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

DISCLAIMER

Portions of this document may be illegible in electronic image products. Images are produced from the best available original document.

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.

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.

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

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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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. JANOWIECKI J. Y. JARVIS P. H. JENKINS R. A. NEFF C. A . PHILLIPS B. ROBINSON W. D. ROSS L. 1. ROUSH W. E. SHEEHAN H. E. SPITZ F. K. TOMLINSON M. K. WINEGARDNER DOCUMENT CONTROL ( 3 )

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