EPA-680/4-75-007 JUNE 1975 Environmental Monitoring Series PRELIMINARY MILK REPORT NATIONAL ENVIRONMENTAL RESEARCH CENTER OFFICE OF RESEARCH AND DEVELOPMENT U.S. ENVIRONMENTAL PROTECTION AGENCY LAS VEGAS, NEVADA 89114 ------- RESEARCH REPORTING SERIES Research reports of the Office of Research and Develop- ment, U. S. Environmental Protection Agency, have been grouped into five series. These five broad categories were established to facilitate further development and application of environmental technology. Elimination of traditional grouping was consciously planned to foster technology transfer and a maximum interface in related fields. The five series are: 1. Environmental Health Effects Research 2. Environmental Protection Technology 3. Ecological Research 4. Environmental Monitoring 5. Socioeconomic Environmental Studies This report has been assigned to the ENVIRONMENTAL MONI- TORING series. This series describes research conducted to develop new or improved methods and instrumentation for the identification and quantification of environ- mental pollutants at the lowest conceivable significant concentrations. It also includes studies to determine the ambient concentrations of pollutants in the environ- ment and/or the variance of pollutants as a function of time or meteorological factors. EPA REVIEW NOTICE This report has been reviewed by the National Environ- mental Research Center-Las Vegas, EPA, and approved for publication. Approval does not signify that the contents necessarily reflect the views and policies of the U.S. Environmental Protection Agency, nor does mention of trade names or commercial products constitute endorse- ment or recommendation of use. Document is available to the public for sale through the National Technical Information Service, Springfield, Virginia 22161. ------- EPA-680/4-75-007 June 1975 PRELIMINARY MILK REPORT by Arthur N. Jarvis and David G. Easterly Quality Assurance Branch Technical Support Laboratory National Environmental Research Center Las Vegas, Nevada ROAP 21BEK/22AAJ Program Element 1HA327 NATIONAL ENVIRONMENTAL RESEARCH CENTER OFFICE OF RESEARCH AND DEVELOPMENT U.S. ENVIRONMENTAL PROTECTION AGENCY LAS VEGAS, NEVADA 89114 ------- ABSTRACT A summary of the results of the milk cross-check program from July 1973 through November 1974 is given. These data indicate a need for improvement in the laboratory analysis of both beta and gamma- emitting radionuclides in milk, Also, the expected relationship, i.e., with increasing sample activity the accuracy of the analysis should improve, was not seen with any consistency at the levels of activity used in these studies. Accurate analysis of strontium-89 was particu- larly difficult for most laboratories to achieve, while the accurate analysis of cesium-137 was the least difficult. These results exemplify the need for improvement in analytical procedures through the adoption of standard reference methods, more frequent calibration and maintenance of counting instruments, improved quality control practices within each laboratory, and greater partici- pation in laboratory intercomparison studies conducted by the National Bureau of Standards, the Energy Research and Development Administration, and the U.S. Environmental Protection Agency. iii ------- CONTENTS Page Abstract • H* List of Tables and Figures v Introduction * Methods and Procedures 2 Results and Discussion 3 Summary 6 References 31 APPENDIX. Statistical Calculations 32 1v ------- TABLES Number Page 1 Summary of Cross-Check Programs ... 8 2 Summary of Milk Analysis Data, July 1973 to November 1974 9 3 Limits Established by the Analytical Quality Control Service 12 4 Results of Milk Cross-Check Analyses, July 1973 to November 1974 12 FIGURES Number Page 1 Sample Analysis and Report of Participant's Data .... 13 2 Control Chart 15 3-A Histogram of Monthly Analysis for Strontium-89 17 3-B Histogram of Monthly Analysis for Stront1um-90 20 3-C Histogram of Monthly Analysis for Sarium-140 23 3-D Histogram of Monthly Analysis for Iodine-131 25 3-E Histogram of Monthly Analysis for Cesium-137 28 ------- PRELIMINARY MILK REPORT INTRODUCTION Environmental radiation measurements are made daily by federal, state, local, and private agencies. The data obtained from these measurements are utilized by the U.S. Environmental Protection Agency (EPA) and other agencies for such purposes as estimating dose and health effects, establishing standards and guides, and conducting regulatory activities. It is therefore imperative that the precision and accuracy of the data be assured so that policy decisions concerning environmental quality are based on valid and comparable data. The present radiation quality assurance program of the EPA is designed to encourage the development and implementation of quality control procedures at all levels of sample collection, analysis, data processing, and reporting. As an integral part of the EPA's program, the Quality Assurance Branch of the National Environmental Research Center-Las Vegas (NERC-LV) distributes calibrated radionuclide solutions for instrument calibration and chemical yield determinations, and con- ducts a number of laboratory performance studies involving the analysis of radionuclides in environmental media. The intercomparison studies program enables participating labora- tories to maintain checks on their analyses and assists them in docu- menting the validity of their data. In addition, this program enables the EPA to obtain an overall estimate of the precision and accuracy of environmental radiation measurements, or more precisely the precision and accuracy of laboratory radioassay procedures of environmental samples. ------- Studies currently in progress involve samples of most environmental media and include milk, air, water, soil, diet, urine, and noble gases. Table 1 is a summary of the cross-check programs. Participants include nuclear facilities or their contractors, state, federal, and inter- national laboratories. The number of participants has increased steadily during the past two years. Because of the large number of participants and the continuing nature of the programs, sufficient data are generated to enable valid periodic statistical assessment of the quality of environmental data. Laboratories perform the analyses and return their data to the Quality Assurance Branch for statistical analysis. Comparisons are made between laboratories and within an individual laboratory for accuracy and precision. A computer report and a periodically updated performance chart are returned to each participant. This enables each laboratory to document the precision and accuracy of its radiation data, to identify instrumental and procedural problems, and to compare performance with other laboratories. METHODS AND PROCEDURES Through December 1973, reconstituted powdered milk was used in the milk cross-check program. Two modifications were made to the program beginning 1n 1974: (1) fresh, whole, pasteurized, homogenized milk was used in preparing the samples, and (2) sample distribution was changed from monthly to a bimonthly basis. The milk was prepared for distribution by thoroughly mixing with 10 ml/gallon of formalin and 3.79 ml/gallon of antifoaming agent (Dow Corning Antifoam,R FG-10 Emulsion, Food Grade). Three aliquots were gamma counted for background determination. The remaining milk was "spiked" using calibrated solutions of the radionuclides. The milk was again thoroughly mixed and three aliquots taken for gamma analysis. If these results Indicated homogeneity, the milk was packaged for ------- shipment. A 4-liter sample containing strontium-89, strontium-90, cesium-137, iodine-131, and barium-140 was distributed to each of approximately 35 participating laboratories. Each participating laboratory made three independent determinations for each radionuclide included in the particular cross-check sample and reported its results to the Quality Assurance Branch. Control limits (sigma limits) previously established by the Analytical Quality Control Service in Winchester, Massachusetts, were used in analyzing the quality of the results obtained by these laboratories (1,2). These limits were based on the purpose for which the data were being obtained and on reasonable laboratory ability. Upon receipt of the reports from all participating laboratories, the data were transferred to punch cards and analyzed using a CDC 6400 computer. This analysis included determi- nation of the experimental average and standard deviation of the sample, the normalized range, standard error normalized deviation, experimental sigma, and the grand average of all laboratories for each radionuclide. Examples of sample calculations to illustrate the computations per- formed by the computer are shown in the appendix. A report was generated containing the data reported by all par- ticipating laboratories, listed according to their identity code, along with the results of the data analysis. Examples are shown in Figure 1. In addition, a control chart was generated for each radionuclide in- cluded in the sample (Figure 2). The control charts are updated each time a laboratory participates in a cross-check study, thus giving each laboratory a continuous record of its performance. A copy of the computer printout and a control chart for each radio- nuclide is mailed to each participant approximately two weeks following the report due date. RESULTS AND DISCUSSION A summary of the results of the milk analysis data is shown in Table 2. All participants received samples containing strontium-89, 3 ------- strontium-90, cesium-137, iodine-131, and barium-140; however, all did not submit results for each analysis. This resulted in a different number, N, being reported for the various radionuclides. A comparison may be made between the experimental standard devia- tion, s, calculated from the data supplied by the participating labora- tories (Table 2) and the standard deviation, a, expected for various analyses listed in Table 3. For the purpose of comparison, the experimental [(s/known)100] and expected [(a/known)100] standard deviations, expressed as a percent of the known values, are shown for each month in Table 2. The experimental standard deviation divided by the known value (s/p) indicates no im- provement in the analytical results when whole milk was used instead of powdered. Figure 3-A shows the results in the form of a histogram for the strontium-89 analysis by month.* The February results were the poorest over the period for which strontium-89 data were analyzed. When com- paring the grand average (X) to the known value (u), a negative bias was observed for all monthly samples except February. No explanation for either the negative bias or the poor analytical performance by the participating laboratories is readily apparent. It is now necessary to determine if this is due to the analytical method(s) being used and if so if a different method of analysis or modification of the existing method(s) is warranted. The monthly results of the strontium-90 analysis are shown in Figure 3-B. On an average the (s/y) values were lower and the devia- tions from y were less than for strontium-89 analysis. Even though the results show some inconsistency from month to month, in general they may be viewed with some optimism since data for at least one * For all data used in this report, Chauvenet's criterion was used as the basis for acceptance or rejection of the X value of each laboratory. ------- month are sufficiently accurate to indicate good results are attainable. More frequent calibration and maintenance of counting instruments, im- proved quality control practices within the laboratories, and greater participation in laboratory intercomparison studies may be beneficial for some of the laboratories having analytical difficulties. The monthly results of the barium-140 analysis are shown in Figure 3-C. Because of the manufacturer's production schedules and the half- life of barium-140, some monthly cross-check samples did not contain this isotope. Unlike strontium-89 and 90, generally no "wet" chemistry is involved in the barium-140 analysis. Most analysts determine the gamma emitters by gamma spectroscopy. This would indicate errors arise from improper, infrequent, or erroneous calibration; faulty or inade- quate instrumentation; or erroneous processing and interpretation of data. Participants obtaining inaccurate results for their barium analysis should restandardize and calibrate their instruments more frequently using the same geometry as that used for sample counting. It appears from this limited amount of data that the barium-140 results are better in terms of accuracy and (s/y) than the strontium analysis. The monthly results of the iodine-131 analysis are shown in Figure 3-D. These results are as good as the barium-140 results in terms of a small deviation from y, and are better than the barium-140 results in terms of s/y. With proper calibration and interpretation, accurate results appear readily attainable. During the six-month period where reconstituted powdered milk was used, the results were relatively good, with two of the six analyses having an experimental sigma value of less than 10 pCi/liter. Results were the best for the September sample. The monthly results of the cesium-137 analysis are shown in Figure 3-E. These results are considerably better in terms of the ratio s/y than those for any of the other radionuclides used in the milk cross- check program. The reason for the better results with cesium may be partially attributed to the fact that many participants standardize their instruments with a cesium-137 source. The cesium-137 peak area ------- may also be somewhat easier defined than the iodine-131 and barium-140 peaks. Even better results for cesium-137 analysis could be attained if improvement was made by a few of the participants, This may best be accomplished through consultation with the laboratories having the analytical problem. Table 3 gives the limits previously established by the Analytical Quality Control Service (1,2). During the period July 1973 to November 1974, with few exceptions, results from the milk cross-check program did not approach these established limits. Examination of these results reveals that 29% of the participants were within the plus or minus 3 sigma control limits for the strontium-89 analysis, 42% for the strontium-90, 52% for barium-140, 60% for iodine-131, and 77% for cesium-137 (Table 4). SUWARY Data compiled for the milk cross-check program from July 1973 to November 1974 indicate the need for improvement in analytical procedures for all radionuclides studied. Accurate analysis of strontium-89 was particularly difficult for most laboratories to achieve, while the accurate analysis of cesium-137 was the least difficult. It is hoped that results similar to those obtained for cesium-137 can be accomplished for analysis of the other radionuclides. The data, although generally having relatively large measures of random devia- tions, indicate this may be possible for all except strontium-89. There was at least one month where the experimental sigma approached the established limits for all radionuclides except strontium-89. In September 1973 the cesium-137 experimental sigma was less than the established limits. These data would indicate the laboratories can achieve good accuracy for most of the samples being analyzed. Two things are apparent from these data. The expected relation- ship, i.e., the accuracy of the analysis should improve with increas- ing sample activity, was not seen with any consistency at the levels ------- of activity used in the studies (Table 2). There is a need for con- siderable improvement in the laboratory analysis of both beta and gamma- emitting radionuclides in milk. One reason for the variability in the results may be due to the expansion of the milk cross-check program to include new participants. The number of participants more than doubled during the first half of 1973. As these laboratories become more familiar with the analysis, hopefully the accuracy of the results will improve. For strontium-89, and possibly strontium-90, it appears that new methods of analysis should be evaluated since less than a third of the participating labora- tories are doing a satisfactory job of strontium-89 analysis and less than half for strontium-90. If data over the next several months indi- cate that the present limits are unrealistic for some radionuclides and cannot be attained by the majority of participants, then the limits should be made more realistic. Available information does indicate good internal precision for most laboratories, but poor accuracy in many cases. This exemplifies the need for improvement in analytical procedures through the adoption of standard reference methods and protocols for establishing equivalency to the reference method, more frequent calibration and maintenance of counting instruments, improved quality control practices within each laboratory, and greater partici- pation in laboratory intercomparison studies conducted by the National Bureau of Standards, the Energy Research and Development Administration, and the Environmental Protection Agency. ------- Table 1. SUMMARY OF CROSS-CHECK PROGRAMS* SAMPLE Milk Water Gross a, 6* Gamma 3H 239pu* 226Ra Air Gross a, 0* 239pu* Soil* Diet Urine Gas ANALYSIS 89Sr, 9<>Sr> 131If 137Cs, '""Ba, K Gross o, B 60Co, 106Ru, 134Cs, 137Cs. 51Cr. 65Zn 3H 239pu 226Ra a.' B» Y 239Pu 239pu 89Sr, 9°Sr, 1311, 137Cs. li.OBa. K 3H 85Kr ACTIVITY PER ISOTOPE < 200 pCi/1 < 100 pCi/1 < 500 pCi/1 < 3500 pCi/1 < 10 pCi/1 < 20 pCi/1 < 200 pCi /sample < 2 pCi/sample < 50 pCi /sample < 200 pCi/kg < 3500 pCi/1 < 20 pCi/ml QUANTITY SUPPLIED ^ 4 liters ^ 4 liters ^ 4 liters •v 60 ml ^ 4 liters \> 4 1 i ters 3 - 2" or 4" diam. air filters 3 - 2" or 4" diam. air filters -b 100 g 3 - 4-liter samples •v 60 ml 10 liters PRESERVATIVE Formalin 0.5 N HN03 0.5 N HN03 none 0.5 N HN03 0.5 N HN03 none none none Formalin Formalin none DISTRIBUTION Bimonthly Bimonthly Bimonthly Bimonthly Semiannual ly Quarterly Quarterly Quarterly Semi annually Quarterly Quarterly Semiannual ly TIME FOR ANALYSIS & REPORT 6 weeks 4 weeks 4 weeks 4 weeks 8 weeks 6 weeks 4 weeks 6 weeks 8 weeks 8 weeks 4 weeks 8 weeks 00 * Laboratories are required to have the necessary licenses before receiving these samples. ------- Table 2. SUMMARY OF MILK ANALYSIS DATA, JULY 1973 TO NOVEMBER 1974 \0 Oul'73 Aug'73 Sep'73 Oct'73 Nov'73 Dec '73 Feb'74 Apr'74 Jul'74 Sep'74 Nov'74 Strontlum-89 Known pCi /liter 1 a limit pCi /liter 1 a/known % N X pCi/liter s pCi /liter s/known % 98 5 5.1 17 87.2 11.0 11.2 96 5 5.2 14 61.5 29.6 30.8 85 5 5.9 13 76.9 12.3 14.5 133 7 5.3 19 112.3 25.4 19.1 123 6 4.9 16 98.3 24.9 20.2 89 5 5.6 18 69.5 30.8 34.6 83 5 6.0 23 92.6 44.0 53.0 204 10 4.9 28 171.9 36.7 18.0 151 8 5.3 26 128.1 27.6 18.3 157 7.9 5.0 23 137.8 25.7 16.4 172 8.6 5.0 30 137.3 39.1 22.7 Strontium-90 Known pCi/liter 1 o limit pCi/liter 1 o/known % N 55 pCi/liter s pCi /liter s/known % 65 3 4.6 23 64.0 8.3 12.8 158 8 5.1 17 130.4 44.5 28.2 72 4 5.6 16 67.6 6.4 8.9 119 6 5.0 23 106.1 19.9 16.7 135 7 5.2 22 115.2 26.9 19.9 103 5 4.9 22 93.1 16.4 15.9 198 10 5.1 21 182.7 20.0 10.1 172 9 5.2 31 169.9 22.9 13.3 152 8 5.3 29 152.7 28.8 18.9 124 6.2 5.0 28 124.1 15.6 12.6 102 5.1 5.0 33 94.1 15.2 14.9 ------- Table 2 (continued). SUMMARY OF MILK ANALYSIS DATA, JULY 1973 TO NOVEMBER 1974 Jul'73 Aug'73 Sep'73 Oct'73 Nov'73 Dec' 73 Feb'74 Apr' 74 Jul'74 Sep'74 Nov'74 Barium- 140 Known pCi/ liter 1 a limit pCi/liter 1 a/known % N X pCi/liter s pCi/liter s/known % 148 7 4.7 27- 152.6 11.0 7.4 152 8 5.3 21 158.4 24.9 16.4 146 7 4.8 22 145.3 27.9 19.1 104 5 4.8 32 107.4 19.2 18.5 0 0 159 8 5.0 35 159.3 11.9 7.5 0 0 193 9.6 5.0 33 195.2 21.9 11.3 0 Iodine- 131 Known pCi/liter 1 a limit pCi/Hter 1 a/known % N X pC1/liter s pCi/liter s/known % 115 6 5.2 33 125.1 18.3 15.9 144 7 4.9 22 147.8 13.7 9.5 123 6 4.9 22 121.3 8.8 7.2 493 25 5.1 34 486.3 28.2 5.7 104 5 4.8 26 99.7 11.0 10.6 177 9 5.1 25 175.8 9.6 5.4 150 8 5.3 40 149.9 27.7 18.5 150 8 5.3 41 154.6 20.7 13.8 142 7 4.9 35 145.8 15.9 11.2 188 9.4 5.0 31 192.2 20.4 10.9 126 6.3 5.0 36 122.4 10.5 8.3 ------- Table 2 (continued). SUMMARY OF MILK ANALYSIS DATA, JULY 1973 TO NOVEMBER 1974 Jul'73 Aug'73 Sep'73 Oct'73 Nov'73 Dec '73 Feb'74 Apr'74 Jul'74 Sep'74 Nov'74 Cesium- 137 Known pCi/liter 1 o limit pCi/liter 1 o/known % N X pCi/Hter s pCi/liter s/ known % 116 6 5.2 34 116.5 6.6 5.7 122 6 4.9 22 120.1 7.7 6.3 84 5 6.0 22 81.6 3.9 4.6 91 5 5.5 35 88.7 8.5 9.3 126 7 5.6 28 123.1 9.3 7.4 101 5 5.0 30 100.1 9.4 9.3 214 11 5.1 38 208.9 12.7 5.9 174 9 5.2 42 171.1 16.1 9.3 155 8 5.2 37 157.3 10.0 6.5 126 6.3 5.0 35 132.2 7.6 6.0 101 5.1 5.0 38 102.8 5.6 5.5 ------- Table 3. LIMITS ESTABLISHED BY THE ANALYTICAL QUALITY CONTROL SERVICE Radionucl ide 131J 137 Cs '""Ba 89Sr 90 Sr la Limits for Single Determination For Levels <100 pCi/1 iter (pCi /liter) 5 5 5 5 For Levels <30 pCi /liter 1.5 For Levels >100 pCi/liter (X) 5 5 5 5 - For Level s >30 pCi/1 iter (*) 1.5 Table 4. RESULTS OF MILK CROSS-CHECK ANALYSES, JULY 1973 TO NOVEMBER 1974 Radionucl ide a Limits <1 <2 <3 >3 89Sr 90Sr llt0Ba 131J 137Cs Laboratories Within a Limits (%) 11.2 20.7 28.5 71.5 19.4 31.6 42.4 57.6 25.3 42.9 52.0 48.0 29.7 49.9 59.7 40.3 39.0 63.1 76.7 23.3 12 ------- NERC-LV RADIONUCLIDES IN MILK CROSS-CHECK PROGRAM — JUNE 1975 6/15/75 SAMPLE - A 137CS KNOWN VALUE = 101 PCI/L EXPECTED LABORATORY PRECISION (IS, 1 DETERMINATION) = 5.1 PCI/L EXPERIMENTAL RNG ANLY NORMALIZED DEVIATION LAB RESULT SIGMA (R + SR) AVERAGE (GRAND AVG) (KNOWN) D 98 D 102 D 102 2.3 .46 101 -.7 -.1 P NO DATA PROVIDED Q 104 Q 104 Q 108 2.3 .46 105 .9 1.5 R 95 R 99 R 93 3.1 .69 96 -2.4 -1.8 S 108 S 105 S 106 1.5 .35 106 1.2 1.8 V 96 V 110 V 98 7.6 2.18 101 -.5 .1 EXPERIMENTAL SIGMA (ALL LABS) = 7 GRAND AVERAGE = 103 * - NOT USED FOR CALCULATING GRAND AVERAGE ** - INSUFFICIENT INFORMATION TO CALCULATE Figure 1. Sample Analysis and Report of Participant's Data 13 ------- Explanation of terms in Figure 1: Title: Column 1: Colume 2: Column 3: Columns 4 and 5: Column 6: Column 7: Column 8: Bottom of Chart: Program name, sample collection date, sample code letter, analysis type, known concentrations of radio- nuclide, expected standard deviation of analysis - single determination. Laboratory identification code (A, B, C, etc.). Laboratory results (0-25 results listed down column). Is (standard deviation) of the experimental results. Normalized range value in "mean range + standard error of the range" (R + aR units for comparability. (See Statistical Techniques for Quality Control of Environ- mental Badioaasay, AQCS Report Stat-1. November 1964, pages 4-8.) (Sp = c^ for printing purposes.) Average value. Normalized deviation from the grand average value of all laboratories expressed in a^ units. Normalized deviation from the known value expressed in cfy units. Is experimental error of all laboratories, and the grand average of all laboratories. 14 ------- RADIONUCLIDES IN MILK CROSSCHECK PROGRAM LAB - D 137CS NORMALIZED DEVIATION FROM KNOWN 1973 1974 1U 9 8 7 6 5 4 3 s 2 ' 1 ® o M A -1 -2 -3 -4 -5 -6 -7 -8 -9 _m . L* r-f i A FA f\ ;^ V^ / L_j A/ * >»-^ — J^v ^" X N^^x^ w CL WL WL CL NORMALIZED RANGE 1973 1974 R +5 R +2 R +1 R +0 O . J F M A M J I J A _J 1 .1 . 1 • SONDJ FMAHJJASUND CL WL Figure 2. Control Chart 15 ------- Explanation of terms used in the control chart (Figure 2). Title: Name of program, laboratory code letter, and type of analysis. Upper Graph: "Normalized deviation from known versus the month of analysis." [The 95.0% (y ± 2 M) and the 99.7% (y ± 3aM) confidence levels were chosen as the warning levels and control limits respectively.] Lower Graph: "Normalized range values (R + OR) versus the month of analysis." [The 97.5% (R + 2cR) and ^100% (R + 3aR) confidence levels were chosen as the warning levels and control limits respec- tively.] 16 ------- STRONTIUM-89 IN MIX JULY 1973 FREQ. 5 . 4 . 3 - 2 - 1 . 0 U - x" = s = i i i i 0 10 20 98 87. 11.0 | 30 pCi/liter 2 | " .. | | 40 I i 50 I 60 I I I I I I I I I 50 60 70 80 90 100 110 120 130 140 150 160 CONCENTRATION IN pCi/liter FREQ. FREQ. 5.. 4 . . 3 -- 2 -. 1 4. 0 STRONTIUM-89 IN MIX AUGUST 1973 Jl = 96 pCi/liter X = 615 S = 296 X + 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 CONCENTRATION IN pCi/liter 5 .. 4 . . 3 -- 2-. 1 .. 0 _ STRONTIUM-89 IN MILK SEPTEMBER 1973 U = 85 pCi/liter X" = 76.9 " S = 12 3 I I I I I 111 I I I I I I 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 CONCENTRATION IN pCi/liter 5 .. 4 .. FREQ. 3 . . 2 -. 1 . . o L STRONTIUM-89 IN MILK OCTOBER 1973 L| = 133 pCi/liter X = 112.3 S = 254 I I I I I I I I I I I I 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 CONCENTRATION IN pCi/liter Figure 3-A. Histogram of Monthly Analysis for Strontium-89 17 ------- 5 , . 4 . . FREQ. 3 . . 2 - . 1 . . o L STRONTIUM-89 IN MILK NOVEMBER 1973 U, « 123 pCi/liter X = 98.3 S = 24 9 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 CONCENTRATION IN pCi/titer STRONTIUM-89 IN MILK 5 . . 4 . . FREQ 3 . . 2. . 1 . . 0 DECEMBER 1973 LI » 89 pCi/litef 7 = 69 5 • S = 308 0 10 20 30 40 5C 60 70 80 90 100 110 120 130 140 150 160 CONCENTRATION IN pCi/liter STRONTIUM-89 IN MILK FEBRUARY 1974 6- - 5- - L) = 83 pCi/liter FREQ 4-- x = 926 • 3T 2- 1 ° I ' ' I I I I I I I I I I I I I I I I | | I ^^ I I I ff I I I I | I I I 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 CONCENTRATION IN pCi/liter STRONTIUM-89 IN MILK APRIL 1974 6- - 5- . L| = 204 pCi/liter FREO 4- . X = 171 9 3- • S = 36 7 2- - o'l I I I I I I I | I | I I I 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140' 150' 160 ' 170' 180' «o' 200 210'220 '230 11'' r^rtJrTvl~"^^~^W~^^~H-^^- CONCENTRATION IN pCi/liter Figure 3-A. Histogram of Monthly Analysis for Strontium-89 (continued), 18 ------- FREQ. STRONTIUM-89 IN MILK JULY 1974 6 "" LI = 151 pCi/liter 4 -~ X = '28.1 •• 27,6 3-- 2- - o'l I | I I I I I I I I I B I I I ^^ m-^^-^^ff fl I I I I M M | M 0 10 20 30 40 50 60 70 80 90 100 "0 120 130 140 150 160 170 180 190 200 210 220 230 CONCENTRATION IN pCi/liter STRONTIUM-89 IN MILK FREQ SEPTEMBER 1974 JJ = 157 pCi/liter 137.8 6-- 5-- 4- - 3-- S = 257 2- - 1 - - 0 < | I I I I I I—| I I I I | I i i—fiii—i—n—i—i ' « i i t «—i i i i i i i i i i i i T—r 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 CONCENTRATION IN pCi/liter STRONTIUM-89 IN MILK FREQ 6- - i". 3- - NOVEMBER 1974 U - 172 pCi/liter X = 137 3 - S = 39.1 - 1 I I | I | I I I | I 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160' 170' CONCENTRATION IN pCi/liter I I I I M 190 200 210 220 230 Figure 3-A. Histogram of Monthly Analysis for Strontium-89 (continued). 19 ------- STRONTIUM-90 IN MILK FRED JULY 1973 i i i i 0 10 20 30 40 50 60 70 80 90 WO 110 120 130 140 150 160 170 180 190 20C 210 220 CONCENTRATION IN pCi/liter FREQ STRONTIUM-90 IN MILK AUGUST 1973 L4 = 158 pCi/liter )T = 130.4 S = 44.5 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 20C 210 220 CONCENTRATION IN pCi/liter FREQ STRONTIUM-90 IN MILK SEPTEMBER 1973 6 - 5 - 4 - 3 - 2 - 1 . 0 ( U = 72 pCi/liter X = 67.6 S = 64 i 1 I I I i | | i i 1 1 1 1 1 1 T 1 1 1 3 10 20 30 40 50 I I I I I I I I I 1 I I I I •! I 1 I I I I I | |l 70 80 90 100 110 120 130 140 150 160 170 180 190 20C 210 220 CONCENTRATION IN pCi/liter STRONTIUM-90 IN MILK FREQ 6 -- 5 -- 4 -- 3 -- 2 -- 1 -- 0 0 OCTOBER 1973 L| - 119 pCi/liter X = 106.1 S = 19.9 I I I I I I I I I I I I |l 10 20 30 40 50 60 70 80 90 WO 110 120 130 140 150 160 170 180 190 20C 210 220 CONCENTRATION IN pCi/liter Figure 3-B. Histogram of Monthly Analysis for Strontium-90 20 ------- STRONTIUM-90 IN MILK FREQ. 6 -- 5 -- 4 - - 3 -- 2 -- 1 -j- 0 NOVEMBER 1973 Lj = 135 pCi/liter X = 115.2 S - 26.9 10 20 30 40 50 60 70 80 90 CO 110 120 130 140 150 160 170 180 190 20C 210 220 CONCENTRATION IN pCi/liter FREQ FREQ. STRONTIUM-90 IN MILK DECEMBER 19/3 M = 103 pCi/liter X = 93.1 S = 16 4 I I I 0 10 20 30 40 50 60 70 80 90 CO 110 120 130 140 150 160 170 180 190 20C 210 220 CONCENTRATION IN pCi/liter , STRONTIUM-90 IN MILK 6 - - 5 -- 4 - - 3 •- 2 -- 1 - - o L- FEBRUARY 1974 M = 198 pCi/liter X = 1827 •• S = 20.0 I I I .11 I I I I I I I I I I I I I I I I I I I I 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 15O 160 170 180 190 20C 210 220 CONCENTRATION IN pCi/liter STRONTIUM-90 IN MILK FREO 6 -- 5 -- 4 -- 3 -- 2 -- 1 -- o L. APRIL 1974 U, = 172 pCi/liter 3? = 169.9 •• S = 22.9 " -H- 0 10 20 30 40 50 60 70 80 90 OO 110 120 130 140 150 160 170 180 190 20C 210 220 CONCENTRATION IN pCi/liter Figure 3-B. Histogram of Monthly Analysis for Strontium-90 (continued), 21 ------- FREQ FREQ STRONTIUM-90 IN MILK JULY 1974 6 I L| = 152 pCi/liter 5 •- X = 1527 3 " S = 288 2 •- 0 T| | | | | | | | | | 0 10 20 30 40 50 60 70 80 90 XX) HO 120 130 140 150 160 170 180 190 20C 210 220 CONCENTRATION IN pCi/liler STRONTIUM-90 IN MILK SEPTEMBER 1974 6 • - H = 124 pCi/liter 4 . _ X = 124.1 3 - - s = 15.6 2 :- 1 . - 0 I I I I I I I I I I I I I I I 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 20C 210 220 CONCENTRATION IN pCi/liter FREO. STRONTIUM-90 IN MILK NOVEMBER 1974 I I I I I I I I I I I I I I I I I I II 10 20 30 40 50 60 70 80 90 100 HO 120 130 140 150 160 170 180 190 20C 210 220 CONCENTRATION IN pCi/liler Figure 3-B. Histogram of Monthly Analysis for Strontium-90 (continued) 22 ------- BARIUM-MO IN MILK FREQ. JULY 1973 L| = 148 pCi/liter 3< = 152.6 •• S = 11.0 I I I i I I I I I I I I I 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230240 CONCENTRATION IN pCi/litec BARIUM-140 IN MILK FREQ FREQ. AUGUST 1973 7 - 6 • 5 - 4 - 3 - 2 - 1 „ 0 M • '52 pCi/liter \ 7 = 158.4 S = 24.9 I-Ul I J I 4. i-L I I 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230240 CONCENTRATION IN pCi/l.ter BARIUM-140 IN MILK 7 •• 6 -- 5 -- 4 - - 3 -- 2 -- 1 - - o L_i SEPTEMBER 1973 U • 146 pCi/Uter X = 145 3 S = 27.9 -M-4 40 5O 60 70 60 90 100 110 120 130 140 (50 160 170 180 190 200 210 220 230240 CONCENTRATION IN pCi/liter BARIUM-(40 IN MILK M I -t I .41 M M I I I I 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230240 CONCENTRATION IN pCi/liter Figure 3-C. Histogram of Monthly Analysis for Barium-140 23 ------- BARIUM-140 IN MILK FREQ. FEBRUARY 1974 7 • • 6 -- 5 -• 4 - - 3 -- 2 -- 1 - - LJ = 159 pCi/liter >T = 159-3 " S = 1V9 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230240 CONCENTRATION IN pCi/liter BARIUM-140 IN MILK 7 -• 6 -- FFREQ. 4 " 3 -- 2 -- 1 - - 0 - SEPTEMBER 1974 Lj = 193 pCi/liter X - 195.2 S = 21 9 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230240 CONCENTRATION IN pCi/liter Figure 3-C. Histogram of Monthly Analysis for Barium-140 (continued). 24 ------- IODINE-131 IN MILK FREQ. FREQ. JULY 9 - 8 - 7 - 6 - 5 - 4 - 3 - 2 - 1 - n 1973 U = X = s = 115 125 18.3 pCi/liter 1 . , J M M I I I I I M I I I I I I 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 CONCENTRATION IN pCi/lrter IODINE-131 IN MILK AUGUST 1973 9 - 8 - - 7 - - 6 - - 5 - - 4 - - 3 - - 2 - - 1 - - 0 I—" L| = 144 pCi/liler H. = 147.8 S = 13.7 I I I I I 1 I I I 1 I I I I I I I I I I I I I I I I I 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 CONCENTRATION N pCi/liter FREQ. IODINE-131 IN MILK SEPTEMBER 1973 9 - • 8 - - 7 - - 6 - - 5 - • 4 - - 3 - - 2 - - 1 - - 0 - \\ 123 pCi/liter = 121.3 S = 8.8 I I I I I I I I I I I 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 2-30 240 250 CONCENTRATION IN pCi/liter FREQ. 9 8 7 6 5 4 4- 3 - . 2 -. OCTOBER 1973 U = 493 pCi/liter X = 4863 S = 282 420 430 440 450 460 470 480 490 500 510 520 530 540 550 560 CONCENTRATION IN pCi/liter Figure 3-D. Histogram of Monthly Analysis for Iodine-131 25 ------- IOOINE-131 IN MILK NOVEMBER 1973 9 - • H = 104 pCi/liter 7 " ! "X • 99 7 6 - - S = 11 0 5 - • FREO. 4 . . 3 - - 2 - - 1 - - 0 ' I I I I I I I I I I I I I I I I I I I I I I I I I I I I I 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 CONCENTRATON N pCi/liter IODINE-131 IN MILK DECEMBER 1973 9 - • L| - 177 pCi/liter 7 '. '. ^ = 1/58 " FREQ. 65:: s = 96 •' 4 . . 3 - - 2 - - 1 - - 0 ' | | I I I I t I I | I I I I I I I I I I I ' 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 CONCENTRATION IN pCi/liter IODINE-131 IN MILK FEBRUARY 1974 U - 150 pCi/liter 7 * 149 9 •• 8-27-7 " I I I I I I I I I 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 CONCENTRATION IN pCi/liter IODINE-131 IN MILK APRIL 1974 9 -• 8 • • 7 - • FREO. | " ~ 4 • • 3 - - 2 - - o T D = 150 pCi/liter X = 154.6 S - 20 7 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 CONCENTRATION IN pCi/liter 230 240 250 Figure 3-D. Histogram of Monthly Analysis for Iodine-131(continued). 26 ------- FREQ. « "*" 4 .. 3 -- 2 -- 1 -- IOOINE-131 IN MILK JULY 1974 9 .- L| - 142 pCi/liter 8 •- X = 1458 - " 7 + S = 159 I I I I I > I I I I I I ^^^—^^^^^^^^^^^^^^^^—^—I—(—f— 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 2-30 240 250 CONCENTRATION IN pCi/liter IODINE-131 IN MILK SEPTEMBER 1974 _ 9 • • 8 - - FREQ. I " ; 4 - - 3 - - 2 -- LJ = 188 pCi/liter X = 1922 " S • 20.4 * JLJL-i j ' I I'll 1H~^^^T~f~+• •1 I I I I I I I I | I I I I I I 40 50 60 70 80 90 100 110 120 130 140 150 160 170 160 190 200 210 220 230 240 250 CONCENTRATION IN pCi/Mer IODINE-131 IN MILK NOVEMBER 1974 9 • • FREQ. 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 2-30 240 250 CONCENTRATION IN pCi/liter Figure 3-D. Histogram of Monthly Analysis for Iodine-131 (continued), 27 ------- CESIUM-137 IN MILK JULY 1973 FREQ. 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 CONCENTRATION IN pCi/liter CESIUM-137 IN MILK AUGUST 1973 12 11 10 9 8 FREQ. 7 6 5 4 3 2 1 0 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 CONCENTRATION IN pCi/liter CESIUM-137 IN MILK SEPTEMBER 1973 • • U « 84 pCi/liter x 7 = 816 •• I - • S = 3.9 M I I I I I I I M I I I I I I I I I I I I M I I 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 CONCENTRATION IN pCi/liter CESIUM-137 IN MILK OCTOBER 1973 FREQ I I I I I I I I I I I I I I I I I I I I I I I I 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 CONCENTRATION IN pCi/liter Figure 3-E. Histogram of Monthly Analysis for Cesium-137 28 ------- CESIUM-137 IN MILK 12 - - FREQ FREO. FREQ 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 CONCENTRATION IN pCi/liter CESIUM-137 IN MILK DECEMBER 1973 I I I I I I I I I I I I I I t I I I I I I I t 40 50 60 70 80 90 100 110 120 130 HO 150 160 170 180 190 200 210 220 230 240 CESIUM-137 IN MILK CONCENTRATION IN pCi/liter 12 11 10 9 8 FREO 7 6 5 4 3 2 1 0 FEBRUARY 1974 (Lj = 214pCi/liter "X » 2089 " S = 127 " I I I I i I I 1 I II I I I I I I I I I ..... 40 50 60 70 80 90 100 110 120 130 140 )50 160 170 180 190 200 210 220 230 240 CONCENTRATION IN pCi/liter CESIUM-137 IN MILK 12 11 10 9 8 7 6 5 4 3 2 1 0 APRIL 1974 174 pCi/liter 171.1 16.1 I ( I I I I I I I I I I I I I I I I 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 CONCENTRATION IN pCi/liter Figure 3-E. Histogram of Monthly Analysis for Cesium-137 (continued) 29 ------- CESIUM-137 IN MILK JULY 1974 12 - - 11 - - 9 -. 8 . . FREQ. 6 '. ". 5 - - 4 . . 3 - - 2 - - U = 155 pCi/Uter S = W.O | | | | I I I I I | | I I I I I I I 40 50 60 70 80 90 100 110 120 130 140 ISO 160 170 180 190 200 210 220 230 240 CONCENTRATION IN pCi/liler CESIUM-137 IN MLK SEPTEMBER 1974 ' ' L| = 126 pCi/liter 10 - • 3( = 1323 9 . . 8 - . 9 - • S - 7.6 FREQ. I 6 - - 5 . . 4 - - 3 - - 2 - - 1 - - I I I I I |^PPPPPM-M-I I I I I I M I 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 CONCENTRATION IN pCi/liter CESIUM-137 IN MIX NOVEMBER 1974 12 J- 11 - - |J * 101 pCi/litef 10 - • 9 - . 8 -. 5=56 FREQ. I ' • 6 - * 5 -- 4 . . 3 - - 2 - - X = 1028 M I I M I I I I F^^^^-t-l I I I II I I I I I I I M I I I I M I 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 CONCENTRATION IN pCi/liler Figure 3-E, Histogram of Monthly Analysis for Cesium-137 (continued), 30 ------- REFERENCES 1. F. Knowles, "Interlaboratory Study of Iodine-131, Cesium-137, Barlun-140, Strontium-89, and Strontium-90 Measurements in Milk, May-July 1970," Technical Experiment 70-MKAQ-l, Analytical Quality Control Service, Bureau of Radiological Health (1970). 2. F. Knowles, "Rapid Field Method for Radiostrontium in Milk," Technical Report 70-TEC-l, Analytical Quality Control Service, Bureau of Radiological Health (1970). 31 ------- APPENDIX. STATISTICAL CALCULATIONS To illustrate the computations performed by the computer, example calculations are given using data for three actual samples analyzed at one laboratory (Laboratory D). The experimental data are listed and the mean, range, and the experimental sigma are computed. These statistics provide measures of the central tendency and dispersion of the data. The normalized range is computed by first finding the mean range, R, the control limit, CL, and the standard error of the range, aD. K The normalized range measures the dispersion of the data (precision) in such a form that control charts may be used. Control charts allow one to readily compare past analytical performance with present per- formance. In the example, the normalized range equals 0.3 R which falls inside the upper warning level, R + 2oR. The precision of the results is acceptable. The normalized ^deviation is calculated by computing the deviation and the standard error of the mean, a. The normalized deviation allows one to readily measure central tendency (accuracy) through the use of control charts. Trends in analytical accuracy can be determined in this manner. For this example, the normalized deviation is -0.7 which falls within the upper and lower warning levels. The accuracy of the data is acceptable. Finally, the experimental error of all laboratories, the grand average, and the normalized deviation from the grand average are cal- culated in order to ascertain the performance of all the laboratories as a group. Any bias in methodology or instrumentation may be found from these results. 32 ------- EXAMPLE CALCULATIONS (Laboratory D Data) Experimental data: Known value = y = 3273 pCi 3H/liter urine on September 24, 1974 Expected laboratory precision = a = 357 pCi /liter Laboratory Samp! e Result D Xi 3060 pCi/liter D x2 3060 pCi /liter D x3 3240 pCi /liter Mean = x N x = - = T- = 312° PCi /liter M j where N = number of results Range = r r = [maximum result - minimum result) = | 3240 - 3060 | = 180 pCi /liter Experimental sigma = s N - 1 - V 3060)' + (3060)^ + (3240)^ - (3060 + 3060 + 3240)^ = 103.9 pCi/liter 33 ------- Normalized range = wR + xaR Mean range = R R = d2a where d2 = 1.693 for N = 3* = (1.693)(357) = 604.4 pCi/liter Control limit = CL CL = R + 3aR = DuR where D* = 2.575 for N = 3* = (2.575)(604.4) = 1556 pCi/liter Standard error of the range = OD K aR = 1/3 (R + 3aR - R) = 1/3 (D*R - R) = 1/3 (1556 - 604.4) = 317.2 pCi/liter wR + xaR = 1R + XCTR 1R r - wR °R on for r > R * Rosensteln, M., and A. S. Goldin, Statistical Techniques for Quality Control of Environmental Radioassay, AQCS Report Stat-1, U.S. Depart- ment of Health, Education and Welfare, PHS, November 1964. 34 ------- wR + xaR = wR + oaR wR Frl R for r < R LRj OTT since 18° < 604-4 = 0.30 R Normalized deviation of the mean from the known value = ND Deviation of mean from the known value = D D = x - y = 3120 - 3273 = - 153 pCi /liter Standard error of the mean = a ND = _ am _ - 153 " 2S57T = - 0.7 = 357 = 206.1 pCi/liter 35 ------- Experimental sigma (all laboratories) = st = 149 pCi/liter Grand average = GA N N 49345 = 3290 pCi/liter Normalized deviation from the grand average = ND1 Deviation of the mean from the grand average = D' D1 = x - GA = 3120 - 3290 = - 170 pCi/liter ND' = . am - - 170 20FT = - 0.8 36 ------- TECHNICAL REPORT DATA (Please read Instructions on the reverse before completing) 1. REPORT NO. EPA-680/4-75-007 3. RECIPIENT'S ACCESSIOWNO. 4. TITLE AND SUBTITLE Preliminary Milk Report 5. REPORT DATE June 1975 6. PERFORMING ORGANIZATION CODE 7. AUTHOR(S) Arthur N. Jarvis and David G. Easterly 8. PERFORMING ORGANIZATION REPORT NO. 9. PERFORMING ORG \NIZATION NAME AND ADDRESS Technical Support Laboratory National Environmental Research Center P. 0. Box 15027 Las. Vegas, Nevada 89114 10. PROGRAM ELEMENT NO. 1HA327 11. CONTRACT/GRANT NO. In-house report 12. SPONSORING AGENCY NAME AND ADDRESS Office of Research and Development U.S. Environmental Protection Agency Washington, D.C. 20460 13. TYPE OF REPORT AND PERIOD COVERED 14. SPONSORING AGENCY CODE 15. SUPPLEMENTARY NOTES 16. ABSTRACT A summary of the results of the milk cross-check program from July 1973 through November 1974 is given. Examination of these results reveals that 29% of the participants were within the plus or minus 3 sigma control limits for strontium-89 analysis, 42% for the strontium-90, 52% for barium-140, 60% for iodine-131, and 77% for cesium-137. These results indicate the need for improvement in analytical procedures for the radionuclides studies. Accurate analysis of strontium-89 was particularly difficult for most laboratories to achieve, while the accurate analysis of cesium-137 was the least difficult. 17. KEY WORDS AND DOCUMENT ANALYSIS DESCRIPTORS b.lDENTIFIERS/OPEN ENDED TERMS c. cos AT I Field/Group milk analysis isotopes 89Sr, 90Sr, quality control quantitative analysis laboratory performance 131I, 13?Cs i sotopes quality assurance radioactivity radiochemistry 07 05 12 02 14 07 18 02, 04, 08 18. DISTRIBUTION STATEMENT Release unlimited 19. SECURITY CLASS (This Report) unclassified 21. NO. OF PAGES 40 20. SECURITY CLASS (Thispage> unclassified 22. PRICE EPA Form 2220-1 (9-73) GPO 693- i-740/4 '60 ------- |