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ENVIRONMENTAL QUALITY CONTROL REPORT
A publication of the Mound Environmental Section
* EPA-NPDES Quality Assurance Program Results for 1988
* DOE Quality Assessment Program Results (1988 - 2nd half)
* Proficiency Environmental Testing Program for the Second Half
of 1988
* Plutonium in Urine Quality Control for 1988
REPORTING PERIOD: July-December, 1988 COORDINATOR: C. T.
Bishop
DATE OF REPORT: REPORT NUMBER: MLM-MU-89-64-0012
April 14, 1989
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DISCLAIMER
Portions of this document may be illegible in electronic image
products. Images are produced from the best available original
document.
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EP..-NPDES QUALITY ASSUR NCE PROGRAM RESULTS FOR 1988
Mound has analyzed the 1988 EPA-NPDES Laboratory Performance
Evaluation samples. These samples are part of a quality control
program for all major permittees in the National Pollutant
Discharge Elimination System CNPDES) . In this programz a private
laboratory under a contract with the EPA, prepares water samples of
known concentrations of trace metals and other miscellaneous
parameters such as oil & grease and Chemical Oxygen Demand ( C
O D ) . Laboratories throughout Ohio and the United States analyze
these samples and report their results to the EPA.
Table 1 summarizes Mound's results. The EPA value is considered
to be the true value and is based on careful weighing of
Constituents. The acceptance limits are a 95% confidence interval
calculated from available performance evaluation data of EPA and
state laboratories. The warning limits are a 95% confidence
interval produced in the same way as the acceptance limits. The
performance evaluation rating of "acceptable" means that the
reported value is within all limits.
Every one of Mound's results w e r e rated acceptable. These
results indicate that Mound is making accurate measurements of
trace metals and other nonradioactive constituents in its liquid
effluents.
DISCLAIMER
This report was prepared as an account of work sponsored by an
agency of the United States Government. Neither the United States
Government nor any agency thereof, nor any of their employees,
makes any warranty, express or implied, or assumes any legal
liability or responsi- bility for the accuraq, completeness, or
usefulness of any information, apparatus, product, or process
disclosed, or represents that its use would not infringe privately
owned rights. Refer- ence herein to any specific commercial
product, process, or service by trade name, trademark,
manufacturer, or otherwise does not necessarily constitute or imply
its endorsement, recom- mendation, or favoring by the United States
Government or any agency thereof. The views and opinions of authors
expressed herein do not necessarily state or reflect those of the
United States Government or any agency thereof.
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<
TABLE 1
1988 MOUND EPA-NPDES QUALITY ASSURANCE PROGRAM RESULTS FOR THE
DETERMINATION OF NON RADIOACTIVE PARAMETERS IN WATER
Cadmium 178 180 158-208 164-202 ACCEPTABLE Chromium 790 832
673-967 709-930 ACCEPTABLE Copper 283 29 1 263-31 9 270-312
ACCEPTABLE Nickel 551 57 1 492-646 51 1-627 ACCEPTABLE
Miscelaneous Parameters
PH 7.53 7.5 7.28-7.66 7.33-7.61 ACCEPTABLE
Total Suspended 62.8 56.3 44.9-67.7 47.7-64.9 ACCEPTABLE
Solids(mg/L )
Oil and Grease 13.9 14.0 6.52-1 8.7 8.04-1 7.2 ACCEPTABLE < m
g / L 1
Total Cyanide 0.456 0.46 0.308-0.587 0.343-0.552 ACCEPTABLE ( m
g / L > Total Residual 3.5 4.14 2.97-4.88 3.22-4.63 ACCEPTABLE
Chlorine(mg/L 1
Demands in Milligrams per Liter
COD 24 25 13.7-34.4 16.3-31 .8 ACCEPTABLE 5-Day BOD 15.4 16
7.54-24.4 9.63-22.3 ACCEPTABLE
(a) Standard deviations (precision) of Mound's Values are
generally 102 or less: for BOD, the standard deviation is closer to
+/- 30%
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DOE QUALITY ASSESSMENT PROGRAM RESULTS
Mound's analytical results from the "1988 - Second Half"
Environmental Measurements laboratory (EM11 Quality Assesment
Program are given here. In this Department of Energy Program,
laboratories from throughout the DOE complex analyze EML
"environmental" samples and report their results, which are then
compared to EML's reference concentrations. Table 2 on the next
page gives Mound's results for the September 1988 s-amples, and
compares them to the EM1 reference concentrations. The data in this
table are taken from the DOE report EML-518 entitled "Semi-Annual
Department of Energy Quality Assessment Program Report", by C. G.
Sanderson and M. S. Feiner, dated January 2, 1989.
Looking at the ratio of the Mound concentration to EM1
concentration ratio in the column on the far right of Table 2, it
can be seen that all but one of the ratios indicates an agreement
of 25% or better between Mound's measured concentration and the
reference EML value. Mound's measured plutonium in vegetation
concentration was higher than the EM1 value by about 80%. The
reason for Mound's discrepancy could not be determined. However,
from the statistical summary of th data from all laboratories that
analyzed this sample, it could be seen that about one out of four
laboratories was off by more than 50%. The generally good agreement
of Mound's results to the standard EM1 values indicate that Mound
is performing quality analytical work in the measurement of
radionuclides in environmental samples.
PROFICIENCY ENVIRONMENTAL TESTING PROGRAM FOR THE SECOND HALF OF
1988
Mound is continuing to participate in a "Proficiency
Environmental Testing Program", the purpose of which is to evaluate
the ability of a laboratory to measure non-radioactive constituents
in water. The program is being administered by Analytical Products
Group, Inc. (APG). A total of about 50 laboratories participate in
each study.
Summaries of the results from the July and October 1988 studies
are given in Tablea 3 and 4. A complete description of the results
is given in the reports prepared by Analytical Products Croup dated
July and October 1988. It can be seen from the data in Tables 3 and
4 that the Mound concentrations agree well with the reference
concentrations. For 90% of the results, the number of standard
deviations from the mean waa less than 1.0. Only in one
measurement, one of the chemical oxygen demands ( C O D ) , was the
number of standard deviations from the mean greater than 2.0.
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TABLE 2
MOUND DOE QUALITY ASSESMENT PROGRAM RESULTS RADIONUCLIDES IN
ENVIRONMENTAL SAMPLES
( SEPTEMBER 1988 SAMPLES 1
U-234
W-238
Soil cs-I 37
Pu-239
Vege- Pu-239 tation
U-234
U-238
Water H-3
Pu-239
U-234
U-238
( a > All samples
Mound Concentration
EM1 Reference Concentration
Ratio Mound Conc.
0.403 +/- 7 X
0.038 +/-I5 96
0.023 +/-43 X
0.019 +/-42 %
10.1 +/- 1 x 0.0049 +/- 4 X
0.0038 +/- 2 %
0.0038 +/- 2 X
were labeled 8809
pCi/(g or mL)d ---_--_--------- I .09 +/- 6 X
2.4 +/- 3 %
2.39 +/- 3 X
0.91 +/- 5 A
0.38 +/- 2 %
0.021 +/- 9 %
0.023 +/= 8 X
0.018 +/- 5 2
10.6 +/- 4 X
0.0054 +/= 8 X
0.0041 +/- 4 %
0.0042 +/- 4 %
to EM1 Conc. ------------- 0.88 +/-0.08
0 .81 +/-0.06
0.76 +/-0.07
1.10 +/-0.12
1.06 +/'-0.08
1.81 +/-0.32
1 .oo +/-0.44
1 - 0 4 +/-0.45
0.95 +/-0.04
0.91 +/-0.08
0.93 +/-0.04
0.90 +/-0.04
( b ) Units are pCi/sample for air filters, pCi/mL for water
and
( c > The Mound error is the two sigma error based on
counting
(d) The EML error is the standard error of the mean.
pCi/g for soil and vegetation.
statistics or based on replicate analyses.
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TABLE 3
PROFICIENCY ENVIRONMENTAL TESTING RESULTS NONRADIOACTIVE
PARAMETERS, ANALYTICAL PRODUCTS GROUP, INC.
JULY 1988 REPORT
CONC. MOUND REF. STD. STD. DEVS. LEVEL CONC. CONC. MEAN DEV.
FROM MEAN ---__- ------ ------ _---_-- ---I-- ---------
BOD ( m g / L )
#I #2
128 125 47 43.1
130 28 41 - 2 7.2
0.1 0.8
COD ( m g / L >
196 80
201 69.3
190 67.1
17 8.7
0.4 1.5
Tot. S. S. (a) #1 ( m g / L > #2
50 305
52.4 31 3
0.1 0 . 2
Oil ,Grease (mg/L >
#I #2
8.1 26.8
8.57 28.5
8.4 25.1
3.3 4.6
0.1 0.4
PH (pH units)
#I w2
5.53 5.73 4.25 6.51
5.42 0.28 4.29 0.24
0.3 0 . 2
Cadmium < ug/L 1 Chromium ( ug/L >
59 184
44 181
59.5 186
51 184
59.1 187
52.9 184
4.4 12
0.1 0.3
1.7 0.2
6.4 20
Copper (ug/L >
#I #2
38 147
34 143
38 143
5.5 12
0.1 0.3
Nickel ( ug/L
75 70.6 160 146
71.4 11.3 150 18
0 . 3 0.4
Cyanide (mg/L
#I #2
0.89 0.90 2.50 2.45
0.9 0.27 2.51 0.39
0.1 0.1
Tot. res. C1 ( m g / L )
#I #2
0.64 2.4
0.77 0.74 0.12 2.82 2.49 0.54
0 . 8 0.2
( a > Suspended solids (b) Each laboratory receives its own
individual sample,
thus no data is provided here.
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TABLE 4
PROFICIENCY ENVIRONMENTAL TESTING RESULTS NONRADIOACTIVE
PARAMETERS, ANALYTICAL PRODUCTS GROUP, INC.
OCTOBER 1988 REPORT
PARAMETER CONC. MOUND REF. STD. STD. DEVS. (Units) LEVEL CONC.
CONC. MEAN DEV. FROM MEAN
BOD ( m g / L )
COD
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PLUTONIUM IN URINE QUALITY CONTROL FOR 1988
During 1988, quality control efforts in evaluating the
measurement of plutonium-238 in urine continued. In order to
evaluate accuracy and precision, 25 reference samples prepared
using National Bureau of Standards traceable plutonium-238, were
prepared and analyzed. Forty nine blanks were measured to evaluate
the lower detection limits.
The precisian is calculated from duplicate reference samples
containing a known amount of Pu-238. Using a series of reference
samples in the concentration range of 0.040 to 1.51 pCi/L with an
average of 0.102 pCi/L, an estimated relative standard deviation of
1 1 % was obtained from 1988 data. The estimated relative standard
deviations in 1986 and 1987 were also 11%. The proposed ANSI
standard requires a precision of 40% or better.
Accuracy is evaluated by calculating the ratio of the measured
plutonium concentration of the analyzed reference sample, to the
"true" value. This ratio averaged 0.912 in 1988, indicating an
average bias of only -9% compared to the 1986 and 1987 values of
+2% and +I316 respectively. The proposed ANSI standard acceptable
relative bias limits are -25% and + 5 0 X , when the plutonium
concentration is ten times the acceptable minimum detectable
activity of 0.06 pCi. For the individual samples, more than 90% of
the results were within 20% of the reference value. The few that
showed a deviatition of more than 20% from the reference values had
concentrations near the acceptable minimum detectable activity of
0.06 pCi.
Lower detection limits (LDLs) were calculated by taking 4.65
times the standard deviation of blanks that were determined weekly.
The LDL for Pu-238 based on 49 blanks for 1988 was calculated to be
0.017 pCi. This compares with LDLs of 0.022 and 0.026 pCi
calculated for 1987 and 1984 respectively. For Pu-239, an LDL of
0.010 pCi was calculated: in 1987 the LDL was 0.011 pCi, in 1986 it
was 0.015 pCi. These values are less than the acceptable lower
detection-limit of 0.06 pCi/L recommended by the Health Physics
Society in their "Draft Performance Criteria for Radiobioassay",
ANSI N13.30, November 1 985.
Lotus spreadsheets have been set up so that reference sample
analyses and blank data can be entered as it is collected.
Accuracy, precision, and lower detection limits for the
determination of plutonium in urine are calculated from data
presently in the spreadsheet. The spreadsheet showing accuracy and
precision of the spiked plutonium-238 samples for 1988 is given in
Table 5.
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TABLE 5
QUALITY CONTROL - ACCURACY AND PRECISION HOUND ENVIRONMENTAL
SECTION DATA (QCPUUR88>
Measured quantity: Plutonium-238 in Urine Starting date: January
, 1988 ACCURACY -8.8 % Ending date: November, 1 988 PREC I S I ON
10.8 X Comments : Measured and reference values are in units of
pCi/L
STANDARD DEVIATION FROM DUPLICATE DETERMINATIONS
Pairs of Duplicates = 12 Average of all values = 0.102087
Standard Deviation = 0.011048 70 Standard Deviation = 10.8
DATE
2/25/88 2/25/88 4/13/88 4/ 1 3/88 5/31 /88 5/31 /88 8/4/88
8/4/88 8/18/88 8/18/88 1 1 /21/88 1 1 /21/88
XI
0.043 0.068 0.106 0 . 0 5 2 0.159
0.0595 0.11 0.206 0.153 0.092 0.052 0.16
x2
0.04 0.056 0.102 0.048 0.173
0.0234 0.091 0.211 0,157 0.072 0.049 0.147
ACCURACY DETERMINATION FROM STANDARDS ANALYSIS
No.of Stds. Analyzed = Accuracy (Bias) in % =
DATE ( XI 0x2 5̂ 2
0.000009 0,0001 44 0.00001 6 0.0OOOl6 0.0001 96 0.001 288
0.000361 0.000025 0.00001 6
0.0004
0.0001 69 0 000289
2/25/88 2/25/88 2/25/88 2/25/88 4/13/88 4/13/88 4/13/88 4/13/88
5/31 /88 5/31 /88 5/31 /88 5/31 /88 8/4/88 8/4/88 8/4/88 8/4/88
8/18/88 8/18/88 8/18/88 8/18/88 I 1 121 /88 1 1 /21/88 1 1 121 188
1 1 /21/88 1 1 121 /88
Meas. Value
0.043 0.04
0 I 068 0.056 0.104 0.102 0.052 0.048 0.159 0.173 0.0595 0.0236
0.1 1 0.091 0.206 0.211 0.153 0.157 0.092 0.072 0.053 0.069
0.16
0.147 1.51
25 -8.8
R e f . Ratio Value Meas/Ref
0.049 0.877551 0.049 0.816326 0.066 1 .0303O3 0.066 0.848484
0.098 1 04081 6 0.054 0.962942 0.054 0.888888 0.. 167 0.952095
0.167 1 .035928 0.062 0.959677 0.042 0.380645 0.114 0.964912 0.114
0.798245 0.221 0.932126 0.221 0.954751 0.163 0.938450 0.163
0.963190 0.108 0.851851 0.1 08 0.666466 0.064 0 -8281 25 0.064 1
-0781 25 0. 'I 54 1 .038961 0.154 0.954545 1 .58 0.955696
0 098 1 . OS1 632
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DISTRIBUTION
D. T. ABBOTT C . T. BISHOP ( 5 ) R. K. BLAWVELT D. C. CARFACNO
J. 1. CLARK R. R. DAILY D. G. DRAPER D . A. EDLINC B. M. FARMER C.
S. FRIEDMAN W. D . CLOEKLER L. C. HOPKINS C. W. HUNTINGTON R. J.
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TOMLINSON M. K. WINEGARDNER DOCUMENT CONTROL ( 3 )
B D - 9 1 E-1 50 B D - 9 1 E-1 50 A - 2 2 1 A BD-91 B D - 1 0 2
A-272 BD-91 E-1 50 E-1 50 E-1 50 A - I 33 BD-91 h-111 T-223 A-270
H-I 1 1 B D - 9 1 A - 2 7 2 E - 1 5 0 E - 1 0 7 B D - 9 1 A-1 90
T-300B A-2 1