ML19345H115
| ML19345H115 | |
| Person / Time | |
|---|---|
| Site: | Framatome ANP Richland |
| Issue date: | 01/21/1981 |
| From: | Estey H, Nilson R SIEMENS POWER CORP. (FORMERLY SIEMENS NUCLEAR POWER |
| To: | Shum E NRC OFFICE OF NUCLEAR MATERIAL SAFETY & SAFEGUARDS (NMSS) |
| Shared Package | |
| ML19345H116 | List: |
| References | |
| 18298, NUDOCS 8104300570 | |
| Download: ML19345H115 (7) | |
Text
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/ Oh A 90-IAS'l zrm EDj(ON NUCLEAR COMPANY,Inc.
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\\Q/K'y) V E. Y. Shum Uranium Process Licensing Section ?
Uranium Fuel Lice %1ng Branch DCCX["f' 3c r
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U.S. Nuclear Regulatory Comissica.;
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g Gentlemen:
Reference:
Your letter of October 8,1980 My letter of January 9,1981 Enclosed are two copies of Exxon Nuclear's responses to cements and questions of sections 4, 5 and 7 of the enclosure to your October 8, i L letter. Our responses to comments and questions of section 6 will be transmitted in the near future.
This partial response is being transmitted to allow your evaluation of our environmental information to continue in a timely manner.
If you have any questions or comments, please call me on (509) 375-8537.
Sincerely, H. Paul Estey, Manager Licensing & Compliance, Operating Facilities HPE/cle cc: Dr. F. Wimpey 4
1710 Goodridge Drive Approved:
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P.O. Box 1303 R. Nilson,*Trariager Corporate Licensing & Compliance th 3 pi the Enclosure)
THIS DOCUMENT CONTAINS
. P00R QUAUTY PAGES 5.Ls ' :3;Lp 18298
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4.
Fus.we ','aste Uraniten Recovery (',T2) PA*itu 4.1
- Ccmment, N*nere vitt i: be construa:ed?
Resconse The Waste Uranium Recovery facility'will be 'onstructed within
~
c the exclusion area of the ENC Horn Rapid: Fuel Fabricaticn plant as shown in Figure 4.1-1 (attached); Item No. 10 is tne WUR facility.
- 4. 2 ccmven:
- 0:c: vil he its con:ribu:icn to ;iqu *d, gaaecus and solid cas:es?
Resconse 4.2.1 Licuid Wastes During the initial operational phase of the WUR facility, during which only solid wastes will be processed for the recovery of uranium, approximately 105,000 gallons per month of liquid wastes will be generated. These liquid wastes will be routed to the on-site evaporation / storage lagoon system.
The approximate characteristics of these liquid wastes will be as follcws:
2 ppm uranium 0.4 molar NH NO 3 3 0.6 molar NH 0H 4
4.2.2 Gaseous Wastes The uranium content of the gaseous effluent from the WUR facility will add approximately 2 uCi to the quarterly value for the plant.
4.2.3 Solid Wastes At the design capacity during the initial operational phase, approximately 5,600 cubic feet of uranium-contaminated solid waste per month will be processed through the WUR facility,
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and approximately 2,400 cubic feet per month of lesser uranium-contaminated solid waste will come out of this facility, thereby resulting in a net reduction in solid waste production in terms of volume and uranium content.
The feed material for the WR facility will be uranium-contamina'ted solid wastes which have been accumulated-on-site, as well as that which will continue to be. generated in the CO2 plant.
- 4. 3 cce en:
Ecu vi;; th.ia affec: :F.a n:cher :f at:a.:ersonna;?
Resconse The initial operation will require approximately 12 technicians.
Indirect support will require approximately 2 man-years per year.
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Fiucride Emissions _
5.1 Com~en:
What are att of the possible chemical configura:'ons of flucride frcm the UF feed ~a:erial throughout the fuel fabrica icn procesa; uha: are tb destinies of these chemidaia (lagccna, stack eff uen:,.
- scrubbers, fuel, etc.) and :he masses.of each product'in these final condi:icns?
Resconse The possible chemical configurations of fluoride throughout to the U0 fuel fabrication process resulting from the UF feed material 7
6 may be best presented by describing the process.
Fluorise is introduced to the process as uranium hexafluoride (UF ).
The UF is reacted with water in the hydrolysis step to g
g form uranyl flGoride (UO F ) and hydrofluoric acid (HF) by the 22 following reaction:
6 + 2 H O - UO F2 2 + 4 HF UF 2
The UO F, and HF are reacted with amonium hydroxide (NH 0H) in 7
3 the prectpitation step to form amonium diurinate (ADU) Ind amonium fluoride (NH F). The classical chemical formula for ADU is (NH )
Most of the ammonium fluoride formed in the ADU precipitation sues,U 0.
3 g
27 is discharged in the process liquid waste stream from the ADU centrifugation step to the on-site liquid waste storage /evaporization lagoon system. However, some ammonium fluoride is carried into the ADU dryer with the wet ADU. The amount of fluoride present in the dry ADU is approximately two night-percent of the total mass.
In the ADU dryer, some of the contained fluoride is removed from the product as ammonium fluoride and is carried to the process offgas (POG) scrubber via the ADU dryer exhaust air ducts.
From the ADU dryer, dried ADU containing chemically bound fluoride is discharged, alang with dried amonium fluorides, into the calciner
- for reduction of ADV to U0,,.
In the calciner the acnonium fluoride and the chemically bound fiuoride are pyrohydrolized with moisture by the high temperatures involved in the reduction step to form HF.
Since the ADU contains excess amonia, which is released in the ADU reduction step, most of the HF formed in the ADU reduction step reacts with the amonia in the calciner offgas collection / scrubber system to form amonium fluoride. Most (s98,) of the amonium fluoride in the calciner offgas is removed by the calciner offgas scrubber and is discharged to the lagoons in the process liquid waste stream.
/
1 Process offgases from the calciner offgas scrubber are vented to the process offgas system and are scrubbed again along with process offgases from other process equipment. Process offgas scrubber solution (containing sG6f. of the fluoride entering the scrubber) is discharged to the lagoons in the process liquid waste stream. The fluoride passing through the P0G scrubber, in the forms of NH F 3
and HF, enter the exhaust air ducts where the~ exhaust air is dried (in-duct heaters) and double-HEPA filtered pr.ior to discha~rge. to atmosphere via elevated stacks. By far, the major portion of the ammonium fluoride is filtered out of the exhaust air stream by the
~
filters (mostly on the first stage), whereas the HF is released to atmosphere.
A small amount (s40 ppm, average, on a uranium weight basis) of fluoride remains in the UO,, powder discharged from the ADU-to-UO2 reduction calciner. The chemical composition of fluoride in the UG, powder has not been determined.
Fluoride in the 007 powder is pyrohydrolized with moisture in the cover gas by the high temperatures involved in the pellet sintering step to form HF. Most of the RF relessed from the pellets reacts with metallic impurities volitized pellets to form metallic fluorides. These metallic from the UO,long with the remaining HF, are collected in the exhaust fluorides, !.
air system for the U07 powder process area. The metallic fluorides are removed from the exhaust air by the filtert, whereas the HF is discharged to atmosphere via an elevated stack (following dcuble-HEPA filtration).
Table 5.1-1 (attached) summarizes the chemical configurations and destinies of the various flucride species, along with the masses of r
each intermediate product in final conditions, on the basis of grams of fluoride and grams of specific chemical species present per kg of uranium processed.
1
- 3. 2 Cce:~en:
Provide descrig:ian of the ccq:rative acni:cring experimen:
1 uhich ui:: ccqcre X3C's f:ucride mani:cring :echnique in :he
.itacks tc :he mcdified %t me9cd for :he high fku scac'<a (X:0, X3:, X3:] and your bes: predia:icn of resuha.
Rescanse The comparative monitoring experiment has been completed. The i
experimental results are described in the attached Technical Report,
" Monitoring of Atmospheric Fluoride Discharges from 00, Fabrication Facility Exhaust Stacks", December 12, 1980, Document No. XN-NF-549. This work has shown that the ENC technique is more sensitive than the modified EPA method and that the fluoride emissions are in the range previously reported.
s I
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o S. 3 Ccm en:
In a telecen bes::een J. F. Wi.qey (SAI) and H. F. Ha:ey (E:iC) cn samcry 22, t.98t, Mr. Wi.mey reques:ed. inf:rm:icn :n the.de::n: ~inati:n factor and type of EF scrubber used in the DF conversjonprdcesa ernaus: a r sys:em.
Rescanse Three types of scrubcers are installed in Exxon Nuclear's UF -UO7 z
conversion facilities. Two of these types are involved in rcutine operations, whereas the third type is a standby emergency system to be activated in the event of a large release of UF6 gas to roca atmosphere. This discussion is limited to the two types of scrubbers in routine operational use.
Each ADV reduction calciner is equipped with a Jet-Vac Corporatior Type 55-30(eductorventuri) scrubber. The efficiencies of these scrubbers have not been measured. However, based on NH,F material balance calculations, tne efficiencies are estimated to#be s985, or a decontamination factor (DF) of 50 (NH F in /NH F out).
4 4
All process offgases from UF -UO, conversion operations, including g
those from the calciner scruebers, are vented to process offgas scrubbers. These scrubbers are Schuette-Kcerting Type 7010 (eductor venturi), which have an average measured efficiency of 86 + 175, or a DF of 57.
/
i XN-NF-549 Issue Date: 01/09/81 Exxon Nuclear Cogany, Inc.
Analytical Laboratory Technical Report:
Monitoring of Atmoscheric Fluoride Discharges from U02 Fabrication Facility Exhaust Stacks 12 December 1980 l
D.J. Hill C.
Manolopoulos bU S.R. Lockhaven[
R.L. Braaten pf,[y
.. e I
I 1-A-13 8104 3 o o g7;
c' Table of Contents XN-NF-549 Monitoring of Atmosaheric Fluoride Discharges from UOp Fabricati' n a
Facility Exnaust Stacks
1.0 INTRODUCTION
2.0
SUMMARY
3.0 DESCRIPTION
3.1 Background Studies 3.2 Sanpling Procedure 3.3 Analytical Procedure 4.0 RESULTS 4.1 Filter Collection Efficiency 4.2 UO2 Plant Atnespheric Fluoride Source Term
5.0 REFERENCES
5.0 APPENDIX 6.1 Table 1: Monitoring Results; K3 and K9 Stacks 6.2 Table 2: Monitoring Results; K10, K31, K32 Stacks 6.3 Table 3: Recorded UO2 Plant Stack Flows During Monitoring Periods a.
K3 and K9 Stack Flows b.
K10, K31 and K32 Stack Flows Attachnent 1: Sampling Procedure, " Determination of Total Fluorides in Gaseous Effluents; Comparison Study" : Analytical ?rocedure, XN-NF-P69261, " Determination of Fluoride as HF in Environmental Filter Sanples or Impinger Solutions" l
i j
1-A-15
i XN-NF-549
- 1. 0 INTRODUCTION The ENC fuel production process is a potential source of environmental fluoride contamination, due to fluoride liberated in the course of UF6 conversion and the use of hydrofluoric acid in the cleaning of zircaloy cladding. Gaseous fluorides produced in these processes must be effectively removed from the discharged gas streams in order to minimize detrimental environmental contamination.
ENC routinely monitors stack fluoride discharges by continuous sampling with l
treated filters.
The study described in this report was intended to exami ne the accuracy of reported fluoride discharge measurements and to evaluate the effectiveness of a revised treated filter samoling method.
The described tests covered two month-long monitoring periods with integrated twenty-four hour sample collection using two different methods.
Five separate exhaust stacks were monitored and the results evaluated to determine the fluoride collection efficiency of sodium carbonate treated filters, as well as the average atmospheric fluoride source term (integrated discharge level) for the UO2 fuel production facility.
2.0 SUMARY The results of the monitoring study are surmiarized as follows:
The sodium carbonate treated filters generally were found to provide a o-collection efficiency for fluoride of approximately 80" or higher, under the conditions of these tests.
o The atnospheric fluoride source term for the U02 production facility was found to be less than 13.5 grams per day or less than 10 grams of fluoride per metric ton of uranium throughput.
1-A-16
XM-NF-549 3.2 Samoling Procedure Since the objective of this study was twofold, a sampling system was constructed to acconplish both goals sin 21taneously:
1)
Measure stack fluoride emissions over an extended period of 9
time to establish an accurate fluoride source term,and 2)
Verify the reliability of the sodium carbonate-treated filter method as a routine monit9 ring procecure.
As described in the ENC sampling procedure (Attachment 1), samples of gaseous effluents were drawn through heated stainless steel lines then split into parallel 1.0 liter per minute (1pm) streams, one of which passed through a water scrubber and the other through two sodium carbonate-treated filters in series.
The water scrubber sample served as a comparison sample, approximating the results expected from the referenced EPA procedure.
The filter samples were set in series so as to evaluate the relative efficiency of the treated filters for fluoride collection by measuring breakthrough to the second filter. The relative fluoride levels observed on the filters (Front ="F",
Backup ="B")
were l
l used to calculate filter collection efficiencies according to the l
l equation
" Efficiency = Mx 100 F
l 1-A-18
XN-NF-549 4.1 Efficiency of Treated Filters (cont)
Of the 120 comparison sarples successfully obtained, four instances were noted in which higher fluoride levels were observed in the second filter than in the first.
At least three of these were probably the result of excessive condensation in the K10 sample line.
Such conden-sation can Teach the soluble fluoride from the leading filter.
The fourth case (K31, 3 Dec. '80) is apparently a spurious analytical result.
The remaining filter comparison data sets present strong evidence that the collection efficiency of the treated filters was normally between 75-100%, under the conditiens of these tests.
Averaging the eight measured positive efficiency values results in an approximate filter efficiency of 75%. If the additional 15 " greater-than" values exceeding an efficiency of 75% are included in the average, a composite measured collection efficiency on the order of 82% is obtained (81.9t15%).
4.2 UO7 Plant Atmascheric Fluoride Source Term l
The measured fluoride level for each location and day of sanpling aay be taken a'eng with the recorded stack airflow for that day (Table 3) to provide a measure of total fluoride emissions during the monitoring period.
For a given day and stack location:
G = C x F x 0.0346 where G = grams fluoride discharged C = maxixuia measured fluoride concentration (u I/ )
1 F = recorded stack flow rate (CFM) 0.0346 = proportionality constant 1
1 1-A-20
XN-NF-549
5.0 REFERENCES
- 1) Letter, R. Nilson (ENC) to R.8. Chitwood (NRC), June 15, 1973; reference ENC'S response to question no. D.7 (Table D.7.2) 2)
Letter, L.J. Maas (Environmental Health Sciences) to Marvin Smith; "K39-A and K-32 Fluoride. Samp ling Study-Exxon P.O. No. R-076134",17 August,1978
- 3) Letter, L.J. Maas (Environmental Health Sciecces) to D.J. Hill; " Particulate and Gaseous Fluoride Sagling, X-32 Exhaust System-Exxon P.O. No. R-086813",
8 June, 1979
- 4) Letter, M.X. Valentine to M.L. Smith, "Fluoridi Monitoring" 21 February 1979
- 5) 41 FR 52299, November 29,1976 " Method 138-Determination of Total Fluoride Emissions From Stationary Sources-Specific ion Electrod Method"
- 6) Study Report: Hanford Envircr$ mental Health Foundation (Rich U.nd, WA)
" Evaluation of the Collection Efficiency of Sodium Carbor.ar;-Treated Filter Pads for Samling of Gaseous Hydrogen Fluoride"; Dom ?d J. Hill, Scott D.
Ager, October,1975
- 7) Washington State Industrial Hygiene Laboratory Procedure for Gaseous Fluoride (1974) 8)
" Determination of Gaseous and Particulate Chloride and Fluoride in the Atmosphere", Toshiich, Okita, Atmoscheric Environment, Vol. 8, p. 927-936, 1974
- 9) Letter, H.P. Estey to 0.L. Cornell, " Determination of ENC's Total Exhaust Air Fluoride Source Term", 23 August,1979 10)
JN-14, Addendum 5 " Applicants Environmental Report", H.P. Estey, April l
1979
- 11) Manufacturing Monthly Progress Report: October, November,1979; October, November 1980 l
l l
f l
l 1-A-22 t
i XN-NF-549
- 6. 0 APPENDIX 6.1 Table 1: Fluoride Monitoring Results. K3 and K9 Stacks (com by Volume Fluoride as HF in Stack Gas)
Date K3 K3 Filters Filter K9 K9 Filters Filter Imoincer Front Back E*
G**
Imoinger Front Back E*,
G**
ppm ppm ppm ppm ppm ppm 2 Oct 79
<.01
<.002
<.002
<3
<.01
<.01
<.002
>80%
2 3 Oct 79
<.01 LIA LIA
<. 01
<.002 <.002
<.4 4 Oct 79
<.01
<.002
<.002
<3
<. 0 7
.01
<.002
>80%
2 8 Oct 79
<.01
.003
<.002
>33%
5
<.01
.01
<.002
>80%
2 9 Oct 79
<.01
.002
<. 0 02 3
<. 01
.002 <.002
.4 iO Oct 79 LIA LIA LIA
<.01
<.005
<.002
>60%
1 11 Oct 79
<.01
<.002
<.002
<3
<.01
.003
<.002
>33%
.6 15 Oc' 79
<.01
<.002
<.002
<3
<.01
.004 <.002
>50%
.8 16 Oct 79
<.01
<.002
<.002
<3
<.01
<.002
<.002
<.4 17 Oct 79
<.01
<.002
<.002
<3
<. 01
<.002
<.002
<. 4 18 Oct 79
<.01
<.002
<.002
<3
<.01
<.002
<.002
<.4 22 Oct 79
<.01
<.002
<.002
<3
<.01
.002
<.002
.4 23 Oct 79
<.01
<.002
<.002
<3
<.01
<.002 <.002
<.4 24 Oct 79
<.01
<.002
<.002
<3
<. 01
.003
<.002
>33%
.6 25 Oct 79
<.02
<.002
<.002
<3
<.01
<.003
<.003
<.6 29 Oct 79
<.01
<.002
<.002
<3
<. 01
.004 <.002
>50%
.8 30 Oct 79
. 01
<.002
<.002
<3
<.01
.02
<.002
>90%
4 31 Oct 79
<. 01
<. 002
<.002
<3
<. 01
.002
<.002
.4 1 Nov 79
<.01
<.002
<.002
<3
<.01
<.002
<.002
<. 4 2-4 Nov 79
<.004
<.001
<. 001 3@<2
<.003
.005
<.001
>80% 301 5-6 Nov 79
<.006
<.001
<. 001 29<2
<.008
.008 <.001
>88% 292 7 Nov 79
<.01
.015
<.002
>87% 23
<.01
<.002 <.002
<. 4 8 Nov 79
<.01
<.002
<.002
<3
<. 01
<.002
<.002
<.4 n=24 iI <4 y_4 g/d n=26_,
K3 G
<1 1 1 g/d K9 LIA - Lost In Analyses E = Calculated Filter Efficiency, Front G = Integrated Grams Fluoride Discharged Per Day 1-A-23
XN-NF-549
- 6. 3 Table 3: Recorded UO9 Plant Stack Flows During Monitoring Periods a.
K3 and K9 Stacks CFM X3 l K9 x 1000 Date 10 79 (45)*
(6200)
K 3 services the UO2 pellet production 10-3-79 (45)
(6200) equipment and area.
10-4-79 (45)
(6200) 10-5-79 45.0 5850 K 9 services the fuel rod etch facility.
10-6-79 45.0 5850 10 79 44.5 5850 10-8-79 44.0 5900 10-9-79 43.0 6200 10-10-79 44.0 6100 10-11-79 45.0 6000 10-12-79 45.0 6000 10-13-79 45.0 6100 10-14-79 44.0 6100 10-15-79 45.0 6100 10-16-79 45.0 6100 10-17-79 45.0 6100 10-18-79 45.0 6000 10-19-79 44.0 5800 10-20-79 44.0 5800 10-21-79 44.0 5800 10-22-79 44.0 5700 10-23-79 44.5 5600 i
10-24-79 44.0 6150 l
10-25-79 43.5 6100 10-26-79 44.0 6150 10-27-79 44.5 6200 10-28-79 45.0 6200 10-29-79 45.0 6200 10-30-79 44.0 6150 l
10-31-79 44.0 6200 11-01-79 44.0 6250 11-02-79 44.0 6250 11-03-79 44.5 6250 11-04-79 44.5 6350 11-05-79 44.5 6400 1
11-06-79 45.0 6450 11-07-79 44.0 6400 11-08-79 44.5 6450 11-09-79 44.5 6400
- ( ) Denotes assumed max. value l
l 1-A-24
i XN-NF-549 Attachment I i
SAMPLING PROCEDURE:
Determination of Total Fluorides in Gaseous Effluents; Comparison Study.
M D. J. Hill September 1979 APPROVALS: m/M
/e/#/6#
Manager, Ana1ytical Lab Date f
Wo+ f, M77 l
Marptge?, LActnsing and Compliance Date l
r l
l l
l
XN-NF-549 SAMPLING PROCEDURE DETERMINATION OF TOTAL FLUORIDES IN GASEOUS EFFLUENTS: COMPARISON STUDY 1.0 SCOPE This sampling procedure specifies the equipment and outlines the steps required to obtain samples to determine the concentration of fluorides in gaseous effluents from Exxon Nuclear's UO2 Fuel Fabrication Facility.
Specifically, this method shall be utilized to obtain correlation data between a modified EPA impinger sampling procedure and the use of carbonate-treated filter pads. Concurrent to the comparison study, the analytical results will be utilized to derive an overall source term for fluorides in gaseous effluents from this facility.
l 2.0
SUMMARY
An air sample is continuously drawn from the gaseous effluent stream being sampled, through a stainless steel sample probe. The probe is heated as necessary to prevent condensation of moisture in the line. The l
l
' gas sample is split into two parallel streams flowing at a set constant rate. These airstreams are treated to collect fluoride using two methods:
1)
One airstream is bubbled through def onized water to dissolve hydrogen fluoride (HF) and other water-soluble fluorides which may be present.
l
XN-NF-549 Page 3 The liquid impinger sampling device consists of a 250 mt.
Erlenmeyer sidearm flask, fitted with a drawn glass impinger tube which extends to within 1/2 inch of the bottom of the flask. At the start of sampling, the flask is filled with 150 mt of deionized water. A similar impinger is connected downstream of the sampler, but is not filled with water.
This serves as a demister to protect the flowmeter. If necessary, another empty impinger flask may be connected upstream of the sampler, to act as a backflow trap. A calibrated rotometer is dsed to monitor the sample flow through the flasks.
The treated filter sampling assembly consists of two plastic (Tennite) cassettes mounted in series and containing 37mm diameter absorbent filters.
l The filters are soaked in 6% sodium carbonate (Na2CO ) solution and dried 3
prior to use. Again, a precalibrated rotometer is used to measure the flow rate through the samplers.
The series configuration is used to i
i permit derivation of the approximate collection efficiency for the sampler, I
and to measure possible fluoride breakthrough.
4.0 PROCEDURE Steps Key Points 1.
Prepare the absorbent filters by soaking 1.
Handle the filters with millipore 37mm cellulose filter pads in clean forceps to avoid 6% Na2CO3 solution until thoroughly contamination.
dampened. Allow to dry in air or oven-0 dry at 50-60 C, then seal in a protec-tive container until used.
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i XN-NF-549 Page 5 Steps Key points 7.
Readjust the flowmeters as necessarf.
8.
Record the date, time, and location 8.
Verify correct sample of sampling. Continue sampling for flows occasionally approximately 24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br />.
during the day.
9.
At the end of the sampling period.
9.
Record the termination close the vacuum shutoff valve, then date and time for the
~
close the probe valve and disconnect samples.
the sample line.
10.
Remove the sample flask and filter
- 10. Submit the samples to cassettes. Rinse liquid clinging to the laboratorf for impinger tube into the flask with a fluoride analysis, small quantity of deionized water.
Label the samples as appropriate, and l
reassemble the system with fresh samplers.
11.
Restart sampling as in steps 5 through 9.
l l
i
o E@ON NUCLEAR COMPANY,Inc. XN-NF-549 A'4ALYTICAL PROCEDURES TITLE: Deter::lination of Fluoride as HF in CCC'JMENT No: XN-NF-103 Environmental Filter Samples or impinger Solutions
%\\
2.4.5 5Y: 00H PROCECURE NO. P69261 Rev: 0 ISSUE DATE: 09/04/30 stPEasECED Issue:
New PAGE 1 CF 5 i
l t
I O
/
Issuec by:Ws ei fa7 Ps Manager, Maiyticai La::s l
\\
bN
/h Approved by:
Managfr,QualityCp:roi Approved by:
88~J[
f /a c/h>
~
Manager, Manufacturing h,
NOTICE
~
This document contains informaten propretary to Esson NucIsar CarPO4ny. IrtC.; it is submitted in conf 4ence arid rs to Ce used Sole 4Y i
for t".e OurDose for enacn it :s furffisned arid returnod upon recufft.
I This document arts such inferrmaten is not to 54 recrocuced. trans-mrtted, or$C:Osed or used otnerwise, in anole or in part, wet,%ut the arrtten autP.or:2at4n of EasCn Nuclear Company. Inc.
XN-NF-549 ERON NUCLEAR COMPANY,Inc.
p ANALYTICAL PROCEDURES PROCEDURE N0: XN-NF-P69261 REV. O PAGE 3 CF 5 5.0 REAGENTS 1.
Sodium Acetate - acetic acid buffer (.001 M in each).
2.
Methyl Orange indicator.
3.
10 N H 504 (Slowly add 278 ml concentrated H 504 to approxi-2 2
mately 600 ml deionized H O cool, and dilute to one liter).
2 4.
Stock Fluoride solution; 1 g/l F standar.d.
(Use reagent grade sodium or ammonium fluoride).
5.
Working fluoride standard;.1 g/l F- (1 ml = 100 pg F-).
6.0 REFERENCES
41 FR 52299 (E?A Method 13b); November 29, 1976 EHS-No. F-5-1 Analytical Procedure ~" Gaseous HF in Air" (HEHF - EHS Laboratory 6-26-75 MK Hamilton) 7.0 PROCEDURE STE?S KEY POINTS & SAFETY CAUTIONS TREATED FILTER SANPLES 1.
Carefully open the sample 1.
Examine the filter for cassette and remove the distortian, discoloration or filter with clean tweezers.
otner signs of damage or excessive moisture.
' 2.
Place the fil er pad in a 2.
Soak for 15 - 30 minutes, clean plastic beaker and add stirring occasionally.
20 ml deionized water.
3.
Add 1 drop methyl orange 3.
The color should change from indicator and neutralize by yellow to pale red. Stir drepwise addition of 10 N H 50.
constantly and allow the color 2 4 to stabili:e before adding additional acid.
4 Prepare a blank (unusec) filter pac in an identical manner.
O i L 5e, 'e='Od uct!Qn, transmattal or Os5C:Q$6re af tn e aOCv e n for*at.Qn 5 EwO eCI
- Q the restr Ction On tNe *irst Of tit e 3498 Jf t%$ doc.m en t.
..u EQCN NUCLEAR COM.*ANY,lnc.
XN-NF-549 O.
ANALYTICAL PROCEDURES PROCEDURE NO: XN-NF-P59251 REY. O PAGE 5 0F 5 STE?S KEY POINTS & SAFETY CAUTIONS LICUID SCRUSSER (IMPINGER) SAMPLES
- 12. Measure the liquid volume in
- 12. Rinse the impinger tube and the imoinger er scrubber.
flask contents into a clean i
gracuated cylinder.
- 13. Withdraw a 10 ml aliquot and
- 13. The sample size may be altered transfer to a 50 mi plastic beaker.
if necessary to oc:ain a reading within the calibraticn range.
14 Proceed as in Steps 3, 5, 10 and 11.
~
- 15. khen the measure: ants are completed, clean up the ecuipment and leave the meter in stancoy and electrodes in deionizec water.
8.0 CALCULATIONS
= ppm lucrMe (soluden) sam le me (ml) ppm fluoride (solution) x volume = = ug flucride (total)
I ug fluorice (total) x 20 ug HF x 22.4 ml W w F-20 m "
Air 5ampie volume titters)
= ppm by volume (flucride as HF inatr7
- " volume" = leacq volume (20 ml) for filter samoles or impinger volume (total ml) for scrutcer secoles l
l O
l L SG. P eO r od t,C tJ O n, i'4 P Sm i tt al or diSCLC$are of tn e aCCwe n fO rra a t:CM tS swo,e:t j
to Ine restf sCT Co Qn t!'e first 3r titf e page of t n.1 sc;am en t.
1-3-26
XN-NF-549 Issue Date: 01/09/81 MONITORING OF ATMOSPHERIC FLUORIDE DISCHARGES FROM UO 2 FABRICATION FACILITY EXHAUST STACKS DISTRIBUTION H.P. Estey D.L. Cornell N.S. Wing D.
Clark R.L. Miles R.H. Purcell M.K. Valentine R.M. Cruford K.P. Galbraith W.S. Nechodom D.J. Hill / LB C.
Manolopoulos S.R. Lockhaven R.L. Braaten J. A. Perry 1
Document Control (5) i 1-A-14
- = *,.
w w
-, +
w.-, - - -
-m
,.,.---,.e---4
,-y..-
w
---y-.*
-.y-,
-=- -
---vi-4.-.
e---, - -
e
-w-w--
TABLE 5.1-1 Sunmary of Fluorides Produced as the Result of Processing UF to U0 6
2 Quantity of Fluoride Fluoride Fluoride Fluoride Quantity Species (9 of Species /kg Process Step Species Destiny (g F/kg U) of U processt *)
Vaporization UF Ilydrolysis 478.99 1478.99 6
liydrolysis 00 f Precipitation 159.66 1294.08 22 IIF Prectpitation 319.33 336.02 Precipitation Nil F Lagoon 452.33 880.85 4
ADU (2% F)
ADU Dryer 26.66 1333.00 ADl1 Dryer ADU (2% F)
Calciner 26.66 1333.00 P0G Scrubber-+
4 ADU > U0 Nil F & ilF Calciner Offgas Scrubber 26.62 51.84 l
I" F in U0 P wder Pellet Sintering Furnace 0.04 1138.95 y,
2 l
l Calciner Offgas Nil F & ilF Nil F Lagoon 26.10 50.82 4
4 S f"hh""
l Nil F & ilF P0G Scrubber 0.52 1.01 4
- + Proce'ss Of fgas (P0G)
Nil F & ilF + Nil F Lagoon 0.45 0.87 4
4 Scrubber Nil F & ilf Conversion Exhaust Air 0.07 0.14 4
Coriversion Exhaust Nil F Filters 0.063 0.12 4
Air Nil F & ilF Atmosphere 0.007 0.02 4
Pellet Sintering Furnace H'F-Il)
Filters 0.037 0.164 IIF Atmosphere 0.003 0.003 Sunma ry Hil F Lagoon 478.88 (99.977 %).
932.556 4
Hil F & M*F-Filters 0.097 (0.020%)
I.
0.19 4
Nil F & ilF Atmosphere 0.01 (0.002%)
0.013 4
(1) ll' F-signifies inetallic fluorides.
7.
F!!uen: and 5nviromental Monit:rina
7.1 Comen
?tecae su~.arize in a table the opera:i<;inal efhuent' ~,cni: ring pragm including stack, liquid diacharge poin:3, camp'e coitiation and analysis frequency, sa~ple type (par:iculate, gas or liquid),
type of anatyaia (alpha, be:a cr iaccopic analysia) and eff;uen:
ac:icn level.
Resconse a)
Liouid Effluents Liquid process wastes containing uranium and high-level chemicals are routed to the on-site storage /evaporization lagoons. The only liquid wastes released from the site are sanitary, cooling water and low-level chemical wastes from feedwater treatment and component cleaning (non-radioactive) operations. All released liquid wastes discharge to the ENC-City Lift Station, where the total combined liquid effluent from the plant is collected and pumped to the Richland municipal sewerage system.
Additional pertinent information for the operational liquid effluent monitoring program is provided in Table 7.1-1 (attached).
b)
Gaseous Effluents All prccess and process areas gaseous effluents are discharged to atmosphere via stacks extending above the respective buildings.
Gaseous effluent sampling is continuous and isokinetic in all cases, and all gaseous effluent samples are collected from the stacks at points downstream of the final HEPA filters.
All samoles for radioactive material analysis are of the particulate type and are collected on high-collection efficiency filter papers.
~
Samples routinely collected for fluoride analysis are collected on fla,CO, treated filter papers to provide a mixed collection of particulate and gaseous components. However, as discussed in the response to Comment flo. 5.2, some gas samples have been collected in a liquid media for the purpose of comparing collection efficiencies.
As previously stated, all samples for radioactive material and fluoride analysis are of a continuous nature. The filter papers are changed and analyzed on a weekly (7-day) frequency.
/
0xides-of-nitrogen sampling and analysis has been conducted at least monthly during periods that scrap recovery operations have operated.
For this purpose, gas samples were obtained from the K-10.and K-32 stacks, as appropriate.
Recently, Exxon Nuclear has installed a continuous NO sampler / monitor to serve both stacks, which automaticllly switches from one stack to' the other on. a preset frequency.
This instrument has been in service for several months and is currently on a routine calibration program.
t l
Additional pertinent information for the dperational gaseous effluent monitoring program is provided in Tables 7.1-2and71-3(attached).
- 7. 2 Carr en:
Picase s:c=arize in a table the envircr. men:ai =cnitoring program including a :-as shcuing ai* the media sc-wiing po *n:
iccasions, sam =le colia::icn and analysis frecuency, sam le type, types of analysis and =inirnan anciycicai, is:ee:icn levels.
Resoonse The current Exxon Nuclear environmental surveillance program consists of sample collection and analysis as shown in Table 7.2-1.
The locations of the environmental sampling stations are shown in Figures 7.2-1 and 7.2-2.
l
- 7. 3 Cce-ent Please surrz: rice the environmental r~sni:oring resuits on cli sa piing media for :he pas: five years. Please in:erpre the da:a as nach as pcssible, i.e., the environ =encai concen:ra:icn in fiucride in nia:icn :: piant release, acnit: ring ueit ia a in relation :: Lagccn leakage, etc.
Rescanse 7.3.1 Environmental Uraniumlesulting from Licuid Effluents l
As previously stated, liquid samples of the following streams are routinely analyzed for uranium content:
o ENC Plant effluent (ENC-City Lift Station) o Richland municipal sewage treatment plant clarifier i
effluent o
ENC plant water supply o
Yakima River (upstream from where the discharge from the Richland municipal sewage treatment plant enters the River).
/
Except in a very few instances for the ENC plant effluent, the uranium content of these samples has been below the lowerThe u detection level (0.1 ppm).
City Lift Station samples exhibiting positive resu l
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Environmental Uranium Resulting'from Gaseous Effluents' I
l 7.3.2 l
Table 7.3-1 (attached) gives the' quarterly amounts of uranium discharged to atmosphere for the years of 1676 through 1980.
It is evident that although the trend is one of' increase with plant expansion and increased production over the years, the uranium conten.t of gaseous effluents has leveled o The higher emissions in 1978 occurred during the startup of conversion facility when problems were the second UF,-UO encountered with excessive moisture in the a p
associated HEPA filters and a greater amount of uranium was air system.
Mcwever, that condition was released during that period.
[
corrected, and the amounts of uranium released in ga l
throughput rates.
consistent with expectations based on UF i
6 Environmental soil and vegetation samples are routinely analyzed for uranium content, which has ranged from <0.1 to 5.5 ppm U.
There is no correlation seen between the amount o l
Nor is there any apparent correlation between the l
principal downwind sectors and environmental samples exhibiting samples.
This lack of correlation is possibly due to positive results.
other potential uranium sources in the area.
Environmental Chemical Characteristics Resultino from l
l 7.3.3 l
As previously stated, liquid samples of the following and pH content:
ENC plant effluent (ENC-City Lift Station) o Richland municipal sewage treatment plant clarifier o
effluent ENC plant water supply o
Yakima River (upstream from where the discharge from the Ricnland municipal sewage treatment plant enters the o
River).
/
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' ' ' - ~ ~ - ' - - - - - - - - - -
The chemical characteristics of liquid effluents from the ENC plant do not differ significantly from those of the plant water supply, the Yakima River nor of the Richland municipal sewage treatment plant clarifier. effluent.
The chemical characteristics of the subject streams are sumarized.
in Table 7.3-2 (attached) for. the ' years of 1976 throu'gh 1980.
7.3.4 Environmental Fluoride Resultinq from Gaseous Effluents Table 7.3-3 (attached) gives the monthly amounts of fluoride conversion operations discharged to atmosphere from UF -UO for the years of 1976 through 1950. 2It is apparent that the g
amount of fluoride discharged is directly related to the amount of UF6 processed through the plant.
The third quarter,1978 peak in the amount of uranium released (see Section 7.3.2) was not accompanied by a fluoride peak because the problem (excessive moisture in the associated exhaust air ductwork) actually improved the removal of fluoride from tne exhaust air stream.
As previously stated, environmental ambient air, as well as environmental vegetation samples, are routinely analyzed for fluoride content. Generally, the fluoride in the environmental ambient air has increased with increased UFc throughput in the ENC plant, whereas the fluoride content of dnvironmental vegetation samples has been more or less random with possibly a slight increase.
The State of Washington Department of Ecology Fluoride Standards are provided in Enclosure 7.3.4 (attached). Table 7.3-4 sumarizes the environmental ambient air concentrations of fluoride (monthly averages), and Table 7.3-5 summarizes the fluoride content of monthly environmental vegetation samples.
7.3.5 Groundwater Contamination Resulting from Lacoon Leaks Until recently, the integrity of the liquid process waste lagoon liners has relied on analytical results of samples collected from a series of test wells located around the lagoon system (see Figure 7.2-2).
The uranium content of these samples has always been below the normal lower detection level (0.1 ppm). However, a special sampling program, along with the use of ultra-sensitive analytical techniques, has shown that uranium (of an enrichment generally
/
matching that of that processed through the EI4C plant) has reached the groundwater (in.the <1 ppb range).
The chemical characteristics of test well sampl'es are sumarized,
in Table 7.3-6.
Review of these data reveals that leaks from the lagoons have occurred over the y. ears, which have prompted ENC to undertake numerous liner. repair and' replacement projects overtheyears,andfinallytoinstall.asystemof{qyble liners with an intermediate leak monitoring system.
All lagoons have now been provided with double liners and the intermediate leak monitoring program has been operational for s 1 year. Results of the intermediate leak monitoring program to-date have alerted ENC to a leak in the upper liner of one of the lagoons, which has subsequently been repaired.
In an attempt to better evaluate the extent and movement of groundwater contamination resulting from lagoon leaks, ENC recently drilled two additional test wells (nos.14 & 15) and instituted a program of pumping the test wells. The two additional test wells were located further downstream of the other test wells in the assumed general direction of groundwater ficw (see Figure 7.2-2).
Pumping of the test wells assures that we are not sampling stagnant water (trapped in plugged well casings).
Results of weekly test well samples, particularly those for test wells nos. 2 & 9, indicate that there are no current leaks from the lagoons (i.e., there is a downward trend in the fluoride, nitrate + amonia, and sulfate values for test well no. 2, and an upward trend in the fluoride and nitrate +
ammonia values for test well no. 9, indicating that the corrective action taken has been effective and t!iat the contamination plume is moving north-northeasterly in the direction of the general groundwater flow; this is further supported by the I
fluoride, nitrate + ammonia, and sulfate values for test wells l
nos.14 & 15).
I 1
^
N See Section 3.4.4 of ENC's " Application for Renewal of Special Nuclear Material License No. SN!1-1227", Document No. XN-2.
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TABLE 7.1-1 Liouid Effluent Monitorina Procram l
l Discharge Point:
ENC-City Lift Station
~
~
Sampling Point:
. ENC-C.ity tift Station
~
i Sample Type:
Liquid-Sample Collection Frequency: Continuous
~
Sample Analysis Frequency:
Daily (Monday through Friday) l
~
l Samples Analytical liinimum Investigate Shutdown &
Analyzed For Method Sensitivity Level Correct Level Uranium Fluorimetry 0.1 1 0.1 ppm 0.1 ppm 1 ppm l
j Fluoride Specific ion 0.1 1 0.1 ppm 1
ppm 3 ppm i
Electrode Nitrate Specific ion 0.1 1 0.1 ppm 10 ppm Electrode (as N)
Ammonia Colorimetry-0.1 1 0.1 ppm 10 ppm Nessler Reagent (as N)
Sulfates Turbidimetrically 1 11 ppm 50 ppm l
(as 50 )
4 pH pH meter 0 to 14 in 0.1
< 6.5 or
< 5 or units
> 8.5
> 10
+
1 l
l l
l 4
/
E
TAllLE 7.1-2 Gaseous Effluent lionitoring Program Analytical Minimum i
Stack ID Building
[rea/ProcessServed Samples Analyzed for Hethod Sensitivity I
-16 K-3 UO Pelletizing Uranium Alpha Count 4x10 C1/mt 2
K-6 110&SF Pu0 -110 & Gd 0 U0 Uranium & Plutonium Alpha Count.2 3x10-16 pCi/mt l
2 2
Pro $ess Equip [,nedt & Areas I
K-9 00 Fuel Rod Etch Facility Uranium
. Alpha Count 2x10-16 Ci/mt I
2 K-10 00 UF -00 Conversion &
Uranium & Fluor 16e Alpha Count 3x10-16 Ci/mt I
2 SchapkecoveryProcess Specific ion
-3 3
5x10 ppb 3
i Equipment Electrode l
-16 K-21 00 Fuel Rod Loading Uranium Alpha Count 1x10 Ci/mt 2
Equipment & Area I
-16 3x10 Ci/mt K-31 UO UF -UO, Conversion &
Uranium & Fluoride Alpha Count 2
SchapRecoveryAreas Specific ion
-3 3
5x10 ppb Electrode s
I
-16 K-12 UD UF -U0 Conversion &
Uranium & Fluoride Alpha Count 3x10 pCi/mt 2
SchapkecoveryProcess Specific iori 5x10 ppb
-3 Equipment Ele *c trode 3 I
-16 T-33 UO UF -00 Conversion Uranium Alpha Count 4x10 C1/mt 2
Prbces$LiquidWaste
()uarantine Tank Galleries II) Anal'yzed for gross alpha activity in the range of 4.1 to 4.8 Mev.
(2) Analyzed for gross alpha activity in the range of 5.1 to 5.8 Mev, and adjusted per isotopic analysis.
(3) Filter paper ignited at 600 C; Na 00 fusion to solubilize fluoride; fluoride steam distilled from 2 3 ll PO -ilCt0 midure.
3 4 3
O
TABLE 7.1-3 Gaseous Effluent Action Levels & Guides A.
Radioactive Materials I.
Concentrations (Individual Stacks)
Action Levels Seven-Day Sample Results (uCi/mi-Aloha)
I4)
U-Oo. U )
MC0o.(2p)
~Reauired Actfons
~
0 6x10 Recount. sample (s). Check operations for possible source if activity is confirmed.
5x10-15 Increase sampling frequency to daily. Check pressure drop across all exhaust HEPA filters. Reevaluate all relative exhaust sampler results. Check for proper seating of related HEPA filtsrs.
lx10-13 Shut down associated intake fans and reduce exhaust flow rate. Prepare to shut down associated process. Inspect all related HEPA filters and replace all that exhibit any indication of inadecuacy.
If final HEPA filters exhibit any def-iciencies, replace them and in-place test the final filter bank. Perform particle size analyses of sampler filter papers. Notify sensitive radiological laboratories within one mile radius.
Update summation of quantity of radio-active material released via gaseous l
effluents on a weekly basis until a l
discharge concentration below this Action Level is sustained for a full calendar quarter.
-13 5x10 Recount samole(s). Check operations for possible source if activity is confirmed.
Increase sampling frequency to daily. Check pressure drop across all exhaest HEPA filters. Reevaluate all relative exhaust sampler results. Check for proper seating of related HEPA filters.
Update summation of quantity of radio-active material released via gaseous effluents on a weekly basis until a discharge concentration below this Action Level is sustained for a full calendar warter.
I
TABLE 7.1-3(continued)
I.
Concentrations (Individual Stacks)-(continued)
Action Levels Seven-Day Sample Results (uCi/mi-Aloha)
U-Oo.(I)
MO-Oo.(2,3)
- Recuired Actions (#)
5x10-12 Shut down associated intake fans and i
reduce exhaust flow rata. Prepare to
- hut down associated process.
Inspect all related HEPA filters and replace all that exhibit any indication of inadequacy.
If final HEPA filters exhibit any def-iciencies, replace them and in-place test the final filter bank. Perform particle size analyses af sampler filter papers. Notify sensitive radiological laboratories within one mile radius.
5x10 5x10-10 Initiate orderly shutdown of associated
-10 process for repair or correction of substandard conditions.
Initiate environ-mental air sampling in downwind sector (s).
2.5x10-7 2.5x10-7 Shut down associated processes and HVAC systems imediately. Notify NRC Region V I&E Office within 24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br /> if this concentration is sustained for a 24-hour period.
2.5x10-6 2.5x10-6 Shut down associated process & HVAC systems imediately. Notify MRC Region V I&E Office imediately if this i
concentration is sustained for a 24-hour period.
l l
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TABLE 7.1-3 (continued)
II. Quantities (Total Gaseous Effluent)
Action Levels (uCi)
Recuired Actions (3) 25 per calendar quarter Evaluate all gaseous effluent sampling data _for the previous quarter to identify potential-problems.
Investigate ident'ified sources of elevated concentra-tiens of radioactive material in gaseous effluents as described in Section I (for Action Levels less than ENC Annual Control Values) of this Table.
40 per calendar quarter Take actions specified for thefollowing)3ctionLevels:
1x10 M0-Op:
5x10-12 uCi/mi U-Op:
uCi/mi Update sumation of quantity of radioactive material released via gaseous effluents on a weekly basis until a weekly discharge rate of <l uCi has been sustained for a full calendar quarter.
>50 per calendar quarter Submit report to flRC within 30 days identifying cause, along with corrective actions taken to reduce release rates.
Prepare to petition the flRC for a variance in accordance with the conditions of 40 CFR 190.11.
In the event that the calculated dose to any member of the public in any consecutive 12-month I
period is about to exceed the limits specified in 40 CFR 190.10, shut down all operations involving unencapsulated radioactive material and all HVAC systems imediately, and notify NRC Region V I&E Office immediately.
b
/
i TABLE 7.1-3(continued) 8.
Fluorides Concentration in Individual Stacks Seven-Day Sample
. g)
Results (com)
Required Actions
>l knvestigate.
Inspect respective gaseous effluent treatment equipment for proper operation.
>10 Initiate orderly shutdown of associated processes and HVAC systems for repair or
~
correction of substandard conditions..
Initiate environmental vegetation sampling in downwind sector (s).
C.
Oxides-of-Nitrogen Concentrations in Individual Stacks Sample Samoling Period Results Required Action (4)
>500 ppm Investigate.
Inspect respective gaseous and/or effluent treatment equipment for proper 24-Hour Average
>20 ppm operation.
>1000 ppm Initiate orderly shutdown of associated and/or processes and HVAC systems for repair 24-Hour Average
>100 ppm or correction of substandard conditions.
l
~(1) Uranium-only operations.
(2) Mixed Oxide (Pu0 -UO ) operations.
7 7
(3) Mixed 0xide Action Levels represent the associated alpha activity only.
-It is to be noted that the 10 CFR 20 limiting value (total alpha activity) for actual uranium-plutonium mixtures is approximately two times higher than that for reactor grade plutonium along; however, for simplicity, Exxon 'gclear's Control Value is conservatively taken as the latter l
I (1x10' uCi/me.).
(
(4) Actions required at any one Action Level include all action that would have been undertaken at lower Action Levels.
/
4 E
TABLE 7.2-1 Environmental Surveillance Program Sample Type of Collection.
Analysis Analyzed Min. Detection Station Samole Frecuency Frecuency For Level 9
l-A Air Continuous tienthly Fluoride -
0.02 ppb Soil Quarterly-
. Quarterly Uranium-0.01 phm Vegetation Monthly (I)
Monthly.
Uranium'&
0.01 ' ppm '
Fluoride 1
ppm 1-B Air Continuous Monthly Fluoride 0.02 ppb Soil Quarterly Quarterly Uranium 0.01 ppm II)
Vegetation Monthly Monthly Uranium &
0.01 ppm Fluoride 1
ppm 2-B Air Continuous Monthly Fluoride 0.02 ppb Soil Quarterly (Held) 3-B Air Continuous Monthly Fluoride 0.02 ppb Soil Quarterly (Held) 4-B Air Continuous Monthly Fluoride 0.02 ppb Soil Quarterly (Held) 5 Air Continuous Monthly Fluoride 0.02 ppb Soil Quarterly (Held)
II)
Vegetation Quarterly Quarterly Fluoride 1
ppm 11 Air Continuous Monthly Fluoride 0.02 ppb Soil Quarterly (Hel3)
II)
Vegetation Quarterly Quarte ly Fluoride 1
ppm 12 Air Continuous lionthly Fluoride 0.02 cpb II)
Vegetation Monthly Monthly Fluoride 1
ppm 13 Air Continuous Monthly Fluoride O.C2 ppb Soil Quarterly (Held) fI)
Vegetation Quarterly Quarterly Fluoride 1
ppm E?iC-City Lift Station (see Table 7.1 -1)
STP(2)
Liquid Daily Monthly Uranium 0.1 ppm Sludge Quarterly Quarterly Uranium 0.01 ppm Yakima River (3)
Liquid Monthly Monthly
- Uranium, 0.1 pom
- Fluoride, 0.1 oca
- flitrate, 0.1 ppm A::roni a.
0.1 pom Sulphates &
1 ppm pH 0.1 unit
/
TABLE 7.2-1 (continued)
Sample Type of Collection Analysis Analyzed Min. Detection Station Samole Frequency Frequency For Level I#I Plant Drinking Water Liquid Weekly Weekly
- Uranium, 0.1 ppm.
-Fluoride.
0.1 ppm Ni t' rate.
0.1 pom
- Amonia, 0.1 ppm Sulphates &
1 ppm pH 0.1 unit Test Wells (15)
Liquid Monthly Monthly Conductivity (5) 0.1 umhos/cm I
(1) Collected monthly during the normal growing season.
(2) Richland Municipal Sewage Treatment Plant.
(3) Washington State Department of Ecology requirement.
(4) For purpose of background determinations.
(5) See Section 3..t.4 of ENC's " Application for Renewal of Special Nuclear Material License No. SNM-1227", Document No. XN-2, for Lagoon Leak Action Guides based upon conductivity levels in Test Well water.
It should be noted that ENC previously collected weekly samples from each Test Well and analyzed them for uranium, fluoride, nitrate, amonia, sulphates and pH, and those data are presented in the response to Comment No. 7.3.
l I
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sissi,,,,
' /' ' ' / s i s
/
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m Liquid Sample
/
Horn Rapids Road
/
a Na2CO Treated Filter 3
Soil Sample f
o Vegetation Sample e
o 00E Property r = 2000 ft.
/
% rs
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e
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e i
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o
//
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13
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/y5 d
- 72 '
W e
CITY OF RICHLAND i /
X ty Sewer Treatment P nt O'
'N i
2 3,
!!! MILES i
~ - ~ ~ ~ ~.....,
=
7 E
,4 T* I4 Ts :s
. ro pi-.
?dl e
- 4. :
1 1'
I i
I 35*.30 t i
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L
. me i
4 353.35 !,
, -T.13 l
I s
352.90 i-hd4
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r
't i
!A ls N
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T-i
,i l,.
i
! 7 o6 js2.co l
.' f*-
l+.
i i
- ; e PJ7 l
Tat? v Ass.3T *~~ ~ ~
-1
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n
<y
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v i
1.
n.,
FIGURE 7.2-2 Test Well Locations (Relatiye to EitC Lagoons)
/
I TABLE 7.3-1 Uranium Discharged In Gasecus Effluents (1976-1980)
Amo'unt of. Uranium
, uarter Discharged (dCi)
Q Year 1976 1st 1.3
- ~
2nd 1.9 3rd 1.5 4th 6.2 1977 1st 1.4 2nd 2.6 3rd 5.0 4th 5.6 1978 1st 6.0 2nd 6.8 3rd 93.7 4th 18.7 1979 1st 12.0 t
2nd 8.7 3rd 12.8 4th 6.1 1980 1st 11.2 2nd 7.0 3rd 7.9 4th 9,9 1
t
/
IABLE 7.3-2 Sunnary of Chemical Characteristics of Liquid Streams (1976-1980) flitrate + Ammonta
_ Fluoride (pp,n)
(asN)(pg Sulfate (ppm) pil Hiql_t Low Ave.
High Low Ave.
Liquid Stream Righ Low Ave.
gish Low Ave.
I2)
II 5.7 7.6 EtlC-City Lif t Station 4
<0.1
<1 28 1
3 28
<1 17 9.8 III Clarifier Ef fluent 2.6
<0.1
<1 115 1
45 3000
<1 40 8.3 6.9 7.5 STP
[IlC Plant Water Supply 3
<0.1
<1 6
<1 2
25
<1 15 9.4 7.0 7.8 Yakima River 7
<0.1
<1 33 1
3 710
<1 22 9.7 S.2 8.1 IId Richland Municipal sewage treatment plant.-
I2) tjuring this period, there were 18 daily ENC-City Lif t Station samples whose pil values were cutside the range of 6.5-8.5.
p
TABLE 7.3-3 Fluoride Discharged In Gaseous Effluents From UF.-UO,, Convers. ion Ocerations (1976-1980)
Amount of Fluoride Year Month Discharged (grams) ~
~~
1976 January
~
25'
~
February-32 11 arch 22 April 40 May
'45 June 61 Jgly 35 August 33 September 45 October 39 November 31 Decemcer 33 1977 January 100 February 36 March 32 April 24
!!ay 24 June 10 July 30 August 9
September 5
October 12 flovember 19 December 3
1978 January 14 February 73 March 48 April 102 May 55 June 46 July 40 August 34 September 98 October 175 November 240 December 155 t
0
TABLE 7.3-3 (continued)
Amount of Fluoride Year Month Discharged (grams) 1979 January.
153 February 130 March
' 78 April 60 75 May 195 June July 198 August 56 September 162 October 99 November 58 December 145 1980 January 88 February 110 March 105 April 255 May 125 June
.105 July 185 August 478 September 441 October
(*)
November
(*)
December
(*)
(*) Sample analytical results not yet available.
/
STAit OF UASillNGTON E:iCLOSU'1E 7.3.4 DEPARTMLt1T OF CCOLOGY Chapter 18-48 WAC FLUORIDC 51/J:DAR05 Ef fective February 4,1971 WAC 18-48-080 PREAMBLE.
In the' interest of the' people of the State of Wsh-Ington, it is the objective of the State Department of Ecolocy to cbtain and maintain tFc cleanest air possible, consistent with,the highest and best prac-ticable control technology.
In areas where existing concentrations are lower than concentrations allowed by the standards enumerated below, degradation of the atmosphere shculd be min-imized. The highest and best practicable control technology shculd be applied a to all scurces emitting fluorides to the atmosphere unless it is determined by the responsible air pollution control agency that application of lesser tech-nology is justified. Air quality standards should not be construed to encourage degradatien of existing air quality.
WAC 18-L8-090 POLICY LIMITATIONS. The standards set forth within these regu-lations are intended to protect lives tock and vegetatice. All sampling to meas -
ure cempliance with said standards will be conducted in areas and during time periods apprepriate to protect vegetatien and livestock.
WAC 18-48-100 DEFiftlTIONS.
(1) Forage
-Grasses, pasture and other vegeta-tien that is consumed or is intended to be consumed by livestock.
(2) Cured Forage - Hay, straw, ensi.lage that is censumed or is Intended to be consumed by livestock.
(3) Ambient Air - The surrounding outside air.
(4) Ambient Air quality Standard - An established concentration, exposure time and frequency of cccurrence of a contaminant or multiple contaminants in the cmbient af. which shal1 not be exceeded.
(5) Standard conditions - Sixty (60) degrees Fahrenheit and fourteen and seven' tenths (14.7) pounds per square Inch absolute.
WAC 18-48-110 It!TEt:T OF REGULATIONS. Two standards are established by these rules. One shall be for the fluoride content of forage and the other,for gas-cous fluorides in the ambient air. No person shall cause, let, permi t, or allcw any cmissicn of cicmental or ebemically combined fluorine, which eiqher alone or inicembination with other fluorides that may be present in forage or the ambient air, to be in excess of the standards in WAC 18-48-120 and 130.
VAC 18-48-120 FORAGE ST/f 0/,PDS.
(1) The f?uoride content of forage calcu-lateu cy cry v,eight shall not exceed:
(a) Forty parts per million flucrlde Icn (40 ppm F ) average for any twelve (12) censecutive months.
~
(b) Sixty pcrts per million fluoride icn (60 ppm F ) cach month fer more than two (2) consecutive mcnths.
(c) Eighty parts per million fluoride ion (SO ppm F ) more than once in any two (2) censecutive months.
(2) in arcas where cattic are not grazed continually, but are fed cured forage part of the year the fluoride centent of the cured forage shall be used es the forge fit.oride centent for as many months as Jt is fed to establish the yearly o ve r at;e.
(3) Co..d forage grcwn for sale as livestock feed shall not exceed forth-parts per mi'iion fluoride ton (40 ppm F ) by dry weight a'fter curing er pre-e paring for sale
~
WAC 18-48-130 AMGIENT AIR STANDARDS. Gasecus ' fluorides in the ambient air -
calculated as HF at s tandord conditions shall not exec *ed:
(1) Three and seven-tenths micrograms per cubic meter (3.7 pg/m ) average 3
for any ' twelve (12) censecutive heurs; (2) Two and nine-tenths micregrams per cubic meter (2.9 pg/m ) average for 3
any twenty-four (24) censecutive hcurs; (3) One and seven-tenths mieregrams per cubic meter (1.7 pg/m ) average for 3
any seven (7) consecutive days; (4) Eighty-four ene hundredths mieregrams per cubic meter (0.84 pg/m )
3 average fer any thirty (30) consecutive days; (5) Five-terths micregrams per cubic meter (0.5 pg/m ) average for the period 3
March I thrcugh Oc:cher 31 cf any year.
WAC 18-43-1 Q COMPLIANCE WITH STANDARDS. When requested by the Director of the State Department of Ecology, persons emitting fluorides to the atmosphere shall be required to establish their cempliance with WAC 18-48-120 and 130 by conducting a menitering program approved in writing by the Of rector of the Department of Ecology and subtricting all data cbtained to the Director.
WAC 18-48-150 SA:*.PLING AND ANALYSIS.
(1) Forage soeples.shall. be taken ence each calencar menth at intervals of twenty five (25) to thirty five (35) days, to determine ccr.pliance with WAC 18-48-120.
(2) Gasceus fluoride shall be sampled according to the approved monitoring using the sodium bicarbonate tube methed.
- program, (3) Samples shall be analy:ed by the Technicon Auto Analyzer or the Mcdified
~
Willard-Winter Distillation Methed. The Orten prebe may be used to analyze the gaseous ambient air sample when the fluo-ide is in soluble form.
(4) Sampling and analysis shell be in acccedance witb techniques approved by, and en file with, the Departrrent of Ecolcgy. Other sampilng and rnetheds of an-l atysis v.hich are equivalent in accuracy, sensitivity, reproducibility znd men t. ' applicability uncer similar conditions may be used af ter appreval by the Depart-WAC 18-48-010 threugh 18-48-070 are cach hereby repealed, l
/
TABLE 7.3-4 Summary of Fluoride Concentrations (Monthly Averages) in Environmental Ambient Air 30-Day 3
Sample Station Concentration (uqF/m )
.No. of S'ampjes Station Location Year Hign Lcw Mean
" Exceeding Standard ())
(2)
^ <0.02
<0.02 1976 0.05 1-A 1977 0.22
<0.02
<0.02 -
1978 0.07
<0.02 0.03 1979 0.6
<0.02 0.06' 1980 0.31
<0.02 0.2 (3) 1976
<0.02
<0.02
<0.02 1-B 1977 0.22
<0.02
<0.02 1978 3.2
<0.02 0.05 1
1979 0.47
<0.02 0.05 1980 0.3
<0.02 0.12 (3) 1976
<0.02
<0.02
<0.02 2-B 1977 0.48
<0.02
<0.02 1978 11.4
<0.02
<0.02 2
1979 0.27
<0.02 0.05 1980 0.8
<0.02 0.14 (2) 1976
<0.02
<0.02
<0.02 3-3 1977
<0.02
<0.02
<0.02 1978 1.2
<0.02 0.06 1
1979 0.26
<0.02 0.05 1980 0.5 0.06 0.14 (2) 1976 0.5
<0.d2
<0.02 4-B 1977 0.45
<0.02
<0.02 1978 0.56
<0.02 0.05.
1979 1.1
<0.02 0.08 1
l 1980 4.0 0.19 0.5 2
(3) 5 1976
<0.02
<0.02
<0.02 1977 0.42
<0.02
<0.02 1978 0.24
<0.02
<0.02 1979 0.6
<0.02 0.05 1980 1.0
<0.02 0.15 1
l L
/
r.
__y
o...
TABLE 7.3-4
~ ntinued) 30-Day 3
Sample Station Concentration hqF/m )
No.ofIamoles Station Location Year High Low tiean
-Exceedine Standard (I)
(3)
' 0.02
<0.02 '
1976 40.02 11 1977 1.7
<0.02
<0.02 1.
1978 6.9
<0.02
O.03 1
1979 2.6
<0.02 0.05 1
1980 0.21 0.03 0.15 (4) 1976
<0.02
<0.02
<0.02 12 1977 2.3
<0.02
<0.02 1
1978 9.0
<0.02
<0.02 1
1979 0.8
<0.02 0.06 1980 0.45 0.03 0.1' (5) 1976 0.09
<0.02
<0.02 13 1977 1.7
<0.02
<0.02 1
1978 3.1
<0.02 0.04 1
1979 0.35
<0.02 0.1 1980 0.31
<0.02 0.12 (1) Reference Enclosure 7.3.4 (WAC 18-48-130(4)).
(2) ENC property - desert land.
(3) DOE property - desert land.
(4) Battelle Pacific Northwest Laboratory property - routinely under cultivation, but no forage grown on this property during this period.
(5) City of Richland procerty - residential area.
(
/
{
L
1 TABLE 7.3-5 Summary of Fluoride Content of Environmental Vegetation Samoles Sample Station Fluoride Content (ccm)
No. of to.?ditions
~
Station Location Year High,
Low Mean Exceedine Standard'))
(2) 1976 65 4
21
-0 ~ ^
l-A 1977 101 8'
36 26 1978 477 6
1979 89 67 81 1980 90 37 73 (3) 1976 49 4
14 1-3 1977 109 1
27 1978 566 3
20 1919 47 40 44 1980 72 10 37 (3) 1976 37 2
11 5 1977 73 12 24 1978 85 14 39
' 1979 133 41 87 1980 34 20 29 (3) 1976 24 9
24 11 1977 39 23 35 1978 190 2
53 1979 50 44 47 1980 61 9
20 (#)
1976 49 10 12 1977 54 14 27 1973 216
<1 21 1979 78 31 58 1980 60 2
36 (3) 1980 29 17 21 13 (1) kcfe-ence E. closure 7.3.4 (WAC 18-J8-120). However, no forage has been raised in the influenced area during this period.
(2) ENC property - desert land.
(3) DOE property - desert land.
(4) Battelle Pacific Northwest 8.aboratory property - routinely under cultivation, but no forage grown on this property during this period.
(5) City of Richland property - resicential area. Vegetation sampics were not collected at this station during 1976-1979.
/
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