ELV-00902, Requests Exemption from 10CFR20,App A,Footnote d-2(c) Re Worker Respiratory Protection Apparatus to Permit Utilization of Air Purifying Respirators in Lieu of Supplied Air or self-contained Breathing Apparatus
| ML20248C949 | |
| Person / Time | |
|---|---|
| Site: | Vogtle  |
| Issue date: | 09/28/1989 |
| From: | Hairston W GEORGIA POWER CO. |
| To: | NRC OFFICE OF INFORMATION RESOURCES MANAGEMENT (IRM) |
| References | |
| RTR-NUREG-CR-3403 ELV-00902, ELV-902, NUDOCS 8910040077 | |
| Download: ML20248C949 (73) | |
Text
,-
. _C i Georgia Power Campany
+ ~ - ",
333 Piedmont twenae 6
_ Atanta, Gewga 30308
'~
. Telephone 404 52G3195 tdanng Address: _
p 40 inverness Center Parkway i'
Post Ofhee Box (295 L
B;rmingham, Alabama 35201 U
. Telephone 205 868 5581 September'28, 1989
" """ "
- h*"i W. G. Hairston, HI L
Senior Vice President V
Nuclear Operahons ELV-00902 0021-Docket No.
50-425' U. S. Nuclear Regulatory Commission ATTN:. Document Control Desk Washington, D. C.
20555 Gentlemen:
V0GTLE ELECTRIC GENERATING PLANT EXEMPTION REQUEST - WORKER RESPIRATORY PROTECTION APPARATUS In accordance with the'prov.isions of 10 CFR 20.103(e) and 10 CFR 20.501, Georgia Power Company-(GPC) hereby requests an exemption for Vogtle' Electric Generating Plant.'- Unit 2 (VEGP) from 10 CFR 20, Appendix A, footnote d-2(c) which ' states, with respect to establishing personnel protection factors, "No allowance is to be made for the use of solvent canisters against-radioactive gases and vapors." GPC proposes to use a protection factor equal to 50 for solvent' iodine canisters in an atmosphere containing radiciodine. A safety analysis is provided as Enclosure I which demonstrates the exemption will not result in an undue h zard to life or property.
The' requested ~ exemption for VEGP - Unit 2 would allow utilization of air purifying respirators in lieu of supplied air or self-contained breathing apparatuses. The air purifying respirators, MSA GMR-1 canisters, which GPC proposes to use would be manufactured by Mine Safety Appliance Company (MSA). A copy of the MSA test report and correspondence justifying Category C storage is included as Enclosures 2, 3, and 4 to this letter.
' A similar exception that would allow the use of the MSA GMR-1 canister was granted by.the NRC for VEGP-Unit 1 on October 27, 1988.
10 CFR 20.103(e) allows the Commission to authorize the use of equipment which has not been certified by NIOSH/MSHA but which has been tested reliable under proposed conditions of use. The MSA GMR-I canister has been adequately tested, as evidenced by the MSA tests and previously granted exemptions. GPC asks that this request for an exemption be acted on by the
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4 8910040077 890928 PDR ADOCK 05000425 P
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. Georgia Power n( -
U.S. Nuclear Regulatory Commission ELV-00902 Paae:Two l'
NRC.by February 1,1990.to allow the use of these canisters in the initial
. refueling outage.
Sincerely, h.f.
- TE.
L W. G. Hairston, III-WGH,III/PAH/gm
Enclosures:
'1.
Safety Analysis
'2.
_MSA Test Report 3.
Letter from MSA dated April 5, 1989 4.
Letter from MSA dated September 18, 1989 xc: Georaia Power Company Mr. C. K McCoy
. Mr. 'G. Bockhold, Jr.
~
Mr. R. Odom Mr. P. D. Rushton NORMS U.
S~. Nuclear Reaulatory Commission Mr. S. Ebneter, Regional Administrator Mr. J. B. Hopkins, Licensing Project Manager Mr. J. F. Rogge, Senior Resident Inspector. - Operations, Vogtle l
.1
ENCLOSURE 1 TO ELV-00902 PROPOSAL FOR EXEMPTION FROM 10 CFR 20, Appendix A, footnote d-2(c)
Allowing Use of the GMR-1 Canister Against Radioiodine ABSTRACT:
This proposal is a request for exemption from 10 CFR 20, Appendix A, footnote d-2(c) in accordance with 10 CFR 20.103 (e) and will cover Georgia Power's facility Vogtle Electric Generating Plant Unit 2.
The desired conclusion is the use of the MSA GMR-1 canister and a full facepiece, that has the capability of providing a protection factor of 100 or greater, to achieve a protection factor of 50 against radioactive iodine and particulate.
JUSTIFICATION:
The benefits associated in using the GMR-1 over Air-lines or SCBA's are an I
increase in worker safety and a reduction in worker exposure to radiation.
Worker Safety is greatly improved by (1) reducing the respiratory protection equipment weight causing a decrease in probability for back injury or falling / tripping injury, (2) eliminating accidents caused by a loss of air situation, (3) reducing worker fatigue by deleting entangled air lines, uncomfortable harnesses and eye irritation caused by the air flow, (4) removing the false feeling of coolness caused by the air flow across the face that can lead to heat stroke and eventually fainting, and (5) reducing workers time in the respiratory protection equipment by 25-50% due to the increased work efficiency.
Exposure Reduction is achieved by the decrease in work time to the corresponding measures of 25-50% in cases that normally require the use of Air-lines or SCBA applications.
OPERATING CONDITIONS:
With guidance from NUREG/CR-3403, the following precautions and limitations are proposed:
(1) The maximum permissible continuous use time for a GMR-1 canister is eight (8) hours after which the canister is discarded. This time will be calculated from the moment the canister is unsealed, and will include periods of non-exposure.
(2) The GMR-1 canister will not be stored or used in the presence of organic solvent vapors.
Procedure will deny the use or storage of these canisters in areas that painting or use of organic vapors / chemical is in progress or has recently been completed.
(3) Canisters will be stored in sealed humidity-barrier packaging in a cool dry environment (Class C).
(4) The GMR-1 canister will be used with full facepiece capable of providing a protection factor equal to er greater than 500. _ - _ _ _ _ _ _ _
,4 (5) The GMR-1 canister will.not be used in temperatures greater than 110
-degrees-Fahrenheit er up to 120 degrees Fahrenheit if the dewpoint is equal-to or less than 107 degrees Fahrenheit. Temperatures will be measured prior to and/or during.the use of the GMR-1 canister to assure the working temperatures are within limits.
c l
(6) Air samples will be taken prior to and during any activities that involve ~
the use of the GMR-1 canister for protection against radioactive iodine.
. (7) The organic vapors and chemicals of concern relative to GMR-1 canister-use at Vogtle Electric Generating Plant:
Xylene 111 Trichloromethane Naphthalene Methyl Ethyl Ketone Methylnamyl Ketone Toulene Cycholexanone Acetone
. Trichlorofluoromethane Butanone These vapors and' chemicals are not of concern is areas where GMR-1 canisters will be routinely stored. The canisters are purchased in a hermetically sealed condition and are not opened until placed in' service.
Vogtle Technical. Specification 4.7.7 defines the availability and surveillance requirements related to the Auxiliary Building Radiation Area.
Filter Exhaust and' Continuous. Exhaust System. The Containment Purification and Clean-up system and the Auxiliary Building Radiation Area Filter Exhaust and Continuous Exhaust System plant procedures, governing the operability and functioning of charcoal beds, are in compliance with Regulatory Guides 1.140 and 1.52 for design, testing and maintenance of filtration systems. These requirements are utilized to demonstrate system operability with respect to HEPA and charcoal filters.
Since GMR-1 canister will be in the same areas served by these systems, assurance of continuing operability of these systems will provide assurance of a proper environment (i.e., no organic vapors or chemicals) for GMR-1 canister use.
(8) A GMR-1 canister found to have exceeded 3 years from date of manufacture will not be used for protection against radioactive iodine.
(9) Canisters are not to be used in total challenge concentrations or organic iodines and other halogenated compounds greater than 1 ppm, including nonradioactive compounds.
l PROGRAM IMPLEMENTATION:
In the initial implementation of the GMR-1 program, the following verification measures will be in effect:
y a.
Weekly whole body counts for individuals using the GMR-1 canisters for radioiodine protection.
b.
A whole body count for individuals that exceed 10 MPC in a week and used the GMR-1 cansiter for respiratory protection in that period.
l
-2, L
c.
Anyone that measure 70 nCi or greater iodine uptake to the thyroid during a whole body count will be restricted from entering a radioiodine atmosphere pending Health Physics evaluation.
1 d.
The radiological survey and whole body count information will be complied to evaluated the effectiveness of the program.
These precautions will be relaxed as the data proves the effectiveness of the program.
RADIATION WASTE REDUCTIONS:
Due to the greater volume of the GMR-1 canister over a standard particulate filter, the particulate filter will normally be used in situations permitted to reduce the generation of radioactive waste.
PROCEDURES AND TRAINING:
Upon approval, procedures will be created or revised to define the proper storage, issuing and use of the GMR-1 canister prior to program implementation.
These revisions will include the restrictions and limitations of the GMR-1 canister that has been formulated in the proposal. The procedures that will be modified are Department VEGP 47001-C and Administrative VEGP 00970-C. Training of the workers on the proper use and the limitations of the GMR-1 canister will be performed prior to issuing and shall be incorporated into the GET respirator training program. The Health Physics staff will be qualified on the procedures and shall receive training on the characteristics of the GMR-1 canister.
Additionally, onsite Quality Assurance audits and surveillance of the Respiratory Protection Program will be expanded to include GMR-1 canister use and associated procedures and controls.
ENGINEERING CONTROLS:
This proposal does not lessen the responsibilities of the licensee in the use of engineering controls to relieve the needs for respiratory protection as required in 10 CFR 20.103 (b) (1). These measures include but are not limited to, degasification of the reactor coolant system, crud burst clean up, process to confine or eliminate airborne radioactivity, delay breaches of primary systems to allow decay of radioisotopes and area decontamination to decrease possibilities of generating airborne radioactive material.
OVALITY ASSURANCE:
The Quality Assurance program established and maintained by the Mine Safety Appliance Company is sufficient in supplying the GMR-1 canister in proper operating condition. Only canisters covered by the MSA GMR-1 Quality Assurance program will be used for the pr3tection against radioactive iodine. To ensure that the MSA GMR-1 canisters meet standards for quality control, procedure number 47001-C or a Department Instruction will require personnel verify that for each canister used with the protection factor that the seal is intact, the canister shelf life has not expired and the following MSA label is attached to the GMR-1 canister: ____- _______ -
l "This canister meets the NRC Quality Assurance Specification required for Radiodine Protection Factor Credit, in addition to the NIOSM/MSHA Requirements.
Credit may only be taken by licensees who have been granted an NRC Exemption."
TEST DATA:
This proposal is based on studies performed by the Mine Safety Appliances Company, enclosure 2, NUREG/CR 3403 and is structured after NRC approved programs at Georgia Power Company Plant Hatch and Union Electric Company. The parameters of the studies specifically air temperature and humidity, cover the conditions that exist at Vogtle Electric Generating Plant.
Enclosures 3 and 4 justify reducing the storage requirements of the canisters from Class A to Class C.
CLOSING STATEMENT:
This proposal is based on data and contains the controls deemed acceptable by the NRC as a proper GMR-1 canister program.
This exemption will allow Georgia Power Company to increase worker safety, by a decrease in work stress and radiation exposure, without effecting the safety of the general public. This proposal also acts as notification of GMR-1 canister use 30 days following exemption approval. - _ _ _ _ _ - _ _ _
l l
i.. :.
l ENCLOSURE 2 To,Ej.V-00902 1
THE MSA GMR-I CANISTER FOR USE AGAINST RADIO IODINE All0 CRGANIC ICDICES Note:
Presented by Dr. E. 5. McKee, Mine Safety Aopliances Company, Pittsburgh, Pennsylvania for Alabama Power Company to Nuclear Regulatory Comission staff on April 25, 1984 at Bethesda, Maryland 4
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REQUIREMENTS FOR NIOSH APPROVAL FOR AN ORGANIC VAPOR CHIN CANISTER PER 30 CFR 11' Test Conditions Challenge cone. 5000 ppm CC1 4 Test Humidity 50 t, St RH Test Temperature 25 t,2.50' C Flow 64 LPM for as received canisters 32 LPM for equilibrated canisters Breakthrough conc. 5 ppm fouilibration Conditions
~
3' Canisters as received.
2 Canisters equilibrated for 6 hrs., 64 LPM, 255 RH. Room Temp.
2 Canisters equilibrated for 6 hrs., 64 LPM, 855 RH, Room Temp.
Total 7 canisters.
Service Time Requirement 12 minutes.
No statistical requirements.
If all seven canisters have service times of' 12 minutes or more, the canister is approved.
e 9
4 11 '
=
4 ELui?LE OF LOT EVALUATION PER MIL.-STD-414 SINGLE SPECIFICATION LIMIT - FORM i VARIABILITY UNCDt?N - STA'iDARD CIVIATION METHOD (P.ET. PAC LEVEL II AQL = 1.0" SPEC. LIMIT 1.0E LOT SIII - 500 CANS SA}2LE SIZE (TABLE A ' I-1)
- 7 (")
2 TEST RESL1 S:
8 EOUR 3RE.aJCTF. ROUGH CAN #
CONCENTRATION (%)
41
.056 42
.028 43
.019 44
.064' 45
.027 6
46
.035
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.170 SAHFLE MEAN =.06129 (i)
ESTIMATE OF LOT STANDARD DEV!ATION =.05354 (s)
TNZ QUANTITT (U-2)/s = 1.00
.06129 = 17.53
.0535%
ACCEPT IILITT CONSTANT (k) = 1.62 (TA3LE 5-1)
LOT.
ACCEPIA3ILITY CRITIF.II:: SINCE U-2/s> k s
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T:tc1 Radictica Doscg:--
Compcrison of D:ta Showing Tina Inv31v:d and Workers Wearing Air-Line Respirators or SCBAs vs. Q4R-I Respirators f
Corresponding No. of Persons Task Time Total Dose Dose Rate Required to Work Hours (Total Task (MR/he)
Perform Task Required to Time x Dose for Each Wearing:
Perform Task Rate) i Task with Workers with Workers Wearing:
Wearing:
A-LR A-LR A-LR or GMR-I or GMR-I or GMR-I SCBA Can SCBA Can SCRA
__Can Pressure 26 6
6 7
5 182 130 Safety Valve Testing Containment 11 6
6 57 37 627 407 Sump Work RCS Seal 55 12 9
180 135 9,900 7,425 Inspect &
Replace Reactor 22 18 18 314 235 6,908 5,170 Cavity Decon 3
RRR Check 37 5
4 52 39 1,924 1,443 Valve Repair Accumulator 45 8
6 77 58 3,465 2,610 Check Valve Repair RER Heat 59 13 10 144 100 8,496 5,900 Exchanger Gasket Replacement Spent Fuel 12 4
4 21 16 252 192 Pool Transfer Canal Work Containment 75 9
6 27 12 2,025 900 Ent ry at 100% Pot er Incore 17 16 12 90 68 1,530 1,156 Thimble Cleaning Totals 97 81 969 705 35,309 25,333
Mine safety Apoliances Cornpany 600 Penn Center Soulevard P;ttsourgh, Pennsylvania 15235 4:24273 5000 4,79) jy jgg4
- 8ter s o.tect o46 Numcor 412-273-5140 PERFORMANCE DATA FOR MSA'S GMt-I CANISTER SUBMITTE In accordance with our agreement, de following report is submitted for your approval.
1.
Gkneral g
It was agreed with Company on March 8,'1984, that MSA would test GMR-! cans to compiegion in order to be able t2 statistic-ally project performance at 110 F and 100% RM.
In addition, other tests had been run prior to the March 8th agreement and the data are shown in Table !.
i ditions:
The tests were conducted under the following con-Challenge Cone.: 5 - 10 com CH J Humidi ty:
60 + 3% and B0 t J31 3(minimum of six cans at end humidity)
Temner.ture- [110*A ICyclic, Flow:1 192 LPM for 0.82 sec.; 0 LPM for 1.64 sec.,
repeating this evele throuchout the test.
Thisgivesaginutevolumeof64L.1 Breakthrough Conc.:
1% of the ena11enge concentration 2.
Test Results During ttfis program 48 GMR-I cans have been tested (47 valid tests).
These cans came from six production lots made over the period Acril 14, 1983, to February 2,1984
'1983,10 at 905 RH and 6 at 60 RH. Sixteen cans were tested from lot April 14, Only eight results at 90% RH were used in the statistical analysis given below, as one test was invalid (No. 47) and another was stopped before completion.
Only a few cans were available from the other lots, so they could not be statistically analyzed; however, all cans run to completion had a service time of i
o e.
}
i 20 hours2.314815e-4 days <br />0.00556 hours <br />3.306878e-5 weeks <br />7.61e-6 months <br /> or greater.
The results are shown in Table 1.
The original 14 cans not run to comolation had service times well in exces hours - much.in excess of the eight hours desired.
'3.
Statistical Analysis of Lot 4/14/83.- Table 2 shows th; data used and the statistical. analysis to give the 99% prediction interval ~for individual values of Log Y humidity) is 1005.
The lower (log service time), when X (relative limit of this interval is calculated to be 15.8 hours9.259259e-5 days <br />0.00222 hours <br />1.322751e-5 weeks <br />3.044e-6 months <br />.
This predicts that over 99% of the individual GMR-I can service times would.be greater than.15.8 hours9.259259e-5 days <br />0.00222 hours <br />1.322751e-5 weeks <br />3.044e-6 months <br /> at 100%~ RH and the other test parameters used in this program.
considerable safety margin over the eight hours desired.This gives a One other interesting point to note from the data in Table 2, as well as all of the test data on the GMR-I cans, 60 to 90%.
close to those at 90% on a log service time--log RH slope were extremely steep--which is not the case.
4.
Proposed Acceptance Plan.
The extremely long service times experienced in this program for the GMR-I cans run to completion, an average of
.over 29 hours3.356481e-4 days <br />0.00806 hours <br />4.794974e-5 weeks <br />1.10345e-5 months <br />, makes testing to completion for routine lot accootance-impractical; therefore, the following clan is proposed.
4.1 Interim Plan.
On an interim basis, until more data can be gathered as explained in section 4.2, the proposed lot acceotance would be as follows:
4.1.1 MIL-STD 414. Level II, AQL 1% would be used to (1) select the proper number of cans to test, depending on lot size, and (2) to interpret the results regarding lot acceptance or failure.
4.1.2 The cans would be tested under the conditions of section however, all tests would be conducted at 905 RH.
Tests would be stopped at eight hours and the percent leakage recorded at tnis time.
From evidence ' presented in the preceding sections, results at 90% are not significant1v different from those at 100%.
4.1.3 The percent leakage values would be compared to the scec.
Ilmit of 1.0%, using the single spec. limit. variables unknown, standard deviation method of MIL-STD 414.
Acceptance would.be based on this analysis.
4.2 Future.
Because the tests in section 4.1 are very time consuming and somewhat difficult to run for regular cuality assurance lot acceptance testing, we plan to do further testing on the GMR-I can in an attempt to reduce the time required for testing and I
also to simplify the test.
Parameters that will be investigated l-are:
L
~
4.2.1 Increasing the challenge concentration of CH,I in an effort to reduce the time to test. - Under current cdaditions, a test to completion might run 40 hours4.62963e-4 days <br />0.0111 hours <br />6.613757e-5 weeks <br />1.522e-5 months <br />; we would like to reduce this to about two hours.
If there were a simple, straight-line. relationship between service time to a it breakthrough and ena11enge concentration. it would indi-cate that a challenge concentration of approximately 200 com would be required to do this. We wish to fimly establish the service time---challenge concentration re--
lationship ov.er a range of challenge concentrations from 1 ppm to 500 pga.
4.2.2 Constant Flow vs. Cyc1tc Flow.
Constant flow tests are much simpler to conduct than cyclic flow tests.
From some preliminary information. it appears that constant flow gives similar service times as cyclic flow.
If, by further tests, this can be verified, constant flow would be used in lot acceptance. tests.
4.2.3 Temperature and Hamidity Effects.
Further tests will be run to study the affects of temperature and humidity on the perfomance of the GMR-I can.
It to test cans for lot acceptance at 25'would be preferable C and 85t RH (standard NIOSH conditions it can be proven that these cenditions are as severe as). i{C and 905 RH. or if a g 43 correlation between these two conditions can be established.
5.
Conclusion.
5.1 Forty-seven GMR-I cans have been validly tested under the conditions specified in section 1.
All of these cans had service times well in excess of 12 hours1.388889e-4 days <br />0.00333 hours <br />1.984127e-5 weeks <br />4.566e-6 months <br />.
This compares to a desired service time of eight hours.
5.2 There were 14 valid tests run on lot 4/j4/83.
Statistical analysis of this data, projected to 1005 RH 110 F, indicate that over 99%
of the GMR-I cans in this lot have service times well over eight hours (15.8 hours9.259259e-5 days <br />0.00222 hours <br />1.322751e-5 weeks <br />3.044e-6 months <br />).
Incidentally, from the data of Table 1 this lot appears to have the shortest average service time of.the lots testad.
5.3 In licht of sections 5.1 and 5.2. Lthe GMR-I can should be considered toualified to aive service times over eight hourst under the con-ditions:
15 breakghrougn, cyclic flow (peak 192 LPM, average 64 LPM) 110,F (43 C) and 100% RH.
O
.f
~
5.4 Lot Acceptance will be determined by using MIL-STD-414, Leve AQL 1%.
The percent leakage at eight hours service time will be variables unknown, standard deviation method of M 5.5 Further tests will be run studying the effects of challenge concentration, constant flow rate, temperature and humidity on the service time of GMR-1 cans.
This program is intended to shorten the required test time and. simplify the test procedure.
5.6 between 60 to 90% has little effect on service canister.
plot, suggests that the service times at 90% and 1 not significantly different.
If you have any further questions, please do not hesitate to contact me Very t,ruly yours,
-d si s 2
Wayde Miller, Jr.
Director of Product & Sales Planning
/jw Attachments / Table I and 2 I
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NUREQ/CA 3403 LA.0827 PR Progress Report RH Criteria and Test Methods for Certifying Air-Purifying Respirator ~ Cartridges and Canisters Against Radiciodine October 1,1978-september 30,1982 Gerry O. Wood Frank O. Valdez Vincent Gutschick ManuscrtDt submetted: June 1943 Date auchenea: August 1983 Preparse for Cocupanonas macianon protocoon Stanca Oswision of Facihty Coeranons Omco of Nuclear Regulatory Aesearen US Nuclear Aegulatory Commesa.on wasnington. DC 20585 NMC FIN No. A7041 OS d
_ d
_ n @ Los Alamos NationalLaboratory W
U G) Los Alamos,New Mexico 87545
. s]
m:
t
,,4. ;
i
- 5. _
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,y CONTENTS
" ABSTRACT L...........................<....................I
!.i INTRODUCTION...... :........................"........ 2 o
II. ELEMENTAL IODINE GENERATION AND ADSORPTION ON-ACTIVATED CHARCOAL ;..........'........................ 2
. A. - Objectives......................................... 2;
- B. Generation.'......................................... 3 C. Retention 3
.r.
I!!. ' RADIO!ODINE STUDIES-EXPERIMENTAL
.....................4 g
A. Flow Systems........................................ 4 B.~ ~ Generation Methods
..............:4 C. Detection Methods 6-
.l D. Reagents.
.................,6-
) $,.;
E. ' Test Beds............,............................. 7 IV. RADIOIODINE STUDIES-RESULTS AND CONCLUSIONS 7-A. Comparisons of Vapor Species 7
i B. ' Methyl Iodide Versus Methyl Radiciodide......................... 9 L
C. Effects of Bed Depth and Contact Time
.........................11 D. ' Effects of Challenge Concentrations....,.....................
12 E. Cartridge Comparisons -.................................
14
' V. EFFECTS OF USE CONDITIONS............................. !$
A. E Relative Humidity.
................15
=B.
Temperature
..................;....................18 i.
C. Flowrate
.........................................21 l'
D. ' Reproducibilities of Service Lifs Measurements
....................21 VI. EFFECTS OF CYCLIC FLOW BREATHING PA'! TERNS
..............22 A. B ack ground........................................ 22
' B.' Computer M odeling Study................................ 22
' C. Experimental! Study
..........................26 D." Conclusions.......................................25 l
^
k-k-
n l.
t VIL DESORPTION OF TEDA FROM IMPREGNATED CHARCOALS...........'29
' A. B ack ground....................................... 2 9 B. Apparatus and Procedures 29 30 C. Results and Conclusions VIII. Test Apparatus Development 32 IX. DEVELOPMENT OF APPROVAL CRITERIA FOR RADIOIODINE CANISTERS 33 A.
History 33 B. Current Recommendations 35 X. ASSISTANCE TO NIOSH IN ESTABLISHING A TESTING AND CERTIFICATION PROGRAM 36 REFERENCES 37 APPENDIX 38 0
sw
____.-._______m_____________._____
I.
p-s e
W CRITERIA AND TEST METHODS FOR CERTIFYING AIR PURIFYING RESPIRATOR CARTRIDGES AND CANISTERS'AGAINST RADIOIODINE October 1,1978 - September 30,1982 bY Geny O. Wood
' Frank O. Valdez Vincent Gatschick Prepared for Office of Nuclear Regulatory Research U.S. Nuclear Regulatory Commission Washington, DC 205$5 NRC FIN No. A7041 ABSTRACT A project has been completed which provides experimental data and recommends-i if i
ifi tions for establishing a standard test procedure and acceptance cr ter a or a r-pur y ng respirator cartridges and canisters used for airborne radioiodine. Previous experimental work with methyl iodide vapor was extended to generate elemental iodine and measure its removal by charcoals. A special apparatus was constructed and used to simultar.e-ously measure penetrations of radiciodine and normal Iodine vapor species through beds of various charcoals. Normal methyl lodide (I 127) was selected as the most representative vapor species for testing and its limitations were identified. EEsets of testing and use conditions (bed depth, contact time, concentration, relative humidity,
' temperature, flowrate, and flow cycling) were studied to identify testing requirements.
Temperature and simulated breathing flow cycling were shown to have much more significance than was previously realized. Recommendations for testing and approval include considering the effects of all these parameters. An apparatus designed and built for testing has been de!!vered to the National Institute for occupational Safety and Heskh. In one related study the desorption of triethylenediamine (TEDA), a chrrcoal,
impregnant for organie iodide removal, was found to be insignificant at normal caniste use conditions-
4
..n lg.
L INTRODUCTION (II) Development of final acceptance tests. ap.
paratus, and criteria to be recommended to NRC for.
, - De main' goal of this project has been to provide the approval of respirator cartridges against radiciodine.
Nuclear Regulatory Commission (NRC), the Nadonal (12) Publication of results of this project and transfer Institute for Occupadonal Safety and Health (NIOSH) of the test procedures and techniques developed to the Tesung' and Certification Branch (TCB), respirator NIOSH TCB and assistance to them in the development manufacturers, and respirator users with data, recom.
of an approval schedule.-
mandations, and proven test methods for certifying air.
Items 8,9, and 10 have been added to the original plan purifying respirators againn radiciodine. Since facepiece to address concerns which have arisen as the project fit is beiig brmined at Los Alamos and elsewhere in developed. In addidon, a complete, ready.to-use test other studies, the main concern in this project was with apparatus has been built for the NIOSH TCB to use for the air. purifying canister or cartridge used with certification testing.
. facepieces.
A preceding progress report covered the first three of 8
~ Steps which have been taken to accomplish this goal the above steps and' included the background for this aret project. This report includes and organizes work re-(1) Survey and analysis of the literature relating to poned since September 1978 in quarterly letter reports, air. purifying respirators, vapor adsorption, and radio.
presentations at professional meetings, and publications.
iodine air. cleaning.. Contacts with professionals ex.
With the excepdons of some journal publicadons to perienced in these fields.
follow, this is the final report for this project.
(2) Design and construction of an experimental
. cpparatus for sorbent testing, including generation and g, etection systems for nonradioactive 88'I vapor species.
II. ELEMENTAL IODINE GENERATION AND (3) Experimental study of the adsorption of methyl ADSORPTION ON AC7WATED CHARCOAL iodide on a variety of potential respirator sorbents and examination of the effects of environmental and cartridge A-Objectives design parameters on this adsorption.
1 (4) Experimental study of the adsorption of elemen.
Testing of a selected adsorbent, an unimpregnated I
tal iodine vapors under limited condidons.
activated charcoal, for adsorption of elementaliodine at (5) Experimental study of the adsorption of ppm challenge concentrations was done to examine the hypoiodous acid (HOI) vapors.
usefulness of f generation and detection methods and to (6) Design and construeden of facilities for the use
. demonstrate the kinds of results that might be expected af radiciodine for sorbent testing and development of in a respirator cartridge test.
radi: iodine generators and detectors.
(7) Experimental study of the adsorption ofiodine vapor species tagged with 8881 for comparisons of results B. Generation with those obtained using stable 88'I species.
(8) Studies of the effects of relative humidity, tem.
One I generation technique used a flow of air (10 perature, flowrate, and concentration on cartridge per.
1/ min) to pick up I, and H 0 evaporating from an 3
form:nce and service life.
aqueous solution (s10-8 moles /L). Reistive humidity (9) Measurements of desorpden rates of charcoal resuhing from H 0 cvaporadon was about 50%. The 3
impregnants used to enhance methyliodide removal.
cha!!enge and test bed breakthrough concentrations were (10) Evaluation of effects cicyclic flow on efficiencies measured using calibrated oxidant meters (Mast Model and service lives of potential radiciodine canisters.
724 5). The challenge concentration (C ) of1 generated 2
L 1-
Q in air was directly proportional to In concentratieri in 3
"1
' ' E solution [C, (mg/m3) = 26400 [I ] (moles /L)]. Both
,E, concentrations decreased linearly with time as I evaporated faster than H 0.
- E 2
Another geneestion technique involved the sublima.
g O
tion of 1 crystals at controlled temperatures into a
- c 3
4 flowing air stream. Cha!!enge concentrations of 8-30
@ 10 mg/m'(1-4 ppm), determined by weight losses and air o
E 0.5."
flow rates (10 L/ min), were relatively steady for up to a g
week.
y acw
.02-sc C. Retention a
,,,,,,g 1
10 100 The activated charcoal used for these studies was 6/16 mesh from Union Carbide.
CH ALLENGE CONCENTR ATION (ppm)
Fractional bed breakthrough C,/C, from I genera.
Fig. I. Iodine breakthrough times for a 6/16-mesh Union tion from solutions increased from zero to a constant Carbide sedvated chsrecal bed,1.25-em deep 2.4-em value in a time intervrJ (10-120 min) dependent on bed dam,10 m s now. Open ermM are for m relative humdicy and solid symbols are for 90% relative condition and challenge concentration. This limit value humidity experiments. Fractional bed penetradonst a for of C,/C, was constant over a wide range (X 300) of C.
0.02, a for 0.1, o for o.s.
and decreased exponentially with bed depth, D,i.e., C, =
C,e-*. All of these observations suggest that this initial bed penetration is controlled by kinetic adsorption radiciodine environments. However, due to the long processes rather than by adsorbent capacity. It should, experimental times involved, the determination of therefore, be equal to adsorption efficiency at much cartridge lifetimes may not be a practical way of lower challenge concentrations.
measuring and comparing cartridge performances. The Retention studies of I generated from crystals used observed initial breakthrough may be a more useful n
beds of 6/16 mesh charcoal,2.4-cm diameter and usually indicator of cartridge performance.
1.25-cm deep, which corresponds at 10 L/ min to a linear Five types of potentiaj radiciodine adsorbents were flow velocity of 22 m/ min. Relative humidities of 50%
compared for I, adsorption efliciency at the following and 90% were used. In these longer term experiments at conditionst constant C., after the initial constant bed breakthrough 2.4-cm diam x 1.25 em deep beds l
was subtracted out, a subsequent increase in penetration 50% relative humidity developed more slowly, requiring up to 7 d to reach an 0.0127 g 1 in 100 ml H O generator solution.
3 2
additional 10% bed penetration. This was due to loss of 10 L/ min (22.1 m/ min) air flow rate.
capacity as active sites were being used up.
The measured penetration fractions were:
This subsequent breakthrough curve was best de-0.27% Westvaco WV.H. coa! charcorJ. not im-scribed by the equations of the Statistical Moments pregnated.
Theory, as was previously found for methy! iodide.8 An 0.14 % Sutcliffe Speakman 207A, 1.5% K1 im-I challenge concentration efTect (Fig.1) was observed:
pregnated.
n t, = kC,* (t, = breakthrough time for a selected 0.15% Coast Engineering Silver Zeelite, AgZ.
fractional penetration C,/C.), similar to what was ob-0.072% Sutcliffe Speakman 20SC, 5% TEDA im.
served for CH 1. Again, this implies that such cartridge pregnated.
i(
lifetimes, determined at ppm levels using normaliodine 0.032% Witco 337, petroleum charcorJ, not im-3 would be conservative for much lower levels expected in pregnated.
[_
7
-l 4
7y..
1
-k III. RADIOIODINE STUDIES-EXPERIMENTAL
' the headspace over a heated water reservoir. A humidit L
monitor / controller (Phys ChemicrJ Research Corp.)
- A. Flow System which regulated water temperature was calibrated with a The apparatus used to measure the penetrations of dew point hygrometer (EG&G 911) at the test bed volatile iodine and radiciodine compounds through test location. Water level was maintained automatically by a '
ecaductive liquid level control (Lumenite Electronic beds, canisters, and cartridges is diagrammed in Fig. 2 Co.).
. and shown in Fig. 3. It was built inside a fume hood to A " Standard Operating Procedure for Use of 888I in
, exhaust any toxic vapors which might have been re-the Testing of Respirator Components"8 leased. Radioiodine solutions and contaminated sorbents was prepared were contained for further safety within a glove box with and approved by internal review. It describes the ex.
charcoal and HEPA exhaust filters. Vapor gent ation perimental apparatus, procedures, and precautions to be used with this radionuclides.
and test bed exposures were done within the glovebox.
Compressed air was filtered, regulated for proper flow.
rate, and humidified before entering the glove box. An B. Generation Methods electronic mass flow meter (Datametrics 300-L) which monitored airlflow was periodically checked using a dry Vapors were generated in two ways shown in Fig. 2.
- test meter (Singer DTM.325) at the test bed location.
Liquid methyliodide and methyl radiciodide sealed in a Humidification was accomplished by passing air through Teflon permention tube were released at a steady rate by 4
TEMPERATURE TEST BED HUMIDITY AND WATER LEVEL-f g
SENSOR CONTROLLED BATH VENT TO _
--i GLOVEB0X I
, A a
n SAMPLING
- MASS FLOW SENSOR GAS I
AR/CH4 VALVES CHROMAT0 GRAPH CARRIE PARTICULATE FILTER WITH ECD A
pugp' CHARC0AL FILTERS U
PRESSURE REGULATOR RAD 1010 DINE CHARC0AL TRAPS kl-.
PARTICULATE FILTER NAl CRYSTALS PHOTOMULTIPLIER PERMEATION SOLUTION TUBES GENERATOR GENERATOR p
Fig.2. Ear awM apparatus for sessing air purifying evepirator cartndses and sanisters usmg radiciodine and normat iodme
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2 permenting into a 500 cm / min airflow. Temperature digital valve sequence programmer (Valco Instrument control (25 70'C t 0.!'C) of this permestion tube was Co.) to alternately inject the upstream and downstream by the Calibration System (Analytical Instrument Devel-air at 5 minute intervals. The chromatographic column opment, Inc., Model 303). Altemately, methyl radio-was 1.8 m x 4 mm id. glass packed with 15% OV-7 on
. iodide (CHj281), elemental radiciodine (8881 ), and 100/120 mesh Chromosorb G. Operating conditions 2
hyporadiciodous acid (HO*8'I) were generated from were 100*C and 20 cm / min 19:1 Ar:CH, carrier gas.
8 aq;eous solutions. A syringe was used to inject 10 mL of An electronic peak integrator (Spectra Physics Mini-solution into 100 mL of distiUed water or other reagent grator) quantitated the methyliodide peaks and recorded solution in the glass container in the lower center of Fig.
elapsed times. Calibrations of this analytical system were
- 2. The volatDe iodine compounds in this stirred mixture made using weighed permestion tubes to generate known 8
entered the head space and were swept by 500 cm / min methyl iodide concentrations in air.
of air through Teflon and glass tubing into the main The radiometric detectors continuously coUected and airflow. Water vapor was also generated. Output of measured 8881 from the 0.8 L/ min air samples passir.g v:latDes from solution dropped exponentially fi im the through the gas chromatograph sampling valve. Fig. 2 time of injection. Generator output and main airstream shows the charcoal trap and 7.6-cm-diam x 7.6-em-thick passed through sufficient length of 2.4 mm-i.d. glass Na1 (71) well type (52 mm deep x 29 mm-diam) scintilla-tubing and two elbows to mix thoroughly before entering tion crystal with integral photomultiplier tube (Harshaw the test bed. Sections of the glass flow system and the Chemical Co.). High-efficiency charcoals were used: 5%
test bed were connected with O ring seals and clamps.
TEDn impregnated (Barnebey Cheney CN 2762) for Challenge air and test bed emuent air were sampled CHj881 and activated charcoal (Union Carbide ACC) continuously through Teflon tubes connected to the glass for 88'I and HO888L The majority of radiciodine was system and into the gas chromatograph and charcoal couceted at the bottom of the well, resulting in good Q beds.
detection efficiencies (-0.5) for the 0.364 MeV gamma-The technique of generating volatDe iodine s,pecies ray. Each detector for upstream and downstream air had from aqueous solutions for the testing of sorbent beds or its own preamplifier, amplifier, single channel analyzer, respirator cartridges has proved to be quite useful.
and counter (aD from Ortec). They shared the power bin Concentrations in water (and in air) decrease with time, (Onec), high voltage power supply (Canberra), timer approximately exponentially, depending on species vola-(Onec), and printer (Onec). Linear log rate rneters tility and,in some cases (CH 1, the rate of stirring of the (Mech Tronics) were used for count rate monitoring.
3 solution. One advantage of this generation method is that Detector counts were taken from 5-minute intervals and a range of. challenge concentrations is produced in a printed together. Each detector trap and crystal was single experiment. This can give information about the shielded by 5 cm oflead to reduce background counts.
adsorption isotherm of the test bed. Another advantage Fresh charcoal was placed in the detector traps for f;r inorganic species, particularly, is that generation is background counts before each new bed was tested. The fr:m a source similar to field sources, such as reactor detectors were compared almost daily for relative coolant waters or spent fuel cooling pools. Jr is also sensitivities by sampling the same radiciodine containing possible that expdmental generator solutions can be air.
m theed (pH, ar..atives, etc.) to actual aqueous field sources.
D. Reagents C. Detection Methods The source for radiciodine 131 was ICN Chemical
{
and Radioisotope Division, Irvine, CA. Methyl radio-l The detector for methyl iodide was a gas chromato-iodide was ordered as 5 mci 88'I in 3 mL of total graph (Varian 1520) with a linearized electron capture methyliodide. Stated purity was a least 99%. Two i~[
detector {Tracor Instru'ments). Air from upstream and milliliters were used to fiU a permention tube and I mL downstream,of.thef est bed-was drawn (0.8 L/ min) was dissolved in 1 L of double distilled water. This t
through matched. Teflon sampling loops anached to a aqueous solution (2.3 g/L or 0.016 mol/L) was used 10 j
10.pon vaFe (~VaicMriitritmSt Co.) of H astalloy-C (for mL at a time for generating as described above. Radio-inertness). This valveNvas'pneumatica!!y actuated by a iodine in the form of Nal in 0.05 N NaOH was t
.v..
N purchased in a 5 mci amount. Stated purity was at least against iodine for radiciodine vapors. Each type con.
- 99% with an trigfis'I ratio less than 10. This material of tained a particulate filter. followed by a sorbent bed chout I mL volume was added to' 1 L H 0 contairdng comaining a coarse grained charcoal. Some of the-
~ 0.127 g of dissolved I, (0.127 g/L or 5 x 10-8 mol/L).
charcoal sorbents were reportedly impregnated with Isotope eachange occurred to form 8881. This solution reactive chemicals for radiciodine removal, such as 3
was used to generate both 888I, and HOI'88. For HO'881, triethylenediamine (TEDA) and KI (KI + 1 ). The 10 mL of this latter solution were injected into 100 mL of distinction which is made in this paper between canisters 3
3 4 x 10-8 mol/L NaIO at pH = 2 to cause the reactions:'
and cartridges is that the latter are used in pairs and are 3
F physically smaller. For some experiments beds of 2.4 em 2Is + 10; + 6H* + 2H,0 = $ H Ol' diam were prepared from charcoals taken from canisters.
2
~ H 01* + H 0 - HO! + H 0*
The term " test bed" will be used in this report to refer to 2
3 3
a canister, a cartridge, or an experimental bed. Table I lists characteristics of the canisters and cartridges and No anempt was made to determine the extent of HOI their charcoal contents.
production, since no analytical method is known which
- distinguishes this unstable species from I.
IV. RADIOIODINE STUDIES-RESULTS AND CONCLUSIONS
- E. Test Beds A. Comparison of Yapor Species
..,g Air purifying respirator cardsters and cartridges were obtained from three U.S. commercial sources: Mine Penetration test results at high humidity (97 s 3% for Safety Appliances Company (MSA), Pittsburgh, PA; the three radiciodine vapor species are tabulated in Table Norton Company, Safety Products Division, Cranston.
II for five canisters (64 L/ min) and in Table III for four R1t and Scon, Health / Safety Products, South Haven, cartridges (32 L/ min). Pulses of challenge vapor were M1. They each claimed by labelling or personal manufac-generated from solution at 2 hour2.314815e-5 days <br />5.555556e-4 hours <br />3.306878e-6 weeks <br />7.61e-7 months <br /> imervals. Two hour turer information, to be of some use for protection average penetrations and standard deviations (given in TABLE I. Characteristics of Canisters and Cartridges Tested Charcoal Bed Geometry
- Cross Charcoal Impregnants' Scuree Type Designation Section (em ) Depth (cm) Volume (em )
(Weight Percent) 2 8
MSA Canister GMR-I
!)0' 3.2 350 5% KI 3 Canister GMR 1(TEDA)*
110' 3.2 350 5% KI,,2% TEDA' Canister GMRS 110' 3.2 350 Metal and Ammonium Salts' Scon Canister 600252 75 87 3.8 330 5%TEDA Canister 282 OAP-R 87 3.8 330 Metal and Ammonium Salts' Cartridge 604550-75 48 1.3 62 5% TEDA Cartridge 604403 75 48 I.3 62 5% TEDA Nsrton Cartridge Typel' 44 2.4 106 5% TEDA Cartridge Type II" 44 2.4 106 5% TEDA
' Measured from opened carusters.
" Rest Information from manufsemrers.
' Oval cross asetion.
"The GMR 1 (TEDA) designation is used for GMR I canisters manufactured after July,1979 through at least April.1980 DA = triethylenedaarrune.
'Whetlerized charcoal.
- Granule size 316 mesh.
j o
TAB 1.E II. Radio:~h Test Results for Canisters' I
Average Percent Instantaneous I'"'ti "5 I""d SL*"d*#d D'YI'*I "'I' Canister Test Type Vapor 02h 24h 4-6 h 68h 810 h 0.24 Scott CH 88'I -
3 (0.02) 600252-75 1.07 0-0.61 (0.06)
(0.05)
"'I, 0- -
HO"81 0-0.10 0.08 0-(0.03). (0.03)
GMR1 C H "'I 0.24 4.43 6.09 3
(TEDA)
(0.08) (0.16)
(0.17) 0.99 2.46 7J4 (0.41) (0.73)
(1.06) 888!,
0.71 0.10 0.10 (0.04)- (0.02)
(0.02) 0.08 0- HO"'I (0.04)
J GMR-1 C H 88'I, 3J4 8.40 21.29 3
(0.52) (0J3)
(0.65) 8881 0.17 0.07 0-3 (0.02) (0.01) 0.07 0.17 0.11 HO"'I (0.03) (0.07)
(0.03)
Scott C H "'I 19 98 100 3
282 OAP R (2)
(4)
(7)
- 8881, 0-0.07 0.18 (0.0!)
(0.02) 0- 0.27 0.75 HO"81 (0.04)
(0.04) l GMRS 8881 0-0-
0-3 H o 'I
-0 0- -
u
'64 Umin.97
- 3% RH.
'Zero value (.0.) means not significandy greater than zero at the 95% confidence level. Dash (-) means not measured-parentheses) were determined by linear regression analy-canister or cartridge was tested.
Methyl iodide was the vapor form of radiciodine that sis of 5-minute counts in the downstream detector versus most readily penettsted the respirator canisters and the upstream detector. Relative sensitivity of the two cartridges which were tested Penetrations of "81, and radiciodine detectors determined by daily calibrations eg HO"'I at high humidity were low (50.15%) and, with l
was taken into account Any penetrations calculated to one exception. did not increase significantly with ex-l be within 95% confidence levels of zero were considered posure and loading. Since methyl iodide is the most as zero and listed as 0. In only two cases were raore volatile organic iodide compound. other organic iodides l
than one caniner or cartridge of a type tested for a given should be retained on these canisters or cartridges with radiciodine vapor.Therefore these results cannot refleet the same or higher c!IIciencies. Therefore. methyliod
-"""-t %W 3 aiven me. At lesst three of each
.j y
,a i
i i
1 was e m st e e
ng nea y canant W t TABLE III. Radioiodine Test Results for Cartridges' 0.5% penetration of both methyliodide and radiciodine 1
Average Percent throughout the experiment. The GMR I ($% KI, 2%
3 i:
- Cartridge -
Test hstantamms Penarshns. MA) was less eNent at abt 10. 2% mahyl Type Vapor- 02h 24h
'4-6 h iodide penetration and ' 5
- 1% methyl radiciodide penetration after an initial equilibration period. The
' Norton Type !
CH 8"!.
0.03
~ 1.94 3.34 3
GMR-I (5% K1 ) charcoal was most emeient at the 3
3 (0.01)*
(0.06) (0.60) beginning of the experimems, but rapidly and steadily
- "Is 0-
.O.
0-deteriorated to give a 60% cumulative fractional methyl Norton Type II 8"If 0- 0-iodide penetration and a 17% cumulative fracdonal-
{
Scott '.
~
CH 8"I 1,18 9.27 11.50 3
methyl radioiodide penetration by 100 minutes.
604403-75 (0J3), (0.29)
(0.34)
Results from seventeen experiments with iodized
'"Is 0.04
+
4 charcoals are compared in Fig. 6, which shows CH 8"I
$01) 3 cumulative percent penetration versus CH 1 cumulative Scott '
CH 8"I 1.98 10.71 12.87 3
3 percent penetration. The data points all fall below the 604550 75 (0.17)
(0.99)
(0.90) equality (dashed)line,i.e., CH 1 penetration greater than 3
'321/ min,9713% RH.
CH 8"I penetration. Also, in the region of practical 3
- Zero value (-0-) means not significantly greater than aero at interest (less than 10% penetration) the difTerence is an-the 95% confidence level.
'(Standard deviations).
apparently only and constant factor, about two in these cases.
A more extensive comparison of fractional penetra-
)(M tions for Scott ($% TEDA) beds is summariaed in Fig. 7.
should be used as the test species to determm' the upper These results are from 14 experiments at two humidities limit penetration of vapors contatmng iodine.
for two generation methods, and for three bed depths Milo Ksbat and coworkers at Ontario Hydro have (1.25 3.75 cm). Each graphed point represents the aver-challenged four cartridges and canisters with CH !, HOI.
age of 20 to 30 measurements for a given experiment.
3 and 1 forms of radiciodine.8 The results shown in Table The penetration valoes all fall close to the theoretical j
3 IV, confirm that HOI and 1 removal and retention (dashed) equality line. Therefore, for this type of sorbent 3
emeiencies are greater than or essentially equal to those (TEDA only) measurements of molecular CH 1 penetra-3 for C H 1.
tions are direct measurements of the 8"I penetration 3
when the radioiodine challenge is in the form of CHj"I.
A fourth type of charcoal, from an MSA GMR.S B. MethylIodide Versus Methyl Radioiodide canister, was tested to compare methyl iodide and radiciodide penetrations. This Whetlerized charcoal is Cumulative percent penetrations through three types impregnated with metal and ammonium salts, but con-of impregnated charcoals are compared for methyl tains no impregnants that react with methyl radiciodide.
iodide (Fig. ~d) and for methyl radioiodide (Fig. 5). The Therefore, removal of 8"I in CH 8"I can occur only by 3
test beds,3.75 cm deep by 2.4.cm diameter consisted of physical adsorption of the molecule. Cumulative frac.
charcoals taken from MS GMR-1, GMR I (TEDA) and tional penetrations of methyl iodide and methyl radio-Scott 600252 75 canisters. Each bed was preconditioned lodide are compared in Fig. 8 for duplicate experiments.
for 2 hours2.314815e-5 days <br />5.555556e-4 hours <br />3.306878e-6 weeks <br />7.61e-7 months <br /> at the test conditions of 3 IJmin airlfow and The data points closely fit the equivalence line until the 86 t 3% relative humidity before being challenged with amount desorbing from the test bed equals that entering 8
I.S ppm (7 mg/m ) methyliodide tagged with 8"I.
it. Then there was a slight deviation in the direction of Cumulative fractional methyl radiciodide penetrations greater radioiodine penetration than methyliodide pene-e(
were calculated directly from 5 minute interval counts of tration. This deviation is explained as the result of radiciodine trapped in the detectors. Cumulative frac-forming volatile iodides other than methyl iodide. The tional penetrations of methyl iodide were calculated by radiciodine detector is not compound specific, but the integrating instantaneous upstream and downstream gas chromatograph is and would not measure the other concentrations determined by gas chromatography.The iodides. Instantaneous fractional penetrations (emuent
. 5% TEDA. impregnated charcoal from the Scott canister concentration /cha!!cnge concentration) of methyl iodide
-\\
s f
j TABLE IV. Comparisons of Radiciodine Species Removal Emelencies by Kabat*
Adsorber Radioiodine -
Airflow b8'
- Type-Species I/ min Adsorption (3h)
Desorption (2h)
GMA.H ~
CH1 20 98.13 99.29 3 3 Canridge HOI 99.24 99.90 0.2-1.5 1
99.92 99.96-
<0.10.11 3
GMI-H CH1 20 99.95 99.96 0-< 0.1 3
Cartridge HOI 99.87 99.92
< 0.1 1
99.92 99.96 0.19-0.33 3
Canadian C1 CH 1 -
40
$2-47 4146-3 Canister HOI 99.2 99.6 0.3 0.5 1
98J 1.I' 3
40 99.91 99.93 0.14 0.59 3
Canister HOI 99.21 99.93 0.1
- 1, 99.87 99.96
<0.1-0.15
- From Refurence 3. 95 persent RH 25'C.
so U
b eo 1
E w
.y -
t ris.4. Meihys i dide cumun.iive percent peneir tions as funeuens or 4o..
y time. for chareoels from three respirator carumers: C. Soort 600252 75 (5% TEDA); o. MSA GMR I (!% KI,. 2% TEDAh A.MSA GMR-!(5% KI,).
^5o
__ _-n
%~r m o
2o 40 60 so
'100 T!?E (nix) 3 20 g
~-
C 3 15 E
k' Fig. 5. Methyl radiciodide cumulative peroem penersuons as fane.
g 10 tions or time for charcoals from three respirator carusiers: C. Scott 600232 75 (!% TEDA); D. MSA GMR 1 (5% KI,
- 2% TEDA);
t MSA GMR 1 (3% K2,).
5 O'
u O
((
E
/U N -@
3n MD. D 5
o 2o 4o 6o so 100 TIME (n N)
{
47 i.
'3 20 80 i
7
/
)
3 l
g
. k 15 h'60 g#
E
/'
5 Ag'
~
d k
200 1 b' ' 10 I'
k:'
INSTANTANEOUS.
e g 40
--PENETRATION i
v sf
~
t 5
y v
m E
N
"(.
3 p
=
0O 20 40 60 80 0'
O 20 40
'60 80 CH 1 CUMULATIVE PENETRATION (%)
3
.cH 1 CUMULATIVE PENETRATION (1) 3 Fig. 6. Comparisons of svaniastive percent pencersdans of Fig. 8. Comparisons af ournulative percent peneurstions or snedryl snethyl radiciodide and methyl iodide for two $% K!, charcoals:
radioiodide and snathyliodide for Whetlerized charcoal (GMRJ)
A. GMR It O, GMR 1 (TEDA).
for two esparate esperunents (A and o ).
9 increased with time and even exceeded 100% as the
- 100; l:
,ej vapor adsorbed at the beginning was displaced in the air.
~'
Breakthrough times of methyliodide averaged 33 2 3 g
minutes at 0.1%, 49
- 6 minutes at 1%, and 68 n 8 g
minutes at 10% instantaneous penetration.
g Normal methyl iodide can be used to determine the
- - 10 k<
upper limit of penetration to be expected for methyl 3
y
@Q,e'
(-
{
radiciodide. Isotope equivalent efficiencies have been demonstrated for sorbents not impregnated with normal iodine or iodide. Normal methyl iodide tests cannot (5
I
,e
' measure the removal of 88'I by isotope exchange on g
iodized charcoals and, therefore. give a high (con-servative) estmate of methyl radiciodide penetranon.
However, there are currently no commercial radiciodine canisters or cartridges which have charcoals im-0.1 Pregnated with iodide only. The GMR.I canister with 5%
0.1 1
to 100 KI packing is no longer available.
3 AVERAGE EH 1 PENETRATION (1) 3 Fig. 7. Comparison of everage percent penetrations of methyl C. Effects of Bed Depth and Contact Time radioiodide and methyl lodida for a $% TIDA impregnasad sharcoal (Scott 600232 75). Permention tube generauoni o,
Another series of experiments with the TED A and K13 97% RH and e,35% RH; aqueous solution generation:A. 97%
RH.
impregnated respirator canister charcoals was done to establish the rate orders of methyliodide and radiciodide
t..
l i
i 4
.)
~ removal. The ranges of test conditions were:
. ylradiciodide concentration. The range of airflow rates Bed depth: 1.25 3.75 cm was not large enough to notice the velocity effects found
[
Bed diameter: 2.4 cm later.
j Airflow rate: 1.8 4.2 Umin or 6.715.3 cm/s Ten such experiments using 5% TEDA charcoal from l
Bed residence time: 0.16 0.75 s ~
Scott 600252 75 canisters were also done at similar Relative humidity: 86 t 3% _
conditions. Semilog plots for penetration percents (both Concentrations:- 61200 aci/m8 8881 and 0.19-72 methyl iodide and radioiodide) versus bed contact times 8
mg/m.CH 1 (Fig. 9) showed that the chemisorption reaction is also 3
Conditioning Period: 2 hours2.314815e-5 days <br />5.555556e-4 hours <br />3.306878e-6 weeks <br />7.61e-7 months <br /> described by a simple first order rate. Both methliodide-
. Seventeen tests with mehtyl radiodide generated from a and radiciodide are removed from air at the same rate.
permeation tube were done using iodized charcoal from Four experiments were also done at different bed depths an MSA.GMR.! canister. In each test the meth-(1.23 5.0 L cm) - using charcoal - from.MSA GMR.I i
ylradioiodide instantaneous penetration remained nearly (TEDA) canisters. Penetrations of methyl iodide and constant, while methyl iodide instantaneous penetration radioiodine during each run were both constant, but not increased steadily with time until it exceeded 100%.
equal. The difference for this mixed impregnant (2%
. When the logarithm of methylradiciodid: penetration TEDA and 5% K1 ) sorbent is due to isotope exchange 3
percents were plotted against bed contact times a straigt which removes the 88'I from the methylradiciodide but line with an intercept of 1.0 resulted (Fig. 9). This leaves a molecule of methyliodide. Average first. order indicates that the methylradiciodine removal reaction rate coefficients calculated from the slopes of pl_ots such (isotope exchange) is simple first order in meth-as Fig. 9 are listed in Table V.
The reaction of TEDA impregnant with methyl iodide vapor is by first order kinetics. The isotope exchange of g
'100 iodide impregnant to remove the radiciodine from meth.
l l
ytradiciodide is also by first order kinetics. Emuent O
vapor concentrations decreased exponentia!!y with bed depth. These results indicate that removal efficiency 'was o
independent of vapor concentrations within the bed. This is an important conchtsion, since the radiolodine concen-O
. C trations to be encountered in nuclear environments are many orders of magnitude lower than the ppm concen-i g
I g
trations required for a nonradiometric test. The first g
order kinetics also implied that contact time of vapor g 10.-
o within the serbent bed is critical. Contact time is g
determined by canister geometry and airflow rate (i.e.,
g l
workload). A high flow rate should be chosen for a canister test to approach the upper limit of average vapor g
W penetration. The arbitrary test standard is 64 Umin for l
canisters and32 Umin for individual cartridges used in pairs.*
Canister charconjs containing 5% TEDA impregnant were more effective for methyliodide removal than those A
containing 3% KI impregnants are more emeiem for 3
methyl radiciodide removal than those without, except
]
0 0.2 0.4 0.6 0.8 f r sh r1 Periods with fresh canisters.
'(
S0REENT BED CONTACT TIME (s)
D. Effecu of Cha!!cnge Concentrations Fis.
- 9. Aversse botantaneous percent pueeirstions as losantheruc functions of bed contact airnest o methyl radio-lodide for a 5% KI, sbarcoal(GMR Ih t methylladide and Five tests were made with 5% K1. impregnated 3
methyl redaolodide for a 5% TED A charscal (Scoct).
charcoal under these conditions:
F 3
TABI.E V. First Order Rate Coefficients for Methyl Iodide and Radiolodide Removal' Rate Coeffielent (s-')
Charcoal Charcoal Total Total isotope Irnpregnant Source CH,83'I CH,I Eachange' 5% TEDA Scott 6.9 0.5 7.1 t 0.3 None 600252 75 5% KI, GMR-I 3.6 t 0.3 3.6
- 0.3 5% KI +
GMR.I 4.9 t 0.1 3.0 t 0.1 1.9 e 0.2 3
2%
- EDA (TEDA)
- 2.h preconditioning at 86% RH.
Tifference of preceeding two columns.
~
3.75.cm depth x 2.5.cm. diam bed The Wheeler adsorption equation predicts the 8
1.8 IJmin airDow: 6.6 cm/st 0.57s bed contact time logarithm of penetration as a linear function of time for 86% RHt 2 hour2.314815e-5 days <br />5.555556e-4 hours <br />3.306878e-6 weeks <br />7.61e-7 months <br /> equilibration before testing 0.19 3.8 low penetrations (<!!%9, and such plots have been reported for CH 1. The penetration curves for the -
mg/m' CH 1 3
3 0.00610.125 pCi/m88881.
experimenu reported here with the iodized charcoal
~
O Challenge concentrations varied over a factor of 20.
consistently fit the Statistical Moments Theory (SMT)
$ breakthrough times (t ) of CH 1 for 1%,10%. and 50%
equations' and an empirical exponential C/C, = at' 3
instantaneous penetrations were nearly the same for all equation better than the Wheeler equation. For example.
challenge concentrations (Table VI.) Individual break.
four data sets at penetrations less than 15% yielded the through times were used to calculate the breakthrough correlations in Table VII.
crpacities plotted versus challenge concentrations in Fig.
The consistent failure of the Wheeler equation to give
- 10. The linearity of these plots indicated that CH I the best fit of penetration reschs from many experiments 3
adsorption and desorption occurred according to a brings to question its use in extrapolating to define initial simple linerar isotherm (Henry's law). Other charcoals penetration at initial exposure. However, it will always which have been tested with CH 1,have not indicated give a conservative (higher) initial value relative to the 3
linear isotherms.8 true one due to the curvature of the breakthrough curve.
TABI.E VI. Effects of Challenge Concentrations CH,I CH, 8"1 Breakthrough Times (min)
Conc.
Conc.
Percent (mg/m )
'1%
'!O%
'50%
(nCi/m')
Penetration' 3
O.;9 6.8 18.0 39.6 6.1 12.3 0.41 2.4 14.7 41.5 13.6 16.0 1.29 3.8 15.4 41.8 42.6 9.7 2.19 7.4 20.5 45.8 72.3 15.4 Jg 3.78 3.4 15.1 38.7 124.7 11.5 Average 4.8 16.7 41J Average 13.0 Std. Dev.
2.2 2.5 2.7 S14. Dev.
2.7 sAverage instantaneous penetration after the inidal period in which physical adsorpc'on was significant.
a q,s J
j L.
l' 0.3 Four cartridges, all containing 5% TEDA.im-pregnated charcoals, were tested with methyltadiciodide at 0,2,and 4 hour4.62963e-5 days <br />0.00111 hours <br />6.613757e-6 weeks <br />1.522e-6 months <br /> exposure times to 32 IJmin,97
- 3%
gg RH air. Methyl lodide penetrations again increased with i
j 0.2 exposure times. Maaimum penetrations (humidity equi.
=
E:
libratiora) were reached in about 3-4 hours. Average a-penetrations. measured during 4-6 hours by gas 30 1 chromatography and by radiometric counting are listed g 0.1 in Table VIII. The values from the two methods are in
=
good agreement. Cartridges with larger sorbent volumes (Table I) of similar sized and impregnated charcoals gave lower penetrations,. That this can be attributed to in-g 0 _'
creaded bed contact time is shown in Fig. II. This 0
I 2
3 4
semilog plot also includes data from Table 11 for the 0(31 C32XTRAT10N (ms/E Scott 600252-75 cansiter. De average first order rate coeficient is 17.6s-" (standard deviation = 1.3 s-"). This Fig.10. Dynamic adsoryuon laadurns at em taman, sansous peneireman frecuous for manyl indide and MsA correlation should be useful for improving efficiencies by GMR.!(2% KI,) shwooal redesigning canisters and cartridges.
The larger canisters (used alone) were more efective For the above expeirments, the Wheeler equation gave for methyl iodide removal than cartridges (used in pairs) even though the flow rate through each cartridge was
( g an initial penetration value of 0.33% (std. dev = 0.18%)
half as much. Also, the cantidges deteriorated in em-to be compared with the SMT initial value of 0.094%.
One of the best fits of the breakthrough curves was for a ciency more rapidly due to high humidity. Magnitudes of C/C = at'. empirical equation which has three dif.
efficiencies can be correlated with volumes of charcoalY and bed contact times.
ficulties: (1) it has no theoretical basis: (2) it does not Insufficient data are available to rate cartridges and allow extrapolation of penetration to initial exposure canisters for radiciodinc remova!. Variations within timet and (3) extrapolated values very rapidly at short times, for this example. 0.020 at 0.5 minutes. 0.073% at brands and types ahve not been established. Also, their contents are subject to change by the manufacturers.
1 minute, and 0.265% at 2 minutes.
These unknowns emphasize the need for an ongoing certification program. Such a program to be carried out in the NIOSH Testing and Certificaiton Branch, is an E. Cartridge Comparions ultimate product of this project.
TABI.E VII. Fits of Penetration Data to Equatio'ns Linear Correlation Coefficient, r Equation Wheeler:
In(C/C.) = In a + b t, 0.9256 Exponential: In(C/C ) = In a + b In 1, 0.9999 t, - m, + m/6m3 m3
- - v% + g X, 0.9999 SMT:
T y
- ,y i
/-
. TABLE VIII. Cartridge Penetration Fractions of Methyl Iodide and Methyl Radioiadide after EquDibration at High Humidity
- Average Percent Instantaneous Penetrations Bed Charcoal
-Cartridge
-(and Standad Maions)
Contact Granule Type CH,I CH,8881 Time (s)
Mesh Norton Type 1 3.75 3.34 0.20 8-16 (0.76)
. (0.06)
Norton Type II 1.50 0.20 -
12 20 (0.15)
Scotr 604403 75 13.24 11JO 0.12 8-16 (0J9)
(0.34) 5:cet 604550-75 16.52 12.87 0.12 8-16 (0.6!)
(0.90)
'32 IJmin. 97
- 3% RH, eh.
100 hile continuously exposed to very hig c.
w
.O' 3% RH) air, increasing penetrations were usually ob-served. This is illustrated by the results in Tables II and -
III. Sach an effect could be due to (1) loading the test bed p
with methyl iodide in previous tests and/or (2)1oading it 10 j
j with water vapor by exposure to large volumes of high t
l F
humidity air. Studies were done to sort out these c!Tects E
using Scott 600252 75 canisters (5% TEDA ch.--aan at E
64.L/ min airflow rate. Methyliodide was generated from
- y
)
aciuscus solutions (0.23 g/100 mL) at selected times
'y I
while a canister was exposed to high (97
- 3% or l
medium (50 t 3%) relative humidity air. Penetration A
l results versus exposure times are shown in Fig.12. Box
\\.
0-0.1 0.2 0.3 0.4 SOP. BENT BED CONTACT TIE (s)
E Fis, !!. Dependence of sverage lamantaneous persent peneurseiona
_E g
/'
~
q s.e had sornact times for camssers and cartridges sentaining $%
2
- TEDA. impregnated characals: O, meshyl imeJes t.. methyl radio- '
indids.
n I
L g
g 1
t' C.1
~
)
l E
V. EFFECTS OF USE CONDITIONS c.01 A. Re!6tive Humidhy 8
II N F.!$1tf tIPDtUri t!T (al 1.' Comparisons of Water Vepor and Methyl lodide Loading.; When canisters or cartridges were tested more Fig.12. Averese instantaneous percem penetrations of methyHoer
.... -... - 15 (!% TID Al caruster, es funcoons or through scort 6002!2'.
sk......4.~.
..u..s..a:.; a:a... *.... :.......
.e-
e pg
- ,7
~
+ 3.. m ; n e
t
[
rt ranges of data obtained. In the first
'8 ij
'open rectangles) a fresh canister was tested 1.
6, and 24. hour exposures to'97% RH air.
_f l
l,
--: increasa,d by over two orders of magnitude.
g-2a :ss succ8d 88P'runent another 88Ai888r '88 ** posed L
. ggg, 3:s==sdity for 16 hours1.851852e-4 days <br />0.00444 hours <br />2.645503e-5 weeks <br />6.088e-6 months <br /> before being tested at 16, gi
_a c,.c, j ;,- % o -:- J a o,
~
y i
3g u.g CO bours. These data (shown as rectangles win b
]
,,,) r.- em ' the same'. curve as those from the first. '$
e 2,-c In the third expenment (solid rectangles) g
[er semister was tested at the 50% RH and 0,2,4 h*'
L M a 4 25-bour exposures. Even for the longest time and g-ges-h.ed loading the penetration at 50% RH was not s,gg,gg !y changed from the be' d.
X Norson Type 1I ca tridge (12 20 mesh 5% TEDA) seg,,,,,,,,,,,,,;,,,,
8
^,,, e. g.er.ged with 1.7 ppm (7.6 mg/m ) methyl iodide Taut (h) at 32 IJ~1in air and 90% RH (Fig.13). During the first 3 Fis.~ u. Efract. of espeews dine on samleyi iodide histansaneous h'our s. ce penetration fraction increased nearly 2 orders -
ponereuen far a fresh Neuen Trpe 12 servuise sessed at 90% RH.
of magr.itude to 1% where it remained constant for at.
3: usin steow, and 1.7 ppm p.6 mishn'l anthrliadide.
least 29 hours3.356481e-4 days <br />0.00806 hours <br />4.794974e-5 weeks <br />1.10345e-5 months <br />. Since the bed was being loaded constantly.
,,;g zoethyl iodide and there was no change in penetra-Ar frag: ion after 3 hours3.472222e-5 days <br />8.333333e-4 hours <br />4.960317e-6 weeks <br />1.1415e-6 months <br />, the initial change must be not exhibit heating due to additional water vapor adrerp.
pributsd to something other than sorbent exhaustion by
. tion (see Section V. A.4.). Also, the penetranc,n is often
.,,cyl iodide loading.'Apparently,3 hours3.472222e-5 days <br />8.333333e-4 hours <br />4.960317e-6 weeks <br />1.1415e-6 months <br /> was' required maximised at such equilibrium. A Scott' cartridge (642
' for ce charcoal to become equilibrated with water vapor TEDA.H) containing 5%.TEDA-impregnated charcea!
gn gnibrium with the 90% RH air.Thelarger canisters
. was exposed at 32 L/ min airflow. 0.57 mg/m (0.13 8
require more tirm (Fig.'12). The adsorbed watcr vapor ppm) CH 1,27
- 0.4'C,and 50,71,and 91% RH. Aher 3
eiger blocks access of methyliodide vapor to the TEDA equilibrium was reached at each humidity penetradon or removes - TEDA - effectiveness by measurements were made at seven or 10 more minute impregnant K
' bydrolysist intervals and averaged.
These values of the equilibrium CH 1 penetration 3
M(CH CH ):N + H 0 = N(CH CH ),NH* + OH-fraction P were related to water vapor concentradon in 2
3 3
3 3
When the challenge of a vapor to a test bed is at a high enough. concentration and continuous,- tL bed will P - exp (-47/[H O}).
g 3
. beceme loaded and will decrease in e!!iciency of vapor removal. The resulting iacesse in penetration with time This is consistent with the simple competitive me:ha-is called a breakthrough curve. Breakthrough times for nism:
/selgeted penetradon fracdons are often dependent on the challenge concentration. At :high relative CH 1 + N(CH CH ),N - N(CH CH )3NCH; + 1-x por 3
3 2
3 3
- humidities charcoal beds become loaded with water
. spor, also, increasing penetration of test vapor with H O + N(CH CH ),N n:: N(CH CH ),NH* + OH-3 3
3 3
2 dme The labove expc.riments have shown that for
,[ cfliciertt'sorbents at low challenge concentradons or where water vapor reacts with TEDA, making it un-1 Jc dings, Inc relative hureddity effect may be the most available for CH 1 remova!.
3
?
. significant. Therefore, the time of crposurs of a canister Larger MSA camsters, also containing 5% TEDA cr cartridge to high humidity air is an imponant charcoa!. were also mcasured for methyl iodide penetta.
. i parameter in a test procedure or a usage protocol..
tion at several humidities. Flow rate was 641./ min and reladve humidities ranged from 50 to 85% Penetrations
- 2. Equilibrium Penetrations. A charcoal bed at equi-at wuer vapor equilibrium,' P, were less sensitive to 3
~ 1ibrium with the water viper in the air en:ering it does (H.O] changes than in the case of the Semt :ar: ridges l
V
l e
wnh one f2fth as much charcoal. Times required for fresh.
canridges decrease with increasing relative humidity of MSA canisters to reach water varm equilibrium varied the air passing through them. This is illustrated by the '
from 9.5 hours5.787037e-5 days <br />0.00139 hours <br />8.267196e-6 weeks <br />1.9025e-6 months <br /> at 75% RH to 16 hours1.851852e-4 days <br />0.00444 hours <br />2.645503e-5 weeks <br />6.088e-6 months <br /> at 50% RH.
resuhs in Fig.14. If 1% is choren as the maximum At teladve humidities above 75% the CH ! penetra.
penetration to be allowed, the service lives t, for fresh 3
tion at water vapor equHibrium was not the highest MSA 5% TEDA canisters decrease from 635 minutes at
/'
penetration value. This is illustrated in Fig.14 with 50% RH to 200 minutes at 85% RH. Another selected penetration fraction versus time curves for MSA penetration vajue would give another set of service lives.
canisters containing 5% TEDA charcoal. At 85% RH a For example, tests of three fresh GMR.! (TEDA) maximum penetration of 7.6% was reached at 450 canisters at 64 Umin yielded the resulu in Table IX.
minutes as compared with an equilibrium penetration of An empirical relationship was found which described
- 4.1% (std dev = 0.2%). This maximum is attributed to the effects of relative humidity on service lives (t,) of the displacement by water of CH 1 previously physically fresh canisters. Lq t, versus log (H 0](or log percent 3
3 adsorbed. Such a maximum is commonly seen at all RH) plots were found to be linear with slopes between 2 humidides with various charcoal beds.
and 3. Fig.15 shows such plots for MSA 5% TEDA Conclusions reached from studying humidity effects canisters at 64 Umin airflow, Scott 5% TEDA canisters for equilibrated canisters are the following:(1) We now (600252 75) at 64 Umin airflow, and Scott 5% TEDA undemand how water vapor reduces the efficiencies of cartridges (642.TEDA.H) at 32 Umin airflow. The two TEDA impregnated charcoal beds. It is by tying up the brands of canisters, which have nearly the same volumes impregnant and making it unavaHable for reaction with of charcoal, had equivtJent service lives (Fig.15). Even g] ' reach humidity equilibrium limit the practicality of using methyliodide,(2) Long times.up to 16 hours1.851852e-4 days <br />0.00444 hours <br />2.645503e-5 weeks <br />6.088e-6 months <br />. required to at half the airflow rate the cantidge with much smaller charcoal volume had much shorter service lives which penetration at humidity equilibration as a measurement were more seriously affected by humidity. Similar data of canister performance. (3) Since the penetradon at high with MSA GMA canisters containing unimpregnated humidity equilibrium is not the highest value wnich activated charcoa! were also linear on a log t, versus log occurs,its usefu! ness for canister or cartridge perform.
[H Oj plot.
3 ance specification is questionable.
The usefulness of this reistionship for a certification L
/
program is for extrapolating from one humidry to T-
- 3. Service 1.ives. Measurement of service life, the another. It may allow the selection of two humidit time required to reach a selected penetration fraction,is conditions for evaluating canisters and canndges. Also, an after::stive to measurement of penetration at humidity the selected test humidities could be high (70-100%)
equilibrium. Service lives of air purifying canisters and where service lives are shoner and where, therefore, test times would be shorter. This is desirable for maximum efficiency of a certification test program.
Et: FJi TABLE IX. Service Life (25 min) at Three 5
Relative Humidities n: M 3
60: PJi Penetration Percent Relative Humidity E
p Fraction 60 80 100 y
[,
d 50: M l
0.0002 145 85 30 e
0.0005 185 105 35 4
0.001 225 135 45 4
0.002 275 155 55
)
0.005 375 195 65 0.1 O.01 455 215 75 0
2110 480 720 950 TIPE (M]N) 0.02 "5
245 95 0.05 705 305 135
' IV 14. Errary errect on meshys iod;de t,reatarough curm as 64 t/ min for MSA !% TEDA charcoat 0.1 855 475 235
.o Ko q
['
A RELATIVE liU!!!DITY AT 25'E Measurcable heating (4.2*C) continued for periods up 1
2 9
'*300 :
to 340 minutes for this series. Other cartndges and
. i 3
canisters (64 Umin) showed similar heating effects.
. Dew points were measured for air leaving test 5
g cartndges as well as for air entering them. This allowed determination of the rates of water vapor adsorption at times throughout an experiment. Temperature increases were proportional to water vapor concentration de-h'100
_ _ ~
"i creases. This relationship was used to calculate heats of '
g-adsorption ranging from 4 to 9 kcal/ mole.
Humidity heating efTects are important to note since g
(1) they. can make air purifying respirators less com-fortable to wear.and (2) they complicate the descriptions of how canisters work. The comfon effect is more
,,,.t relevant to the user than to the certification test.
1 10 100 WATER VAPOR FRE!!URE (Tenn)
Fig. !$. Correlations of relsove bunndity and earnee life (I%
B. Temperature besakthrough) for canisters C. Seou and A. MSA) and a
- ""d ' I C. 388") **** 8 WD A *h*"**"-
8
- 1. Equilibrium Penetrations.' Ambient air g.
temperatures for applications of air-purifyit;g respirators can vary. In addition, as memioned above, air drawn -
- 4. Humidity Heating. The adsorption of wpvapor from air passing through charcoal packed caasters and through a canister can be. heated by water vapor.
adsorption on the adsorbent. Temperature effects can be i cartridges heated the air to significant extents for long complex since higher temperatures enhance chemical l
g4 periods. Temperature rises for Scott canisters (642 reactions (chemisorption) with impregnants, but reduce TEDA.H) at 32 Umin airflow and three humidities are physical adsorption of vapors.
shown in Fig.16. The maximum increase of 10*C In a series of experimems with Scott cartridges (642-(IE*F) was observed for the highest (85%) relative TEDA H) at 32 Umin airflow. temperature of entering humidity at about 5 minutes from initial exposure.
air was varied from 26.4 to 38.0*C. Test cartridges were equilibrated at dew points from 15.1 to 25.7'C before methyl iodide penetrations were measured at the equi.
libration humidities (50-75% RH). Fig.17 shows a plot 12 4,6
-[lo O
g.
g E,q
.$ g W
25! M i-3 w6
+-
3' 4.2
(
{-
[
50: M 24.0 2
30: M ve-N.
3.8 O
O 10 20 30 40 50 60 3.20 3.25 3.30 3.35 3.40 TIME him) 3 10 n (*K-3)
}
Fe.16. Humidity besang effects for a Scott 5% TIDA carindge as Fis.17. Clapeyron plot to correlate equilibrium enetiryl
{
.y m._~-~----
1 v
c( In (-[H 0) In P ) versus 1/T, which turns out to be Company (MSA) canister containing charcoal with two 3
g knear Mth a slope of 3020'k.
impregnants,2% TEDA and 5% K!.The breakthrough 3
The usefulness of this data is in sorung out the curves show increased penetrations for increase:-
interrelated erects of relative humidity, ambient temper-temperatures at all experimental times. When logarithms ature, and dew point temperature. The following semiem-of percents penetration were plotted against pirical equations were derived from data for this temperatures, we obtained apparently straight lines. Fig.
cartridge:
19 shows such plots for the MSA canister (2% TEDA, 5% KI ) and a Scott 642 cartridge (5% TED A). Similar 3
5300 3020 results were obtained with an MSA-GMA ' canister In P = -0.0096 t, exp T** * " ~ T^** *"
containing unimpregnated activated charcoal. !n a!! three g
cases, the temperature effects corresponded to approx-imately doubling the penetration for each 5'C (9'F) 0.96 t, 2280 In P =
increase in temperature.
3%RH) *P c
T nsstem.,
The parameters of air temperature (T), relative A
humidity (RH), and dew point temperature (DP) are The exponent 5300/Tec,
,oi,,, comes from the de-interrelated and cannot independemly afTect service lives pendence of saturation vapor pressure of water en (breakthrough times at selected penetrations). Therefore.
temperature. At constant dew point, i.e., at constant we have studied temperature effects first with RH water vapor concentration, equilibrium penetration of constant and then with DP constant. As before, methyl methyl iodide decreases with increasing ambient temper-iodide is the test vapor, since it is the most penetrating ature. However, when relative humidity is held constant, vapor form ofiodine we have found.
equilibrium penetration actually increases at higher am-At constant RH, increasing temperatures sh./t break-bient temperature. This is due to the higher water vapor through curves to higher penetrations and, consequently, concentration for fixed humidity at higher temperatures.
result in shorter service lives (Fig. 20). Canisters and cartridges containing three types of charcoal were
- 2. Penetration and Service I.!ves. We have done studied at constant RH. The result (Table X) show experiments to determine how much effect the tempera-significant service life decreases with increasing ture of inspired air has on the ef!iciencies and service temperatures, up to 15% decrease per *C (8% per 'F).
I lives of fresh (unequi!!brated) canisters and cartadges for methyl iodide. First, we observed that such an efTect does exist. even over a limited expected range of use temperatures (15 35'C or 59 95'F). This is illustrated in 0*".
8 Fig.18 by data obtained with a Mine Safety Appliances
. Sc n[
2M 32 L/m =
10; 1
5% M 4
4 4
4 e
e 6
4 4
~
g 3,
3 E
g h
2
~
35 *C E 0,2 9
i E
Q g"*
31^*C-KSA CA= stra t
a q"
- f
[
3 h
[
f2I M
- 3 KI )
l 3
a 4
e 5=,
[
25'c
~
2x
~
=
9 t
9 e
e g
g,y 0
1 2
3 4
5 6
7 8
9 20 23 25 33 35 4D
~
wC w wnmm cC1 Fig.18. Air temperature efect on awthyl lodide tyrtakthrough curves at H L/rrun and 50% RH for ao MSA 2% TEDA. 5% KI, Fig.19. EKsets of air temperature on methyl iodide Pene:rsoon at caruser.
selected tunes after iruusung nows of $0% RH air.
s.
I; 1
/
400-na
'b.300 m.
54 r
200 2
l3
.ta u.5 100 02 Ct."
c.a en oz:
0 20 30 40 AIJE TEMPERATURE (OC) ris. 2o rs.a r.ir m.mi.y
- m. >= =
ses au r.r an us4 (2% rr.or,as x2,j m u umia..
4 TAB 1.E X. Temperature ENects on Service !.!ves at Constant Humidity Charcoal Percent T Range Percent CH I Service 1.ife Decrease 3
Type RH
('C)
Penetration (Percent Per*C) 2% TEDA,5% KI, 52 30-35 1
4 50 31 35 1
.4 26-35 0J 7
26 31 0.2 15 Activated 50 25 34 1
7 70 25 30 50 5
25 30 10 5
25 30 1
5 5% TEDA 50 29 38 1
9 L In one case (2% TEDA,5% KI ), the temperature effect turn out to be the case. Average increases in servicelives 3
varied with penetration fraction selected to define service life.
at 1% penetration were 12% per *C at 19'C DP and 3%
per *C at 24'C DP.
At constant DP (i.e., constant water vapor concentra-The cench: sics of these studies is that temperature can tion in air), service lives increased significantly with affect service lives much more than the 1 10% reduction increasing temperatures (Fig. 21). This is due to the per 10*C increase reported in the literature.' Therefore, combined effects of less water adsorption (air / charcoal temperatures at which cartridges and canisters are rested
- l equilibrium shift) and enhanced reaction ormethyliodide must be more closely controlled than *2.5'C specified with triethylenediamine (TEDA) impregnant. The main in CFR 30, Part II.* Also, the units must be tested at reason for doing constant DP studies was our hope that maximum T and RH of expected use or tested at lower temperature efTects would be less significant. This did not values with extrapolations of service lives to the worst k
i g
I L
j L
200-aos
.,=%
..E.lll
- ~
E v
m g
200-s Di g
0 2D
' f0 40 un nMPEunmE (* C)
Fig. 21. Effect of air temperature on esmer Eves at sonstant 24'C eswposit for sa MSA canamer (2% TEDA. 5% K! ) at W Lhnin.
3 case conditions. Users must be made aware of the D. Reproducibilides of Service I.Jfe Measurements
) potential for reduced service life when these units are used at even more elevated temperatures.
The question was raised ss to what reproducibilities can be expected for senice life determmations, consider.
l C, Flowrate ing variabilities due to manufacturing and testmg. Re.
suits oflimited studies are shown in Table XII. Precision A canister with 2% TEDA. 5% K! impregnated was worst for high protection factors and short times where bed deterioration due to humidity was most rapid.
q 3
cha?ccal was tested at 30*C and two RH's, DP's, and These results and other experiences indicate that at 1% i airflow rates. The results shown in Table XI clearly indicate that service life is inversely proportional to penetration for one batch of cartridges or canisters a \\
3 airflow rate. This confirmation of a well established reproducibility of 10% relative standard deviations of service life is reasonable. Reproducibility between relationship was necessary, since in this case service life batches can only be determined with more extensive is Getermined by water vapor loading rather than the testing.
contar:inant (methyl iodide) vapor loading.
TABI.E XI. Effects of Airflow Rate and Humidity on Senice IJfe*
Service Ilfe ( $ min)
Flowrate Dew Point Reladve Humidity at Penetradons (1/ min)
('C)
Percent
! Percent 10 Percent 32 19 52 173 300 64 19 5I 80 32 24 71 115 195 64 24 67
$5 105
'30*Ct 2% TEDA. 5% K1, canisters.
- - - - - - - - - - - - - - _ ~ _ _ - - - - -.. - - -, - - - - _ _ _ -, - - - _ - - - - _ _ - -. - - - - - - - - _
4.
TAaLE XII. Roweducibilnes of s= wee tJfs M-
_ _,.s Chareen! Te wa % aalmive Fluuruna Number of _
poems 8"'"' M' N
% aelse,e Trwe
(*C1 Numidny (1/mmi) id _ _._
peuerauen A*ersee : set Dev. - sat Dev.
s%TEDA 30 10 32 6
3 de L3 14 65 4.4 7
30 98 4.2 4
30 ISO 12.2 8
3% TEDA.
30 10 64 3
1 128 30A 8
s% K2, 3% TEDA 1s 90 32 3
ele 2 3s 24 96 a.os as as as e.
as o
o a2 ses no no OJ 132 1
S VI. EFFECTS OF CYCLIC FLOW (BREATHING breathing cycle (work load) were measured for calcu.
. PATTERNS) lated and related to instantaneous emeiencies throughout the cyc!c.
A.' Background The effects of variable flow rates and flow (breathing)
B. Computer Modehng Study rg panerns on the average emeiency needed to be.de.
termined also. Evidence is available (Section IV. C.) that A computer program was written which could calcu.
the emeiency of a sorbent bed for removing vapors from late canister penetrations of methyl iodide based on ai7 decreases with increasing airnow rate. There are data assumed airflow rate and reaction kinetics of removal.
which demonstrate, among other things, that peak Breathing patterns of airflow were taken from the work inspiration flow rates can be very high (200 Umin) at of Silverman, et al ' who measured and characterized moderate work loads.sa Therefore, at the peak of inhalation and exhalation curves at ten work rates for inspiration in the breathing cycle, the eficiency may be resistances approximating those of gas masks and other very poor and certainly will be very di5erent from that at breathing apparatus. Their Table 4 provided four the standard 64 Umin test airflow.
parameters used to simulate he varpng flows:
The work of Gary Nelson 'is widely misinterpreted as R = respiration rate (per minute) 8 showmg no such efTect. Actually, he demonstrated only A = maximum inspiratory flowrate (Umin) that, in a limited number of cases, the cartridge capacity I
= fraction of total cycle that is inspiration (lifetime) was unasected by airCow rate or cycling. In the F = minute volume, mean inspiratory flowrate over cases of highly toxic vapors (radiciodine, other radio.
an entire breathing cycle (Umin) nuclides, carcinogens, etc.) the aorbent bed emeiency, Only the inspiration flow was considered since exhala-rather than its capacity, is the limiting factor in determin.
tion is usually through an exhalation valve, rather than ing usefulness. This is because only low levels in air are through the canister. During expiration, flow through the expected to be encountered. resulting in low bed loading, canister was set at zero.
Experimental measurements and theoretical computa.
The equation which best ih the experimental breathing tions were done to identify and quantitate the c!Tects of curves was a linear combination of sinusoidal and cyclic flow patterns. Average emeiencies for a given ellipsoidal functions:
i
- A.
./
/ mi) f 2t i
8" 8
~
F = A, sm. l A:
1-i
-I l where 1
( 8/
(
'8
/
Osts1 P = penetration fraction of methyliodide 8
k = first order rate coefficient for removal (per see) where t, = bed contact time (sec) = 60V/F V = charcoal bed volume (L)
F.F.
= instantaneous.and average volumetric Howrates Wmin)
These equations were combined to calculate instan.
t,
= 1/R, the average time for inspiration (min) taneous and integral flowrates and penetration fractions A,A = constams selected for each work rate to match for steady and cyclic flows for selected values of k and V 3
the experimemal values of maximum flowrote' in the ranges of experimental values. The constant A, such that flowrate required to give a penetration equal to that of the cyclie flow was also calculated.
The simplest case, where k is a velocity. independent A = A, + A and F" =
A C nst*M. Was C mpmed Mt Mth the rdts shown b (x-A I 2[I Table XIV for k = 17.6 s-8 and Y = 330 cm. both s
8 8
Table XIII lists the input parameters and calculated experimental values (Section IV. E.). Average cyclic flow values of A, and A for ten workrates.The(trapezoidal) ~ penetrations were much higher than t i
steady flowrates. Higher steady flowrates (2.0 to 3.6 integrated flowrates for the best fit curves are given in the times) were required to give penetrations equal to the last column.
cyclic flow penetrations. The efTects of varying the A second assumption was that the canister was product k V on the cyclic penetration (PJ staady O
- "iiib'd " ' *"*" '"d *i"* *"*idi* "'"'""("J'""d'**"*""'
conditions, where the removal of methyl iodide was dese:ibed by first order kinetics (Section IV. C.):
In P, = -c (k V).
P = exp [-kt,)
In P, = -s (k V),
P/P, = exp [(s - c)(k V)},
TABLE XIll. Input and Calculated Parameters for Fitting Experimental Breathing Curves Average Maximum Respiration Best Fit Constants Imegrated Flowrate Flowrate Rate Inspiration A
A Flowrate (Umin)
(Umin)
(per mint Fraction (Umin)
(Umin)
(Umin) 9.1 37 14.8 DJ82 35.20 1.79 9.0 13.2 44 17J 0.431 26.42 17.58 13.1 19.8 60 18.7 0.464 29.92 30.08 19.6 27.0 78 20.7 0.479 32.89 45.!!
26.7 28.2 79 22.0 0.487 27.83 51.17 27.9 36.2 101 22.5 0.490 36.62 64.38 35.8 48.9 128 27.4 0J12 33.76 94.24 48.4 64.4 160 32.5 0.519 10.61 149.39 63.7 81.3 192 34.2 0.539
-0.26 W 26 80.4 90.3 240 42.0 0.514 86.13
!$3.87 89.3
______---_------a
p 3,
TABLE XIV. Cyclic.and Steady Flow Resuhs Calculated for a Constant Rate Coemeient*
Amage Penetradon Fracoon Equivalent Staady - Flowrate Integrated.
Plowrote (L/ min) Cyclic Flow Steady Plow Ratio Plowrote (IJmin)
Ratio 9.0 2 x 10-8 2 x 10-"
I x 1088 -
32.2 3J8 13.1 1 x 10-*
3 x 10-82 3 x 10' 38.2 2.92.
19.6 0.0011 2 x 10-'
5 x IO*
$0.9 2.60 26.7 0.0047 2 x 10-'
2 x 10' 64.9 2.43 27.9 0.0051 4 x 10-*
1280 66.0 2J6 35J 0.0145 6 x 10-8 244 82.3 2JO 48.4 0.0340 0.0007 46 102.0 2.13 63.7 0.0675 0.0042 16 129.3 2.03 80.4 0.1046 0.0131 8
154.4 1.92 89J 0.1423 0.0202 1
178.7 2.00
- k = 17.6 s-'. Y = 330 cm' where for each workrate e and : are average values of phenomenon.22. s including the velocity, va (crr/sec).
60/F for cyclic and steady flows, respectively. The dependence,
.O penetration ratio is a function of k V and, therefore, a runction or the,c=eir. tion fraction (P, or P,).*At the In P = -k v*V/F a
penetration fraction of most interest for determining cartridge service life, P, = 0.01, and at a total breathing where k is a "true" constant. Wheeler has shown rate of 64 L/ min (32 L/ min through each of two theoretically that the value of n should be 0.5 for the case cartridges of volume 165 cm ), k V = 4.962. P, =
of a mass transfer limited rate.8 Dietz, et al " obtained n 8
0.000087, and P/P, = 115.
value: of 0.45 to 0.58 for their hex-Since experiments were showing much smaller cyclic amethylenetetramine/ iodine / sodium hydroxide.im.
flow efTects (see b'elow), the simplest model was modified pregnated charcoals. The data of May and Poison" has to include velocity dependence of the rate coemeient.
been used to calculate the n values for a 5 per cent Dietz, B!achly, and Jonas observed a nonlinear increase TEDA-impregnated charcoal shown in Table XV.These of the first order rate coemeient with increases in linear results show a relative humidity dependence for n, which flow velocity for methyl iodide removal by impregnated ranged from 0.23 to 0.42.
charcoals.85 Others have also observed this TABLE XV. Rate Coemeient Velocity Dependence Calculated from the Data of May and Poison' e
Leg Log Least Squares Fit Percent Velocity Coemeient Relative Range Range Number Correls-tion Humidity (em/s)
(s-')
of Points n
(r')
50 17.5 101.3 40.7 85.8 4
0.42 1.000 60 17.7 101.7 34.5 67.1 4
0J8 0.999 80 17.3 103.2 25.4 42.3 8
0.29 0.970 94 17.5 101.5 21.2 31.8 4
0.23 0.994
- Reference 13.
l.
- kv.
a
- /-
/
, The computer program was modified to include linear wJocity dependence in the above penetration equation.
Cyclic / steady penetration rados for P, = 0.01 varied Results shown in Table XVI were computed from n = 0 from 2.49 to 5.13. Steady / cyclic flowrate ratios for P.
to 0.75, average F = 64 Umin (32 Umin through each of P, = 0.01 ranged from 1.90 to 2.76, with all but the two canridges), and k V seJected so that P, = 0.01.
lowest two workrates in the range 2.0
- 0.2. The Computed equivalent (P, = P, = 0.01) steady flowrates flowrate ratios for the extreme case of n = 0 wer are listed in the last column.
this range for cyclie breathing rates of 48 Umin and The value of n = 0.7 was used with the computer above (Table XIV). The cyclic / steady flowrate ratio is program and the parameters of Table XIII to calculate less variabic than the penetration rado, and is a possible way to take into account cyclic flow efTects.
the results in Table XVII for ten workrates.
TABLE XVI. Computed Values for Selected Velocity Parameters
- Steady Amage Pmtradon Fraedon Equivalent Steady n
Cyclic Flow Steady Flow Rado Flowrate (Umin) 0.00 0.01 8.7 x I0-8 115 64.6 0.50 0.01 0.0019 5.3 58.9 0.67 0.01 0.0036 2.8 58.1 0
0.70 0.02 0.0040 2.5 58.6 0.75 0.01 0.0046 2.2 59.3
' Assumed 32 Umin through each of two cartridges and breathing curve corresponding to 64 Umin total flowrote.
TABLE XVII. Results Computed a for Velocity. Dependent Rate Coef!Icient* and One Percent Cyclic Flow Penetration Integrated Amage Penetradon Fraed f Equivalent Steady Flowrate Flowrate (Umin)
Steady Flow Ratio Flowrste (Umin)
Ratio 9.0 0.0019,5 5.13 24.8 2.76 13.1 0.00254 3.94 31.2 2.38 19.6 0.00296 3.38 42.8 2.18 i
26.7 0.00318 3.14 56.0 2.10 27.9 0.00328 3.05 57.5 2.06 35.8 0.00335 2.99 72.9 2.04 48.4 0.00364 2.75 93.6 1.93 63.7 0.00375 2.67 121.2 1.90 80.4 0.00402 2.49 146.8 1.83 89.3 0.00378 2.65 169.2 1J9
'k. = k V,", Y = 330 em.
2
=
4 The computer program was modified to include linear veJoeity dependence in the above penetration equation.
Cyclic / steady penetration ratios for P, = 0.01 Results shown in Table XVI were computed from n = 0 from 2.49 to 5.13. Steady / cyclic Dowrate to 0.75, average F = 64 Umin (32 Umin through each of P, = 0.01 ranged from 1.90 to 2.76, with all bu two camidges), and k V selected so that P, = 0.01lowest two workrates in the range 10
- 0.2. The Computed equivalent (P, = P, = 0.01) teady flowrates flowrate ratios for the extreme case o are listed in the last column.
this range for cyclic breathing rates of 48 Umin a The value of n = 0.7 was used with the computer above (Table XIV). The cyclic / steady flowrate ra program and the parameters of Table XIII to calculateless variable than the penetration ratio, and is a the results in Table XVII for ten wortrates.
way to take into account cyclic flow effects, TABLE XVI. Computed Values for Selected Velocity Parameters
- Steady Amage Penetradon Fracdon Equivalent Steady n
Cyclic Flow Steady Flow Ratio Flowrate (Umin) 0.00 0.01 8.7 x 10-8 115 64.6 0.50 0.01 0.0019 5.3 58.9 0.67 0.01 0.0036 2.8 58.1 g.
0.70 0.01 0.0040 2.5 58.6 0.75 0.01
- 0.0046 2.2 59.3
- Assumed 32 Umin through each of two eartndges and breathing c I
corresponding to 64 Umin total floweste.
urve TABLE XVil. Results Computed a for Velocity Dependent Rate Coeff Percent Cyclic Flow Penetradon n
ne Integrated Amage Penetrador Fraedon Equivalent Steady Flowrate Flowrate (Umin)
Steady Flow Ratio Flowrate (Umin)
Ratio 9.0 0.00195 5.13 13.1 24.8 2.76 0.00254 3.94 19.6 31.2 2.38 0.00296 3.38 26.7 42.8 2.18 0.00318 3.14 27.9 56.0 2.10 0.00328 3.05 57.5 2.06 35.8 0.00335 2.99 48.4 72.9 2.04 0.00364 2.75 93.6 1.93 63.7 0.00375 2.67 121.2 1.90 80.4 0.00402 2.49 89.3 146.8 1.83 0.00378 2.65
- k.
k V.". V = 330 cm.
169.2 1J9 2
i k
s l
/!
C Experimental Study
~
Additional experiments were done with other charcoals to explore the generality of the cyclic flow A Scott Breathing Simulator (Scott Aviation Carper-effect. Comparisons of penetrations at cyclic and steady adon. Lancaster NY. Part No. 800!!6) was used to flow conditions (32 L/ min) were done with several produce cyclic flow patterns. It is a dual-piston pump cartridges, canisters, and beds packed with $2 55g of operated by a motorized cam to simulate a breathing charcoa! (7.5.cm-diam). The measured cyclic / steady pattem. The cam used in these experiments was desig-penetration ratios and experimental conditions are given mated 622 KGM. Total volumetric flowrate of air was in Table XIX. Figure 22 shows breakthrough curves adjusted with the pump speed control and measured obtained for two 5% TEDA charcoals, one which downsucam of the test bed with a dry test meter (Singer showed a definite cyclic flow effect (1.6 times higher Model DTM 325) over at least 20 cycles. A series of penetrations) and one which did not. Likewise for the check valves and a filtered air supply was used so that other charcoals, some showed an effect and others did during half of the cyc!c backflow through the cartridge not. There was no obvious way to predict when the was prevented. This was to simulate one way (inspira-cyclic flow would give a higher methyliodide pencuation tion) flow through a cartridge on a typical air purifying or how much higher it would be.
respirator. A 20-L polyethylene bottle was used to mix The significance of the cyclic flow efTect is seenin Fig.
methyl iodide from the pe mention tube with the main 22 for the Scott charcoal. There appear to be two airflow to smooth out possibic variations in cha!!enge separate breakthrough curves differing by the factor of concentrations due to cycling airflow. Total flow volume 1.6. The end-of service life, defined as penetration reach-over a time corresponding to a full number of cycles ing 1%, is 300 min for steady airflow, but only 180 for 20-25) was measured with a dry test meter downstream cyclic aidlow at 32 L/ min. At 1.5% the differences are g
(of the test htd to determme average flowrate. Other than much greater (>>$00 min vs. 260 min).
these modifications. the experimental apparatus was the A maximum penetration at about 120 min was same as that described in Sections III and VIII.
observed for the Willson/Ince 5% TEDA charcoal Test beds of 7.5-cm diam and 0.5 to 1.5-cm depth breakthrough curve (Fig. 22). This has been seen before were packed with varying amounts of 5 percent TEDA-for this and other charcoals and is attributed to bed impregnated charcoal (Bamebey Cheney CU 2762) to heating by water vapor adsorption (see Section V.A.4.).
obtain a range of penetration fractions at selected Both the cyclic flow and steady flow penetration fol-relative humidities (25 95 per cent) and ambient temper-lowed the same breakthrough curve.
ature (23 l'C). Airflow was maintained at 321/=in for both steady and cyclic (20.5 cycles / min) situations.
After the test bed was equilibrated at the selected reladve D. Conclusions humidity, penetration fractions of methy! iodide were determined at 10 min intervals, altemating steady and Both the computaticaal and experimental approaches cyclic flow for about 2-hour periods. The resulting to determining cyclic / steady peneration ratios led to the measurements were averaged and a standard deviation same conclusion: significant differences between break-was calculated. Alternating flow patterns for the same through fractions at a selected bed conditions (time of test bed eliminated the significant between bed variations use, humidity, temperature average flowrate, etc.) can experienced in earlier experiments.
exist for a variety of charcoals.The limited experimental Results summarized in Table XVIII show definite and computed data acquired so far does not reveal the j peneustion differences for the cyclic and steady flow factors determining the existence or mr.gnitude of this {
cases. Cyclic flow penetration was greater by factors effect for any given charcoal.1 is of great interest for a from 1.2 to 4.2. However,
- c was no consistent variety of respirator applications, not merely radiciodide correlation of ratio with penetration fraction, contrary to removal, to identify these critical parameters. The ex-(
the computer calculations. This suggests that the real istence of a cyclic flow effect impacts on manufacturing.
situation is complicated by unknown factors (e.g., rela-testing. certification approval, and use of chemical air tive humidity, granule size, packing density, bed depth.
c! caning respirator cartridges and canisters.
etc.) having unknown effects.
TABLE XVill. EW.. utal Resuhs of Cyclic Flow Study at 321./ min for one 5% TEDA charcoal (BC CU 2762)
Relative Cyclic (C) or
' Average
' Standard Ratio Humidity % - Steady (S) Flow Penetration Deviadon -
(C/S)
' 25 '
C 0.025 0.003.
. 4.2 5
0.006 0.001 C
0.145 0.019 '
- !J S-0.112 0.010 50 C
0.045 0.005-
' I.9 5.
0.023 0.002 C
0.076 0.013 1.7 S
0.045 0.005 C
0.086 0.007 1.6 5
0455 0.012 75 C
0J04 0.027
-IJ i
S 0.238 0.022 86 C
0.081 0.005 2J S
0.032 0.003
.g C
0.067 0.008 3.5 5
0.020 0.001 95 C
0J12 0.012 1.2 5
0.443 0.028 C
0.177 0.008 1.7 S
0.101 0.007 An immediate concern for this project is how to take The second option, doubling the steady airflow, is
- into account cyclic flow efTects on methyliodide penetra.
based on the computed results in Tables XVI and XVII.
-)A, tion.Three options have been considered:
which show that this approximately compensates for
- 1) Define end of service life of a canister or cyclic flow at a variety of conditions. Unfortunately, the j
cartirdge at a lower penetration fraction (e.g.,
expenmental resuhs reveal a more complicated situation.
N 0.5% instead of 1%).
This option also has the same objections as the first.
- 2) Double the testing airflow rate.
~
Humidity effects would be more than doubled by'
- 3). Use's breathing simulator pump for testing.
doubling the airflow rate. And modifications would be The first option would require identifying a constant required for the existing testing apparatus. The third or average eyelic/ steady flow penetration factor. Tables option also would' require modifying the existing XVIII and XIX show a significant range for this ratio.
apparatus by I) inserting a breathing simuistor
~ Furthermore, this option would penalize those manufac.
pump and one way valves between the fihered air supply turers using charcoals which have no such effect and and the humidity chamber, 2) inserting a 20 L buffer y [. may hinder the development of more efTective sorbents.
volume between the methyliodide generator and the test For example. the Willson/Inco cartridge in Fig. 22 would have failed (> 1%) entirely instead of having a service life bed and 3) changing the method of average flow rate morutoring (volumetric averag. instead of an instan.
of about a5 min.
taneous flowmeter readout). The question remains as to w
se.<:-> c o
i
. '/
l
\\
~
TABLE XIX. Cyclic / Steady Flow Penetration Ratios for a Vasiety of Charcoals.
Charcoal Original Packed Preconditioned? Run Relative Number of Average Cyclic / Steady Source and Type' Unit Bed'
(% RH)
Humidity (%)
Comparisons Penetration Ratio Nonen OV Cartridge.
X No 75 2
1.0 t 0.1 (7500-l)
X No 85 2
1.0
35 50 3
1.3 i 0.1 GMA (44.35)
X 50 85 3
1.0 0.1 GMAC MSA Canister.
X No 85 4
1.0 0.1 GMR-1,5% KI, MSA Canister,'
X No 85 4
1.720.2 5% K1,2% TEDA 3
MSA Canister,'
X 95 95 4
1.0
- 0.1 5% TEDA '
Scon Canister, X
No 85 7
1.6 0.1 5% TEDA (600252 75)
X 85 95 2
1.7 0.2 Barnebey Cheney X
No 85 1
1.9 t 0.2 5% TEDA (CU 2762)
X 85 85 4
1.8
- 0.2 Willson/Inco Cartridge,'
X No 85 2
1.3 0.1 5% TEDA (Lot B)
X 95 95 1
1J 0.1 Willson/Inco Cartrid"ge,'
X No 85 4
1.0 0.1 l
5% TEDA (Lot Y)
X No 85 1
0.9 0.2 X
No 85 2
1.2
- 0.2
- 1mpregnants and amounts based on manufacturers'information.
' Prototypes supplied by manufseturers.
'55 g in 7.5 em-diam bed.
i 34 Thir compound has a normal boiling point of 174'C, w-A,,, '
but is known to sublime readily at room temperatures.
j *""
E Ag The volatility of the pure crysuls has brought up the 5,.
A question of the volatility of TEDA impregnated in f
~~~~~~a activaud charcoals. The reason for this concern is the
[ **
F possible release of significant amounts of this amine of unestablished toxicity from sorbents, especially in air
,e g e/
purifying canister applications.
om.
/e
'e There are no toxicological data available for TEDAt e
however, TEDA belongs to the class of organic aliphatic amines, may of which have been shown to be toaic.
e ao ion iso ano no son ano =.ao ano ano Threshold Limit Values (1982)" for similar amines are:
en e
faon*
mg/m' ppm 5
Ethylamine 18 10 4
g e oio.
'e Diethylamine 30 10 5
j Triethylamine 40 10 E
Ethylenediamine 25 10 Diethylenetriamine 4
1 asao By structural and functional similarities. TEDA can be considered moderately toxic with a concem level of I smecac Tmc (sminut )
ppm or greater. Vapor pressures measured over the Fig. 22. Sreshhrough curves ahemaring sseady flow ( o ) and cyclic range 50-110*C have been extrapolated to give 0.58 torr now W for two $% TEDA charcoals.1)pper cwver Scan (!!g. 7.s.
at 25'C. However, there was no information available em diamb Lo er surve: willsorance ts:s. 7.0-cm diamk IS% RH.
on the volatility of desorption rate of TEDA impregnated 32 t/ nun.
on activate charcoal.
To supply data to answer these concems we have measured TEDA desorption from commeries) im-which breathing curve parameters to use and how critical pregnated charcoals, are they to the final penetration results.
The third option appears to be the most desirable, at leas? until more data is developed. The selection of B. Apparatus and Procedures parameters would be no more arbitrary than the selec-tion of an average breathing rate, usually 64 IJmin, for The apparatus used for measuring TEDA desorption testing. The data of Silverman, et al,'is available to make is diagrammed in Fig. 23. The detector for TEDA in air these selections less arbitrary.
was a photoionization detector through which air sam-pies are drant. Detector response was amplified and attenuated with the electrometer component and re.
VII. DESORPTION OF TED A FROM IM-corded on a suip chart. The detector was calibrated by PREGNATED RESPIRATOR CHARCOALS sublimation of TEDA crystals at 30.0'C into flowing air. Weight loss rate and diluent air flow rates were A. Background measured and used to calculate calibration concentra-tions.
Data reported earlier (Section IV.) have been shown A gas chromatograph oven was used to control
(.
that TIDA [N(C,H.),N]is an effective charcoalimpreg-temperatures (70-120'C) of test beds, the air entering nant for the trapping of organic forms of radiciodine them, and the sampling lines. Charcos] samples of 1-4 from air. Four canister manufacturers have plans to em' volume were packed into stainless steel tubes and continue or begin packing their radiciodine canisters held in place by glass wool. This resuhed in bed depths of with 5% by weigth TEDA impregnated charcoals.
1.4 5.6 cm.
{
. l
~
,s 4
z was also tested under the same conditfor.3 to provide a
!!!ectrometer a
Pumo-O,
c,",,
reference and to identify any iodine release upon heating.
l\\ l 00 Oven C. Results and Conclusions 0
1 j
i v
o V*nt Since breathing through a respirator cartridge is not at Blenk Test a fixed, constant flow rate, we first studied the effen of Bed Bed airDow velocity. The resuits shown in Fig. 24 for one of the 5% TEDA charcoals show the absen:e of effe:t of ~
flow rate over the range 1.6-6.8 cmh. This implies that g
y the air was TEDA saturated and the volat.ilization rate Recorder Filtereci A;,
was rapis.
Since bed depths also vary for different designs of Fig. M. The appa.rst.is used for snadies of 77.DA desorpuon frotri car *. ridges and canisters, we also varied this parameter, czareonh.
Again, no effect was observed (Fig. 25). This resch.
combined with no velocity effect, implies that the air Compressed air from cylinders was passed drough a passed through the impregnated charcoal was saturated filter of activated charcoal before use. It was quite dry witn TEDA vapor;in other words, at equilibrium.
initially. For higher humidity studies a fraction or all of Humidity was also varied over a range from 5% to -
. the airflow was passed through the headspace of a water 99% RH at 25*C. Dew points of-18 = 4*C. !!.1 =
@ reservoir. Resulting relative humidites were deter =:ned 1.4 *C, and - 24.8 0.7'C were measured at test using a dew point hygrometer.
conditions of 70*C. 90'C. and 110*C. At 25'C these
. Two charcoal beds were placed in the even in such a dew points correspond to relative humidities of 4%. 54%,
way that the airnow could be switched by a valve to and 99%. Increasing water vapor cone:ntratiens de.
either. One bed contained unimpregnated activated creased the response of the photoioni:stion dete=cr.
charcoal and the other the test charcoal. Air flowed When this response change was taken into ac: cunt. no through the former to the detector during even equi!! bra.
detemable changes in TEDA desorption rates were tson. Upon reaching a steady dete=or baseline signal the airnow was switched to the test bed. An upscale signal shift o::urred.
ie
'C*C Such signal shift measurements were repeated at the same conditions, often using a fresh bed. At least three q
m-nperatures were used for each charcoal. Signal shifts
} m-recorded on the strip were measured with h ruler,
~
multiplied by attenuation factors, and compared with calibrauen curves to get TEDA concentrations (mg/m ).
{.
3 Three kindt of TEDA-impregnated charcoals frem 5 commer::al sources have been studied for TEDA de.
serpuen. Four of these contained a 5% by weight g,,
7e c a
loading of TEDA. Another had a mixed im.
pregnated-2% TEDA and 5% KI,. And one char:ca]
was impregnated !% with a new compound called "C-Alkyl TEDA" or " Heavy TEDA." which has an alkyl e
i s
a s
6 7
( group, such as ethyl, added to one or more of the Amtow vnocrrr c e.>
ethylene bridges. The main objective is to mait a higher Fig. 24. ESet of alrnow velaerry on TEDA vapor desorpuon molecular weight cornpound with lower Volatility. The concentration at twc temperatum.
added alkyl group should not affe= the reactive nitro-gens. Another char: cal impregnated with 5% KI, orJy,
- s chuacteristics (activity, surface ater pore structure.
{
pore size, etc.).
)
F:g. 27 shows a comparison of desorption concentra.
J tions of TEDA and Heavy TEDA. Both charcoals were 3 ** j from the same tr,anufactt:rer who said the same base charcoal was used. Note that the Heavy TEDA desorp.
I.
tien was about 10 times lower than that for TEDA.This
{
is what was expected. E!T!:iencies for trapping methyl w m-iodide have been found to be simile for both impreg.
E
?
cants.
0 7e*c As we have seen from Figs. 26 and 27. Clapeyron E
equation plots (log C versus 1/T) are linear. Thts was
~
i expected from analogy with evaporation and sublimation 8
2 8
processes. The slopes of these plots are directly proper.
8"""**
tional to heats of desorption. The range of rneasured Fig. :. Effect of bed dep:.h on TIDA vapor desorpoon concentre-heats of desorption are shown in Table XIX. The.
non as three mnpersnires.
average is 25 kcal/mol, much higher than the 14 kcal/mol heat of TEDA sublimation from pure crystals.
The difference is due to EDA cht.rcer.! interactions.
observed over these ranges of experirnental parameters.
The 25 kcal/mol average corresponds to a doubling of
' y Only dry air was used in other expenments.
desorption concentration with every 5'C rise in tempera.
For the ordinary 5% " EDA charcoals desor; tion tzre.
concentrations varied widely (Fig. 26). For example, at Another use of the Clapeyron equation plots is 2
90*C the range was 4 to 48 mg/m. The mixed excapolation to lower temperatures where TEDA de-3 impregnant charcom] gave a value of 6 mg/m, at the sorption is too small to measure directly. Such extrapola-lower end of this range. No iodine or other desorbing tiens to 25'C yidded the TEDA vapor concentrations vapors were detected from the 5% KI (only)-im.
shown in Table XX.
3 pregnated charcoal up to 120*C.
The most important conclusion from these studies is The ditTer:nces in desorpuen rates for the four 5%
shown in this table: The maximum desorbed TEDA TEDA charcoals are significant. They may be due to vapor concentration at 25'C was cajeulated to be 0.12 impregnation methods or due to the charcor.1 base TE#PtE ATURE (*c3 TEAPft ATutt ((3 h6 30 0 to ae
!!O le0 to 30 70
- 88 -
3 I
~
S
~
T SZ TEDA
$a TeoA e
tf sPtt A TOf I
CMARCOALs y 20 -
r
=0; E
E:
E 5*
$1H-TEDA g'
E "I a
w m.
3 s
p 5
O::
i i
ts 26 er 2
29 23 26 27 to 39 30 afCP90 CAL TimPf't Atuff 210 (*K7 RicPtOCAL TEmPit Atuet ricater "3 Iig. 25. C:ssewen picts for TED A *eoor oeert=c frem 8 % TED A Fig :" Clavoton plots /g, spor dcwreed frern a w# M A
w j ' so : xi:clegical data is available for TEDA but of methyl iodide peaks to the electron capture dete: tor -
- .. *cil below the Threshold Li=it Values for similar (Valco Instrument Co. Model 140B). Each sampic
, min es, which range from 4 mg/m3 for passes through its own column (LO or 0.6 m long) with 3
c edylenetrizmine to 40 mg/m for triethylamine.8' its individually controlled carrier ges flow rate to ac.
herefere, there should be no toxic hazard from using complish this. A third valve momentarily vents the TEDA-impregnated charcoals up to the 5% by weight effluent from both columns to keep air from passing icvel.
through the detector. A downstream sampling loop 10 times larger than tne upstream one gives methyliodide VIII. TEST APPARATUS DEVELOPMENT Peaks closer together in size during the earlier stages of bed penetration. These improvements, the substitution of During the course of this project several experimental a dew point hygrometer (EG&G. Model 911) for a appuatuses have been built and used for challenging and resistance type hygrometer, and high output generation
. ::stng serbent beds, canisters, and cartridges. The two of methyl iodide from permeation tubn were major steps ts.rliest apparatuses have been described elsewhere and to the final test apparatus design.
8
.n Section III and Fig. 2 of this report.
The finaj test apparatus, pictured in Fig. 25. contains After experiments with radiciodine were completed the in one unit on wheels: (1) air flow, humidity and snalyti:al instrumentation for sampling and measuring temperature control. (2) methyl iodide generator. (3) metnyl iodide in air was redesigned and rebuilt. Goals sampling pumps and automatic samplers. (4) dual col-were compactness. simplicity, automation, and low cost.
umn gas chromatograph with sampling valves and Sarnpling valves and loops were mounted in a heat valve electron capture dete: tor, and (5) data integrator with even (Carle Instrument Inc., Model 4300) to over:ome chart recorder. It requires for operation: (1) compressed the problem of water condensation during high humidity air. (2) distilled water. (3) argon / methane carrier gas. and
- sts. A more efficient gas chromatograph column pack-(4) electri: power. Two Respirator Cartridge / Canister h,Porapak Q.5) for separating methyliodide from air Test Systems have been built, one for our use and one for was found. This made possible smaller columns inat also - NIOSH.The capabilities are:
- ould be mcunted in the valve oven and eliminated the Temperature: Ambient--10'C l
Seed for a separate large gas chromatograph. Two Dew Point: s25'C l
ampling valves were ganged by gears for simn!taneous Airflow Rate: s100 L/ min (Constant) ampling upstream and downstream of a test canister.
Penetration Fraction: 20.001 his chminated the need for interpolating between peak Challenge Concemration: 20.1 ppm CH 1 3
.rees of alte-nate samples when making comparisons.
Advantages of having two units in !ude the capabilities 3 simultaneous sampling requires di!Terent umes of amval to confirm testing resuhs, to help NIOSH with TABLE XX. Triethylenediamine Desorption g
Charcoal Heat of Desorption Vapor Concentration Impregnants
'keal/mo!)
at 25'C (mg/m')
5% TEDA 19.6 0.12 23.2 0.032 31.6 0.0003 26.6 0.0025 2% TEDA 2S.5 0.0011
+5% KI, 5% H TEDA 19.0 0.016 32
t
- )
troub! shooting, and to provide backup in case of major In November 1981, meetings were held in Rockville, breakdowns.
A detailed and descriptive operations manual for this MD. with NRC and NIOSH personnel to renne some of I
these proposals. We identified probable maximum use test system has been written" and will not be repeated here. The table of contents is given in the Appendix of conditions (90'F or 32*Ct 100% RH).The proposal of this report to i!!ustrate the information provided to the user discretion in setting service life based on data to be NRC and NIOSH. It includes diagrams, photographs.
provided on work rates and breathing volumes was rejected, since it was felt that user knowledge was often spe:ineations, instru:tions, precautions and component inadequate and the radiciodine has no wartung tnanuals.
properties in case of overuse. We identified some addi.
The nrst draft was. subjected to an evaluation sug-gested by Donald Campbell of NIOSH. Five te:hnicians tional use restrictions (interferences. storage, maaimum and staff members not familiar with the apparatus were conce::tration, facepiece performances et:.) that must be given the ins;: ructions and apparatus and asked to part of the approval. Another revised set of testing pe: form a cartridge test. These evaluations revealed conditions (30'C and 25'C at 50% RH and 85% RH) was proposed. Steps necessary for follow up of this some un:! car and out cf sequence instn::tions and meeting were agreed upon.
provided useful suggestions for improvements. Tne Enal draft was once again evaluated in this way to make sure The ANSI Ad Hoc Re:pirator Testing and Approval the changes had been effe:tive.
Subcommittee meeting in Los Alamos in De:emoer 1981
[
In the light of the discovery of signiE: ant cyclic flow was another good opportunity te discuss relevant sub-effects, this apparatus and manual will need to be jects with representatives from many industry and gov.
r ernment organizations.
modined to include a breathing simulator pump and g
associated parts (See:. ion VLD.).
Approval requirements were modined to allow several '
classes of approvals by humidity range (high and moderate) and minimum service life for 1% penetration:
DC. DEVELOPMENT OF APPROVAL CRITERIA FOR RADIO!ODINE CANISTERS High Humidity, 30 mmutes at 30*C and Half-Hour 100% RH A. History High Humidity.
60 minutes at 30'C and One Hour 100% RH Preliminary proposals for approval (acceptance) er:teria were presemed and discussed at NRC and Moderate Humidity, 60 minutes at 30'C :.nd NIOSH in February 1981. Testing conditions proposed One. Hour 75% RH we e: 0.3 ppm CH'I challenge at 64 L/ min. 25'C, and two humidities. 50% and 85% RH for freshly opened Moderate Humidity.
120 minutes at 30*C and Two. Hour 75% RH (not equilibrated) canisters. Ac:eptable servi:e lives proposed were 8 hours9.259259e-5 days <br />0.00222 hours <br />1.322751e-5 weeks <br />3.044e-6 months <br /> at 50% RH and 3 hours3.472222e-5 days <br />8.333333e-4 hours <br />4.960317e-6 weeks <br />1.1415e-6 months <br /> at 85%
The reasons for more than one class of approvals are:(1)
RH which extrapolates to 2 hours2.314815e-5 days <br />5.555556e-4 hours <br />3.306878e-6 weeks <br />7.61e-7 months <br /> mi.imum at 100%
to allow some current canisters to be approved and (2) to RH.
provide incemive for manufs:turers to develop improved Ftriher discussions and additional experime::ts led to canisters for higher classes (i.e., High Humidity, Eight a revised set of proposals in Apnl 1981. Testing at a Hour) of approval.
higher temperature (30'C) was added. Close control of The approval schedule should also include periodie RH (:2%) and T (e1*C) was required. A testmg to verify shelflife claims of manufa:rurers, reproducibility requirement of 10% on service life Additional use restrictions that must be put imo the measurements was preposed, as was identifying service regulations for use and on approvallabels include:
life in te ms of total breathed volume. instead ofin terms L Not to be used in the presen:e of organic solvent of time of use. A knowledgeable industnal hygienist or vapors.
'/
suoervisor would then be able to calculate a service life
- 2. To be stored in sealed, humidity barrier pa:kaging based on T. RH, and work level. These ideas were in cool, dry environments.
a dis:ussed over the next several momhs with vanous
- 3. Service life is to be ca!:ulated from the trne of intereste: parues.
unsenhng in:!uding penods of non enposure.
s:
j O
.w I
I 4
i l
i
~
d il "_ _ %!
m
==
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O w
e M T' I
a 4 I 84 4.
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... ~ w 1
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.. - u. =
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samaq-J e
g
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se
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y 4
-7
- *rfy a
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---4=
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y k.,p. ig,9:
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Q g
as e enume es.
m.
o m
k m
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g Iu.[_ [.T-== - W h.,-
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- m..,.<7r- -.,2,-. y, Q3.
,, ' q
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N' y< *_
,... --...3
--- e..c h e t a, 3Y-T ec'*~p2f.1*2 tt*s y? T
--=~p.'-
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- =
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- n
- * =dt
,. _.'e:. 7 g
- f
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..y.. 4, =
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. = e..
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.g F. 28. Appanrus developed for tesung radiciodine cartndges and canist.cre using methyllodida.
4
O
- 4. To be used with a fa:epiece capable of providing dition and provides a safety factor for use at less severe protection factors greater than 100, as det ised by conditkas. The maximum testing hurradity was reduced
.asting with a HEPA filter and aerosol.
from 85% to 75%. since at 30'C the latter corresponds
- 5. Not to be used in chauense concentrations of total to a dew point of 25'C. the maximum practically organic iodide, including nenradiometric iodide, greater anainable without placirg the testing apparatus in a than 1 ppm.
warm (>25'C) room or envirormtal chamber. Linear Also in December 1981, NIOSH initiated by imernal extrapolation of results to 100% at 30*C using tog memo procedures for establishing an approval schedule ' service life versus log RH plots is recommended.
on the following conditions: (1) NRC will first establish Triplicate inster.d of dupli:ste service life deternunations administrative controls, (2) Los Alamos will provide will better define reproducibility and the need for addi.
NIOSH with the testing equipment. (3) approval will be tional testing.
for me6yliodide, the testing agent, only. NRC then can allow use for other iodine vapor species based on Los Alamos and other data.
X. ASSISTANCE TO NIOSH IN ESTABLISHING A TESTING AND CERTIFICATION PROGRAM B. Current Recommendations All data, conclusion, and proposa!: generated from this project have been shared with the NIOSH TCB from The current recommendations for radiciodine the beginning. This has been accomplished by visits to cartridge and canister testing conditions and acceptance one another's laboratories, in-person and telephone con.
criteria are summarized in Table XXL Also listed are the versations, trip repons. progress reports, public presenta-current criteria from the U.S. Code of Federal Regula.
tions, and publications.
(
tions* for organic vapor canisters for comparison. The A final test apparatus described in Section VIII was latter are caDed current recommendations, rather than built and shipped to the NIOSH TCB for their use in final ones, since discussions wi!! continue in the regula, certification testing. An extensive operation manual was tory process.
prepared and also given to NIOSH. Followup visits to Testing should be done at two relative humidities and the Morgantown, WV, laboratories are planned to help at 64 Umin cycli: airflow for canisters and 32 IJmin NIOSH in setting up and using this equipmem. Los cyclic ai-fiow for cartridges used in pairs. Cha!!cnge Alamos will also be available for telephone consultations, cen:entration should be I ppm medyl iodide. aldough as needed. The duplicate apparatus at Los Alamos will this is not a criti:al parameter. Units are to be tested as be useful for identifying and correcting problems NIOSH re:eived and freshly ope::ed. Tests at 25'C were may encounter as well as for performmg interlaboratory climinated sin:e 30'C represents a more severe con.
comparisons of test results.
e Tf
m.
C.:
TABLE XXI. Testing Conditions and Acceptance Criteria for Organic Vapor Chin. Style Gas Mask Canisters Test CFR TrJe 30 Radiciodine Parameter Part !!.102 Proposaj Vapor
- CCl, CH1 3
Concentration 5000 ppm I ppm Relative Humidity 50 5%
50; 75% (e 2%)
Temperature 25 2.5 'C 30 1*C Total Airflow As Received 64 Umin 64 Umin Cyclic Flow 4 Equihbrated 32 UMin EquDibration 3.As Received All As Received (6 H at 64 Umin) 2.At 25% R.H 3.At 50% RH 2-At 85% RH 3 At 75% RH Maximum Penetration 0.1% (5 ppm) 1% (0.01 ppm)
Minimum Service Life 12 min 30 min at 100% RH' 60 min at 75% RH
' Extrapolated from 50% and 75% RH.
REFERENCES
- 5. A. Wheeler in Catalysis. Vol. II. p.150. P. H.
Emmet, ed Reinhold Publishi::s Co New York.
- 1. G. O. Wood. G. J. Vogt. D. C. Gray, and C. A.
NY (1955).
Kasuni:."Critena and Test Methods for Certifying Air Perifying Resp:rators Against Radiciodine."
- 6. O. Grubner and D. W. Underhi!!. "Caj:ulation of Los Alamos Scient:5: Laboratory Progress Report Bed Capacity by the Theory of Statisti:a! Mo.
NUREG/CR-1055. LA 8029-PR (September ments." Separation Scien:e 5. 555 (1970).
1979) AvaDable from the National TechnicalInfor-mation Semce, Sp: ngneld. VA 22161.
- 7. G. O. Nelson. A. N. Correia. and C. A. Harder.
" Respirator Can.:dse E5:iency Studies: Vll. Efre:t
- 2. G. O. Wood. " SOP for Use of 22'1 in the Testing of of Relative Hum:dity and Temperature." Am. Ind.
Respirator Components." Unpublished document.
Hyg. Assoc. J. 37,281 (1976).
Los Alamos National Laboratory,' Industrial Hygiene Group. Los Alamos. NM 87544 (February S. R. C.1.4e and L. Silveman. "An Apparatus for l
1979).
Measuring Air Flow During Inspiration." Rev.
l 5:icnt. Instruments 14, 174 (1943).
- 3. M. J. Kabat, private co== uni:ation of unpublished I
data. Ontano Hydro. Heahh and Safety Division,
- 9. L SDverman, et al. " Air Flow Measurements on Toronto. Canada (19E2).
Human Subjects with and without Res;:ratory Re.
sistance at Several Work Rates." A. M. A. Arch.
- 4. Department of the Interior. Dureau of Mines, Ind. Health 13.(1956).
" Respiratory Protective Devices: Tests for Fees." Tj' e 30. Code of Federal
- 10. G. O. Nelson and C. A. Harder. -Resp: rater Pe=rssibility:
J Regulations. Part i1. Fed. Reg. 37. No. 59 (March Carindge Em iency Studies !Y. E!Te:ts of Steady-
- 25. 1972).
State and Pulsateg Flow." Am. Ind. Hyg. Asso:. J.
- 33. 797 (1974).
,o 12.' V. R. Deita, C. H. Blachly, and L. A. Jonas, Available from the National Technical Information
" Dependence of Gas Penetration of charcoal sees service Springfield. VA 22161.
. on Residen:= Time and Linear Velocity," Proceed-ings of the 14th ERDA Air Cleaning Conferen:c,
- 15. R. D. Ackley," Removal of Raden 220 for HTGR CONF 760822, Vol 1, p. 233, M. W. First. ed.
Fuel Reprocessing and Prefabrication Off-Gas (1977). Available from the National Technical Infor.
Streams by Adsorption, DRNL TM-4883 (April mation Service, Springfield, VA 22161.
1975). Available from the National Technica! Infor.
mation Service, Springfield, VA 22561.
P
- 12. L. A. Jonas and J. A. Rehrmann. Carbon 12, 93
- 16. Threshold Limit Values for Chemi:a] Substances (1974).
and Physical Agents in the Workroom Environment
- 13. F. G. May. e.nd H. J. Poison, "Medyl Iodide with Intended Changes for 1982, Ameri:an Con.
Penetration of Charcoa! Beds: Variation with Rela.
ference of GovernmentalIndustns] Hygienists, Cin.
tive Humidity and Face Velocity," Australian cinnati. Ohio (1982).
Atomi: Enegy Com=:ssion repon AAEC.E322
- 17. G. O. Wood, V. Guts: hick, and F. O. Valde:.
(1974).
" Operating Manual. Respirator Cartridge / Canister
- 14. D. W. Underhill " Mass Transfer of Krypten.E5 in Test System Using Methyl lodide." Industrial Charcoal Adsorbers," Proceedir.gs of the 9th AEC Hygiene Group, Los Alamos National Laboratory, Air Cleaning Conference. AEC-660904, Vol. 2, p.
Los Alamos, NM 87545 (1982).
E24. J. M. Morgan and M. W. First, eds. (1967).
f l'
l l
l 37
.e
.F 1
u 1
APPENDIX - Table of Contents from Reference 17.
1, OPERATING MANUAL. RESPIRATOR CARTRIDGE / CANISTER TEST SYSmf USING METHYL IODIDE Contents -
Page
- 1. GENERAL PRINCIPLES OF OPERATION A. Introduction -
.........................,.............. 1 B. System Description
.................................... I
- 1. Block 1: Main Air Supply
.............................. 2
- 2. Block 2: Methyl lodide Challenge Generater 3
- 3. Block 3: Humidifying and Heating Se: don, Main Air Flow 4
4 ~ Block 4: Measurement Section
............................ 5
- 5. Block 5: Gas Chromatograph and Ac:sssories 7
C.. Component Identities and Specifi:ations
........................10
- 1. Commercial Compenents
..................,...........10
- 2. Components Built at Los Alamos National Laboratory
..............14 II. INITIAL SET.UP TO STANDBY CONDITION A.
Input Requirements: Power. Air. Water. Carrier Gas
.................15 B: Connections and Adjustments to Reach Sta.ndby Condition
..............16 III. CHOOSING AIR FLOW RATE, TEMPERATURE. AND RELATIVE HUMIDITY A.
Flow Rate
.......................................18 B. Temperature and Relative Humidity
..........................18
.IV. STARTUP FROM STANDBY TO RUN CONDITION
.................19 V. CALIBRATING AIR FLOW RATE AND GAS CHROMATOGRAPH SENSITIVITY A. ~ Calibrate the Main Air Flowmeter...........................
24.
B. Check Gas Chromatograph's Peak Resolution
.....................25 C. Measure the GC Sensitivity Ratio (Upstrez ::: Downstream)
.............26 VI. INITIATING A TEST RUN A.
Preparauon
.......................................27 B. Periodic Checks During Automated Run........................30 VII. RESETTING THE SYSTEM FOR A NEW RUN A.
New Air Flow Rate...................................31 B. New Min Air Temperature
..............................32 C. New f. elative Hunudity.................................32
,m
.cW:
- VIII. '. TREATMENT OF DATA.
L, A. For Each Individual Run................................ 3 2 B. Extrapolating a Set of Runs to Reference Conditions'
..................i33 IX.' SHUTDOWN FROM RUN TO STANDBY' CONDITION...............
34-
~ X.1 SHUTDOWN FROM STANDBY TO " FULL OFF" CONDITION
....... -.... 3 5
'XL MAINTENANCE AND REPAIRS.............................
37 A.. Air Supply Filters (Both).
B. Carrier Gas Purifier
. C. Permention Tube
~ D.~
GC Packed Columns E.
Ecetron Capture Detector F. Humidifying Water Bath G. Main Air Flowmeter
- APPENDIX I.
CHECKLIST OF CONTROL SETTINGS FOR FULL OFF, STANDBY. AND RUN CONDITIO NS........................................ 3 9 A,PPENDIX II.. INSTRUCTION MANUALS FOR COMMERCIAL COMPONENTS
...43-
'A.
Main Air Digital Flow Meter: Datametrics Model 810L Flowmeter -
-.B.
Liquid Level Controller Relay: Pope Scientific Company. Lab Monitor III.-
C. Digital Humidity Analyzer /Contrc'!!ct: EG/G Model 9II Dew.A!! Digital Humidity Analyzer.
D. Dual Ten-Port Multi-Functional Sampling Va*ves: Valco Instruments Co. Model AH.V.10 HPa which includes Valve Actuators (Model A60), Valve Oven (Model HVE.2). and Sampling Loops for Application 32.
E. Digital Valve Programmer: Valco Instruments Co.
F. Temperature Controllers: Valco Instruments Co.
G. - Carrier Gas Purifier: Supelco H. Electron Capture Detector: Valco Instruments Co. Mode! 140.
I. ECD Chan Recorder: Cole.Parmer Instrument Co. Model 8377 10.
- J. ' Auton;atic Peak Integrator: Spectra. Physics "Minigrator" l
ENCLOSURE 3
{
)
3.
I l
Mine Saft ty Appliances Company
- P.O. Box 426
- Pittsburgh, PA 15230 Writers Direct DialNo.
Telephone:(412)%7 3000 (412) 967-3194 April 5, 1989 Mr. Tim Kirkham Southern Company Services P.O. Box 1295 Birmingham, Al 35201
Dear Mr. Kirkham:
The purpose of this letter is to confirm our telephone conversation regarding MSA's recommendations on the storage of the GMR-I Canister (MSA P/N 466220) at nuclear facilities having NRC exemptions for radiciodine protection factor credit.
The original exemptions (including Farley Nucler.r Diant) required that GMR-I canisters be *,tored in a Class A environment. MSA did not feel this level of storage was necessary and we began a test program to determine if any special storage was required. Accelerated storage and moisture permeation tests were conducted and they indicated that Class C storage was sufficient. Storage for all canister inventory at MSA is Class C.
Later exemptions (e.g. Callaway) reflect the Class C storage requirements. You may want to contact them to obtain a copy of the data they submitted to the NRC.
Sincerely,
.5 Eric J. Beck Product Line Manager
'.~
s
.s t.
LOCATION: RIDC Industrial Park
- 121 Gamma Drive
- Pittsburgh, PA 15238 wasos nev.oc
]
L
- r i
.vi ENCLOSURE 4 l
A i
Mine Safety A;pliances Company
- P.O. Box 426
- Pittsburgh, PA 15230 Writers Direct Dial No.
Telephone:((12)967 3000 (412) 967-3194 1
i September 18, 1989 Mr. Tim Kirkham Southern Company Services 42 Inverness Center Parkway Birmingham, AL 35242
Dear Mr. Kirkham:
The purpose of this letter is to update you on the further testing we have done on GMR-I canisters.
ACCELERATED STORAGE TESTS In August 1985 we randomly selected 24 canisters from Lot 96 (which were manufactured on April 18, 1985), and placed them in 120*F,100% RH storage. The initial inspection on Lot 96 showed an average instantaneous methyliodide penetration of.43% at 480 minutes-(challenge concentration was 10 ppm methyliodide).
After 6 months storage, three canisters were removed and tested. No detectable penetrations (<0.1%) occurred at 480 minutes (5 ppm methyliodide concentration).
The te: ting was continued to the end of service life and the elapsed time to a 1% breakthrough was 44 hours5.092593e-4 days <br />0.0122 hours <br />7.275132e-5 weeks <br />1.6742e-5 months <br />.
After 1 year, another canister was drawn from storage. Penetration after 480 minutes was below 0.5% (8 ppm methyliodide challenge concentration),
i CLASS B STORAGE TESTS l
A larger sample of Lot 96 canisters are under class B storage at our X-Stores L
warehouse. Samples were drawn at three-and four-years storage and penetrations at 480 minutes were at or below the initial lot inspection results.
i MDISTURE PERMEATION OF BOTTOM SEAL g
In October 1984, we conducted a moisture permention study on the canister seal material at 100'F and 100% RH. After three years (maximum shelf-life for the canister) moisture incursion was found to be insignificant.
l
~
m hs Wukinnlir%utSafety IDCATION: RIDC Industrial Park
- 121 Gamma Drive
- Pittsbur6, PA 15238 h
i
c, s,
p-
'Mr. Tia Kirkham-Mine Saft,ty Appli:nces Company
?-
September 18, 1989 CONCLUSION Storage of GMR-I canisters under Class C storage will not degrade the methyliodide perforinance of an unopened canister.
Please do not hesitate to contact me'if you have questions or need further information.
Sincerely, Eric J. Beck Product Line Manager cc: Al Faircloth L
__ ___