
* NOT RECOVERED
** IN SCANS V 2. SEC.
NOTE 1: EXCESS WATER '
NOTE 2: EXTERNAL CONT/
2 NG '
**
R.T.
43
56
69
78
101
133
144
163
178
186
203
228
238
252
288
297
315
327
329
331
409
488
505
546
586
651
147
368
505
I\POR I
«NATI
NG ;
REC.
*
*
*
*
*
8.9
*
5.0
7.0
7.4
*
12
2.1
1.7
3.2
*
2.4
1.9
3.2
*
2.6
*
*
0.5
1.8
2.3
NTERFE
ON >
%
REC.
448
250
350
327
602
106
86
161
121
98
162
128
26
_89
112
122
104
83
RENCE
200%
SD
(*)
*
110
18
61
62
47
12
15
10
12
25
33
86
18
8.1
1C
20
9
25
m '
REC.
8.3
9.7
8.8
6.5
5.6
4.4
6.7
6.7
6.9
7.8
7.5 _
7.4_
7.4
6.9
8.4
4.9
8.4
7.3 j
6.3
7.0
7.5
5.9
7.7.
8.9
6.4
6.3
10 NG 20 NG 40 NQ 80 NG
' %
REC.
83
97
88
65
56
44
67
67
69
78
75
74
74
69
84
49
84
73
63
70
75
59...
77_ .
89
64
63
95
97
92
SD -
(X)
10
7.2
13
14
12
6.3
13
17
2.3
4.8
16
8.9
7.7
10
6.2
..M.
6.9
9.0
17
8.8
14
3.9
5.3 .
7.3
6.9
3.9
17
8.1
27
-- - -
_.. -.
-
--
~m-
REC.
23.1
24.8
20.4
25.4
15.3
21.3
18.0
17.8
16.7
18.6
17.8
16.9
15.3
16.0
18.3
13.7
16.2
14.2
23
16.4
13.6
15.4
16.5
16.5
15.9
15.8
~
-f-
REC.
116
124
102
127.._
J.L..
106
90
89
83
93
89
84
76
80
92
68
81
71
113
82
68
-77_
83
83
80
79
113
105
100
3D
%
8.1
14
11
13
15
15
6.3
6.5
7.2
5.2
6.5
5.2
8.5
6.4
6.8
3.4
8.6
7
7.6
9.7
10
20
8.5
8.2
6.4
8.2
3.4
2.9
13
. _. .
NG
REC.
51.8
46.5
42.4
37.5
24.4
NOT
32.3
35
NOT
32.5
33.8
31.8
30.9
30.8
32.4
27.1
30.9
29.8
28.6
29.5
28.0
28.7
30.7
25.4
29.2
28.8
._ . ..
't
REC.
132
116
106
94
61
: 2
81.1
87.5
E 1
69
85
79
77
76
81
68 _
77
74
71
74
70
72
77
64
73
72
90
101
102
SD
%
13
8.4
3.8
13
3.9
2.3
2.1
27
2.9
4.4
2.3
7.5
3.3
7.1
5.9
4.2
6.1
7.2
6.2
9.6
3.1
12
3.8
4.6
27
7.1
11
-
- -
NG
REC.
72.7
61.0
59.9
50.8
51.4
82. 8
67.1
56.8
62.2___
62.7
64.5
74.1
BO. 3
74.5
70. 4_
56.6
78.7
59.4
66.0
51.5
52.9
18.1
59.9
51.2
55.5
51.4
%
REC.
91
77
87
76
77
103
84
84
78
77
81
93
01
93
88
71
99
87
83
77
79
60
88
77
81
80
73
74
60
SD
%
13
15
2.4
20
17
37
20
29
32
35
31
1.3
3.3
'24
18 _
21
12
33
10
35
41
33
7.6
8.8
13
8.0
24
18
28
^,=,,
_..
CORR
CO-E
.9659
.9508
.9916
.9725
.9928
.9971
.9988
.9986
.9994
,9985
9990
.9975
.9924
,9960
9984
9996
9935
9968
9831
9992
9980
9917
9978
mi.
9982
9990
___,
LATIO
Fieri
_:'-_:
T:;. v_
11 ''';
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~
,
"' '^'-' '
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------- |