5- of feb 12-1997 glneerlng data transmittal ledt
TRANSCRIPT
5%- 5- FEB 12-1997 GlNEERlNG DATA TRANSMITTAL
P.0.1 Of 1 lEDT 620717
____ 2. To: (Receiv ing Organizat ion)
L. F . Perkins , 222-S Laborator ies 5. P r o j ./Prog./Dept./Div.:
11. Receiver Remarks: 11A. Design B a s e l i n e Docunent7 [ ] Yes [XI No
For review and approval .
3. From: ( D f i g i n a t i n g o r g a n i z a t i o n )
D . S . Mantooth, Indus t r ia l Safe ty & Health 6. Design A u t h o r i t y / Design Agent/Cog.
15. DATA IAI IC1
IBI DocumentIDrawing No. NO NO
Hanford Analyt ical Serv ices
HNF-SD-SUP-LB-001 I
Engr.: 0. S. Penfield
IEl Title or Description of Data Tranammad
Airborne Chemical Basel ine Evaluation of t h e 222-S Laboratory Complex
Approval Designator IF1 Reason for Transmittal IGI
E, s . a. D or NIA 1. Approval 4. Review (see WHC-CM-3-5. 2 . Release 5. Post-Review Sec.12.71 3. Information 6 . Dist. IRecsipt Acknow. Required)
1. R e l a t e d ED1 No.: None
'. Purchase Order No.:
MGK-SVV-186918 ). Equip./Conponent No.:
IO. System/B/Bldg./Facility:
12. Major Assm. Dug. No.:
Not Applicable
222-S Laboratory Complex
None
Not Applicable
Februarv 7. 1997
13. P e r m i t l P e r m i t A p p l i c a t i o n No.:
4 . Requi red Response Date:
Disposition IHI & Ill 1. Approved 4. Reviewed nolcommant 2. Approved wlcomment 5. Reviewed wlcommant 3. Disapproved wlcomment 6. Receipt acknowledged
- Approval
Desig- nator
0
- S
IGI in) IGI Dilp, (J) Name I K I Signature ILL Date IMI MSlN ba.
son SO"
Desion A u t h o r i t v
(HI Disp IJI Name IKI Slgnature ILI Date IMI MSlN
1
ED-7400-172-2 (D5/96) GEF097
80-7-172-1
Design Agent
Cog.Eng. - D. P e n f k i ! + & ? k A A g j z/y/
cog. Mgr. - D. M a n t o o t h 2 i k L & Jhfq7 Ral QA
S a f e t y - D. P e n f l e l b @ & y d 7 / / Y r
Env. /
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1101
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I1 1Al'
1121
1131
1141
1151'
1161
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1181
1191
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a EDT
INSTRUCTIONS FOR COMPLETION OF THE ENGINEERING DATA TRANSMITTAL USE BLACK INK OR TYPE)
0 Pm-a.*igMd EDT number.
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Roj.IFma.IDspt.lDiv.
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Enter tho signature and date of the Dosign AcdmitvlCwnizant Manager. [This signamre is authorhation for reka.o.1 Entor DOE appmval lit required) by sipnature or contml number that tracks the appmval to a signatum. and indicate DOE amion.
'Asterisk danoto the required minimum items Check by Configuration Documentation prior to re10a.e; these are the minlmum mkass requiremants
BD-7400172-1
S HNF-SD-SUP-LE-001, Rev. 0
Airborne Chemical Baseline Evaluation of the 222- S Laboratory Complex
Bartley, Philip L; Hartman, Allison J ; Peters, Brian B; Foster Wheeler Environmental Corporation, Richland, WA 99352 U.S. Department of Energy Contract DE-AC06-87RL10930
EDT/ECN: 620717 uc: uc-2020 Org Code: 31114 Charge Code: J31HA B&R Code: YNOlOOOOO Total Pages: 139
Key Words: Industrial Hygiene, Baseline, Laboratory Monitoring, 222-S
Abstract: An evaluation of the potential for elevated laboratory airborne chemical concentrations in the 222-S Laboratory Complex was performed. evaluation of the 222-S Laboratory Complex, and was designed to determine airborne chemical monitoring requirements in accordance with the Chemical Hygiene Plan and OSHA 29 CFR 1910.1450. Elements of this evaluation included summarizing past monitoring data, performing task specific evaluations, reviewing chemical inventories, developing and utilizing airborne chemical generation and distribution models, and providing monitoring and activity recomendations.
This evaluation was part of a comprehensive baseline
TRADEMARK DISCLAIMER. Reference herein to any specific comnercial product, process, or service by trade name. trademark. manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommlation. or favoring by the United States Goverrment or any agency thereof or its contractors or subcontractors.
Printed in the United States of Oocunent Control Services, P.O. FC.X (509) 376-6989.
America. To obtain copies of this d o c w n t , contact: UHC/BCS BOX 1970, Maitstop ~ 6 - 0 8 , Richlard UA 99352, Phone (509) 372-2420:
Approved for Public Release
A-6600-073 (10/95) GEF321
THIS PAGE INTENTIONALLY LEFl'BLANK
Airborne Chemical Baseline Evaluation of the 222-S Laboratory Complex
HNF-SD-SUP-LB-001 Rev. 0
January 22, 1997
Prepared by
P . L . Bartley, C I H A.J . Hartman
B.B. Peters, PE
Foster Wheeler Environmental Corporation
Prepared for
Rust Federal Services of Hanford, Inc.
Task 023 of Order No. MGK-SVV-186918 with Lockheed Martin Hanford Corp.
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HNF-SD-SUP-LB-001, Rev. 0
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HNF-SD-SUP-LE-001. Rev, 0
PREFACE
T h i s document was w r i t t e n during the per iod t h a t the opera t ing c o n t r a c t f o r t h e Hanford S i t e was awarded t o Flour Daniel Hanford, Inc. w i t h Rust Federal Serv ices of Hanford, Inc. assuming control of the 222-S Labora tor ies , while many of the general hea l th and s a f e t y func t ions a r e being c o n t r o l l e d by Lockheed Martin Hanford Corp. As a r e s u l t of t h i s change, a l l of the manual names and numbers a r e i n t h e process of changing. In t h a t t h e s e changes a r e not complete, and addi t iona l changes a r e l i k e l y , the Westinghouse Hanford Company manual and document names and numbers have been re ta ined f o r th is document.
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HNF-SD-SUP-LB-001, Rev. 0
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HNF-SD-SUP-LE-001, Rev. 0
EXECUTIVE SUMMARY
The 222-S Laboratory complex s t o r e s and uses over 400 chemicals. Many
of t h e s e chemicals a r e used i n labora tory a n a l y s i s and some a r e used f o r
maintenance a c t i v i t i e s . The major i ty of labora tory a n a l y s i s chemicals a r e
only used i n s i d e of fume hoods o r glove boxes t o control both chemical and
rad ionucl ide a i rborne concent ra t ions .
This eva lua t ion was designed t o determine t h e p o t e n t i a l f o r l a b o r a t o r y
a n a l y s i s chemicals a t t h e 222-S Laboratory complex t o cause e leva ted a i rborne
chemical concent ra t ions under normal condi t ions . This was done t o i d e n t i f y
condi t ions and a c t i v i t i e s t h a t should be s u b j e c t t o a i rborne chemical
monitoring i n accordance with t h e Westinghouse Hanford Company Chemical
Hygiene Plan.
To i d e n t i f y condi t ions assoc ia ted with poten t ia l e leva ted a i rborne
concent ra t ions , work a reas were inspected, v e n t i l a t i o n and s torage condi t ions
were eva lua ted , and p a s t and c u r r e n t monitoring a c t i v i t i e s were reviewed. In
addi t ion , chemicals of concern were i d e n t i f i e d and models were developed t o
p r e d i c t a i rborne concent ra t ions .
Airborne chemical monitoring has been performed i n the pas t a t the 222-S
Laboratory complex.
1 ,2 ,4- t r imethyl benzene, the primary mater ia l i n Insta-Gel ( Insta-Gel i s a
trademark of Packard Ins t ruments ) .
Chemicals monitored included methylene c h l o r i d e and
Since 1989, monitoring has been performed f o r 57 l abora tory chemicals
None were g r e a t e r than a i rborne l i m i t s and 27 were l e s s than d e t e c t a b l e
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HNF-SD-SUP-LB-001, Rev. 0
concentrations.
for methylene chloride use outside of the hood.
The highest airborne concentration monitoring results were
Conditions with potential elevated concentrations were initially
identified in room 4L when opening flammable material storage cabinets, room
2B during decontamination, in the 222-SA Standards Laboratory while weighing
solids, and during general activities performed outside of hoods. A mercury
distillation unit was also present in room 4L, that was previously in room 4E,
that could result in elevated levels but was not evaluated because the system
is reportedly not currently operational.
Chemicals of concern were chosen for evaluation based on activity
performed and usage frequency. Airborne chemical concentrations were
estimated based on activity, predicted contaminate generation rate, and
predicted airborne distribution using models from the EPA and nationally
recognized organizations.
Storage Cabinets
There are many chemicals in the cabinets evaluated in room 4L. Xylene
and methylene chloride were used for modeling.
exposures when opening the flammable storage cabinets in room 4L could
temporarily be high but would not likely result in exceeding airborne limits.
Recommended actions for these cabinets include: 1) better characterize the
contents, 2) monitor the air upon opening the cabinet to demonstrate
compliance, and 3) annually repeat the monitoring while chemicals remain in
the cabinet.
The models indicated that
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HNF-SO-SUP-LE-001, Rev. 0
Removing the material will eliminate all exposure. I f monitoring
indicates elevated airborne concentrations that approach or exceed 1 imits,
removal should be done as soon as possible.
concentration control, installation of ventilation systems in the cabinets
should be evaluated.
I f necessary for airborne
Decontamination
No model was identified which could reasonably approximate airborne
concentrations resulting from use of the decontamination station in room 2B.
This activity should be monitored for lead and nitric acid initially, and then
whenever decontamination methods change.
should be established based on the initial monitoring results.
Periodic monitoring requirements
Solids Weighing
Several solids are weighed in the 222-SA Standards Laboratory, generally
in small amounts. This evaluation indicated that there is very little
potential for elevated airborne chemical concentrations and no monitoring or
other actions are recommended.
Chemical Usage Outside of Hoods
Few chemicals are used outside of a fume hood. To be conservative, for
this evaluation it was assumed that any chemical in the inventory could be
used outside o f the hood. Based on frequency of use and physical properties
of the chemicals, a list of 10 chemicals of concern was identified. Airborne
concentrations were modeled with the scenario of an open beaker of the
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HNF-SD-SUP-LB-001, Rev. 0
chemical of concern evaporating for various time periods.
scenarios were modeled:
results were in close agreement with actual monitoring results and the typical
case was generally used for summary information and making recommendations.
Based on this evaluation, airborne limits could be exceeded within minutes
with small liquid volumes for the following chemicals:
Two ventilation
typical and worst case. The typical case modeling
Bromine
Benzene
Hydrochloric Acid (> 30%)
Ammonium Hydroxide (> 6m)
Hydrofluoric Acid
According to facility personnel, these chemicals are only used inside of
hoods.
unless dilutions are used. Dilutions of these chemicals should be further
eval uated.
Any use outside of hoods should be strictly controlled and monitored
The airborne limits for epichlorohydrin and hydrogen peroxide could be
exceeded with relatively small liquid volumes if the chemical was open outside
of the hood for approximately 5 hours.
chloride could be exceeded in approximately 4 hours but would require the
evaporation of approximately 1 liter of liquid. These conditions are not
likely unless an error i s made.
The airborne limit for methylene
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HNF-SD-SUP-LB-001, Rev. 0
Limits probably would not be exceeded for the other chemicals used in
the lab because they have high exposure limits or are not very volatile.
Activities that force evaporation or particulates into the air should be
further evaluated.
Although this analysis identified no other organic chemicals with
potential exposures greater than 1 imits, to demonstrate compliance monitoring
should be performed annually if these chemicals are used outside of fume
hoods.
regulatory efforts to reduce limits for this chemical.
This is particularly true for methylene chloride in light of current
To assist in this evaluation an airborne factor model was developed that
accurately identified chemicals of concern.
used to screen activities anticipated to be performed outside of hoods.
process could be incorporated in the Chemical Hygiene Plan.
airborne factor screening level of 170 could be used to identify those
chemicals that should be used inside of hoods or monitored. Volumes of
chemicals required to exceed limits could also be incorporated.
This airborne factor should be
This
The recommended
Mercury Distillation
Airborne chemical concentrations from the mercury distillation,
currently in room 4L, were not modelled because it is not in service.
However, the inspection identified some areas of concern. There was no
apparent ventilation system. No previous airborne mercury monitoring has been
identified, and no surveys have been identified that clear the area of surface
mercury. It is recommended that this unit not be operated until surface
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HNF-SD-SUP-LB-001, Rev. 0
monitoring is performed and engineering controls are implemented to ensure
vapors are captured.
Concl usi on
This evaluation indicates that airborne chemical concentrations in the
222-S Laboratory are low if current practices, including use o f fume hoods,
continue. However, airborne limits can easily be exceeded if certain
chemicals of concern are used improperly.
monitoring is recommended because models do not adequately predict exposures.
In other cases, monitoring is recommended to confirm low predicted
concentrations.
In some cases, additional
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HNF.SD.SUP.LB.001, R e v . 0
TABLE OF CONTENTS
ACRONYMS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . v
1 . 0
2 . 0
3.0
4.0
5 . 0
6 . 0
7.0
8.0
9.0
INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-1 1.1 PURPOSE . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-1 1.2 REPORT ORGANIZATION . . . . . . . . . . . . . . . . . . . . . 1-1
SCOPE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 - 1
CHEMICAL HYGIENE PLAN . . . . . . . . . . . . . . . . . . . . . . . 3-1 3.1 CHEMICAL CATEGORIES . . . . . . . . . . . . . . . . . . . . . 3 - 1 3 .2 MONITORING REQUIREMENTS . . . . . . . . . . . . . . . . . . . 3 - 2
F A C I L I T Y INFORMATION . . . . . . . . . . . . . . . . . . . . . . . . 4-1 4.1 VENTILATION . . . . . . . . . . . . . . . . . . . . . . . . . 4 - 1 4.2 CHEMICAL STORAGE . . . . . . . . . . . . . . . . . . . . . . . 4 - 1
WORK PRACTICES . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 - 1 5.1 LABORATORY ROOM PRACTICES . . . . . . . . . . . . . . . . . . 5 - 1
5 . 1 . 1 Room 4L . . . . . . . . . . . . . . . . . . . . . . . 5 - 1 5 . 1 . 2 Room 2 8 . . . . . . . . . . . . . . . . . . . . . . . 5 - 1 5 . 1 . 3 Room 4 P O r g a n i c L a b o r a t o r y . . . . . . . . . . . . . . 5 - 2 5 . 1 . 4 Room 4A E n v i r o n m e n t a l L a b o r a t o r y . . . . . . . . . . . 5 - 2 5.1.5 Room 1J I C P Room . . . . . . . . . . . . . . . . . . . 5 - 2
5 . 2 222 -SA STANDARDS LABORATORY PRACTICES . . . . . . . . . . . . 5 - 2 5 . 3 INSTA-GEL USAGE . . . . . . . . . . . . . . . . . . . . . . . 5 - 3 5.4 CHEMICAL HYGIENE PLAN IMPLEMENTATION . . . . . . . . . . . . . 5 - 3
CHEMICAL INFORMATION . . . . . . . . . . . . . . . . . . . . . . . . 6 - 1 6 . 1 FREQUENTLY ORDERED CHEMICALS . . . . . . . . . . . . . . . . . 6-1 6 . 2 H IGH POTENTIAL AIRBORNE CONCENTRATION CHEMICALS . . . . . . . 6 - 1
PREVIOUS AND CURRENT MONITORING EFFORTS . . . . . . . . . . . . . . 7 - 1
ASSESSMENT MODELS . . . . . . . . . . . . . . . . . . . . . . . . . 8-1 8.1 SCENARIOS . . . . . . . . . . . . . . . . . . . . . . . . . . 8 - 1 8 .2 STORAGE CABINET MODELS . . . . . . . . . . . . . . . . . . . . 8-1
8 . 2 . 1 S t o r a g e C a b i n e t G e n e r a t i o n M o d e l . . . . . . . . . . . 8 - 2 8.3 DECONTAMINATION MODEL . . . . . . . . . . . . . . . . . . . . 8 - 4 8.4 222-SA STANDARDS LABORATORY SOLIDS WEIGHING MODEL . . . . . . 8-4 8.5 GENERAL CHEMICAL TRANSFER MODELS . . . . . . . . . . . . . . . 8 - 4
8 . 5 . 1 D i s p l a c e m e n t V a p o r s G e n e r a t i o n R a t e . . . . . . . . . 8-5 8 .5 .2 D i s p l a c e m e n t V a p o r s D i s p e r s i o n . . . . . . . . . . . . 8-6 8.5.3 E v a p o r a t i o n G e n e r a t i o n M o d e l . . . . . . . . . . . . . 8 - 6 8.5.4 E v a p o r a t i o n D i s p e r s i o n M o d e l . . . . . . . . . . . . . 8 -7
AIRBORNE CHEMICAL CONCENTRATION ESTIMATES . . . . . . . . . . . . . 9-1 9.1 STORAGE CABINET ESTIMATE . . . . . . . . . . . . . . . . . . . 9 - 1 9 .2 DECONTAMINATION ESTIMATES . . . . . . . . . . . . . . . . . 9-1 9.3 2 2 2 - S A STANDARDS LABORATORY SOLIDS WEIGHING ESTIMATES . . . . 9-2
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HNF.SD.SUP.LB.001, Rev . 0
9.4 GENERAL CHEMICAL TRANSFER ESTIMATES . . . . . . . . . . . . . 9-3 9.4.1 Chemicals Evaluated . . . . . . . . . . . . . . . . . 9-3 9.4.2 Displacement Vapors Ai rborne Concentrat ion Est imates . 9-5 9.4.3 Evaporat ion Ai rborne Concentrat ion Est imates . . . . . 9-6
10.0 MODEL VALIDATION . . . . . . . . . . . . . . . . . . . . . . . . . 10-1 10.1 EXPOSURE MODEL VALIDATION . . . . . . . . . . . . . . . . . . 10-1 10.2 SCREENING MODEL VALIDATION . . . . . . . . . . . . . . . . . 10-1
11.0 AIRBORNE CHEMICAL MONITORING RECOMMENDED . . . . . . . . . . . . . 11-1 11.1 ROOM 4L FLAMMABLE STORAGE CABINET . . . . . . . . . . . . . . 11-1
11.3 CHEMICAL USAGE OUTSIDE OF HOODS . . . . . . . . . . . . . . . 11-1 11.2 ROOM 28 DECONTAMINATION STATION . . . . . . . . . . . . . . . 11-1
11.4 MERCURY DISTILLATION . . . . . . . . . . . . . . . . . . . . 11-2 11.5 MAINTENANCE CHEMICALS . . . . . . . . . . . . . . . . . . . . 11-2
12.0 MONITORING NOT RECOMMENDED . . . . . . . . . . . . . . . . . . . . 12-1 12.1 SOLIDS MONITORING I N THE 222-SA STANDARDS LABORATORY . . . . 12-1 12.2 MOST CHEMICALS . . . . . . . . . . . . . . . . . . . . . . . 12-1
13.0 CONCLUSIONS AND OTHER RECOMMENDATIONS . . . . . . . . . . . . . . . 13-1 13.1 PERFORM P E R I O D I C AND TASK SPECIFIC MONITORING . . . . . . . . 13-1 13.2 EVALUATE HOOD USAGE . . . . . . . . . . . . . . . . . . . . . 13-1 13.3 FURTHER EVALUATE AND MODIFY MERCURY DISTILLATION . . . . . . 13-1 13.4 UTILIZE AIRBORNE SCREENING FACTOR AND VOLUME COMPARISON . . . 13-1
EVALUATE VENTING STORAGE CABINETS I F NEEDED . . . . . . . . . 13-1 13.5 MONITOR STORAGE CABINETS AND EITHER REMOVE CHEMICALS OR
14.0 REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14-1
APPENDIXES
Appendix A Laboratory Chemical I nven to ry In fo rma t ion Appendix B Storage Cabinet Model I n fo rma t ion Appendix C 222-SA Standards Laboratory S o l i d s Weighing Model I n f o r m a t i o n Appendix D General Chemical T rans fe r Model I n fo rma t ion Appendix E Maximum A i rbo rne Concentrat ions Under Typ ica l V e n t i l a t i o n
Appendix F Average A i rbo rne Concentrat ions Under Typ ica l V e n t i l a t i o n Condi t ions
Condi t ions
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HNF-SD-SUP-LB-001, Rev. 0
LIST OF FIGURES
Ai rbo rne Concentrat ion o f N i t r i c Ac id (57%) Based Upon Displacement . . . . . . . . . . . . . . . . 9-6 Instantaneous Concentrat ion o f Methylene Ch lo r ide i n R o o m . . . . . . . . . . . . . . . . . . . . . . . . 9-9 Maximum Concentrat ion o f Methylene Ch lo r ide i n Room . . 9-10 Averaged Concentrat ion o f Methylene Ch lo r ide i n Room . 9-11 Maximum Concentrat ion o f Hyd roch lo r i c Ac id i n Room a t Var ious Concentrat ions . . . . . . . . . . . . . . . . 9-14
F igu re 9 - 1
F igu re 9-2
F igu re 9-3 F igu re 9-4 F igu re 9-5
Table 6 - 1
Table 6-2
Table 7 -1 Table 9 - 1
Table 9-2
Table 9-3 Table 9-4
Table 9 -5 Table 9-6 Table 9-7 Table 9-8. Table 10-1 Table 13-1
LIST OF TABLES
Most Frequent ly Ordered Chemicals a t 222-S Laborator ies . . . . . . . . . . . . . . . . . . 6-2 Chemicals With P o t e n t i a l f o r E levated A i rbo rne Concentrat ions . . . . . . , . . . . . . . . . . . . . 6-4 222-S Exposure Mon i to r i ng . . . . . . . . . . . . . . . 7-2 Storage Cabinet A i rborne Chemical Concentrat ion Estimates . . . . . . . . . . . . . . . . . . . . . . . 9 -1 Eva lua t i on o f 222-SA Standards Laboratory P o t e n t i a l A i rbo rne Concentrat ion . . . . . . . . . . . . . . . . 9-3 Chemicals o f Concern - A i rbo rne L i m i t s . . . . . . . . 9-4 Maximum Airborne Concentrat ions Estimated from Displacement . . . . . . . . . . . . . . . . . . . . . 9-5 Chemicals o f Concern Evaporat ion Rates . . . . . . . . 9-8 Chemicals o f Concern - Times t o Reach A i rbo rne L i m i t s . 9-12 Chemicals o f Concern - E q u i l i b r i u m Concentrat ions . . . 9-13 Chemicals o f Concern - Volumes o f Chemical Required . . 9-15 Comparison o f Screening Factors and Exposures . . . . . 10-2 Chemicals o f Concern - Summary In fo rma t ion . . . . . . 13-2
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ACGIH AIHA ALARA AMCA CAS CEIL cfm CFR csu DOE EPA HEPA IDLH 1 f m NFPA OSHA PEL PNL PPm RWP STEL TLV TWA WSCF WHC
ACRONYMS
American Conference o f Governmental I n d u s t r i a l Hyg ien i s t s American I n d u s t r i a l Hygiene Assoc ia t i on as l ow as reasonably achievable A i r Movers Contract Assoc ia t i on Chemical Abs t rac t Serv ice c e i l i n g exposure cub ic f e e t pe r minute Code o f Federal Regulat ions Chemical Storage U n i t U.S. Department o f Energy U.S. Environmental P r o t e c t i o n Agency h i g h - e f f i c i e n c y p a r t i c u l a t e a i r immediately dangerous t o l i f e o r h e a l t h l i n e a r f e e t pe r minute Na t iona l F i r e P r o t e c t i o n Assoc ia t i on Occupational Safety and Hea l th A d m i n i s t r a t i o n pe rm iss ib le exposure 1 i m i t P a c i f i c Northwest Nat ional Laboratory p a r t s pe r m i l l i o n r a d i a t i o n work pe rm i t sho r t - t e rm exposure l i m i t t h r e s h o l d l i m i t va lue t ime weighted average Waste Sampling and Charac te r i za t i on F a c i l i t y Westinghouse Hanford Company.
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1.0 INTRODUCTION
The 222-S Laboratory complex stores and uses over 400 chemicals. of these chemicals are used in laboratory analysis and some are used for maintenance activities. The majority of laboratory analysis chemicals are used only inside of fume hoods or glove boxes to control both chemical and radionuclide airborne concentrations.
Many
This evaluation was designed to determine the potential for laboratory analysis chemicals at the 222-S Laboratory complex to cause elevated airborne chemical concentrations during non-emergency conditions. Conditions and activities that should be subject to airborne chemical monitoring in accordance with the Westinghouse Hanford Company (WHC) Chemical Hygiene Plan were identified. To identify conditions associated with potential elevated concentrations, work areas were inspected, ventilation and storage conditions were reviewed, and past and current monitoring activities were reviewed. In addition, chemicals of concern were identified and models were developed to Dredi ct airborne concentrations.
1.1 PURPOSE
The purpose of this report was to document the evaluation of potential chemical airborne concentrations and controls at the 222-S Laboratory complex to determine the appropriate monitoring. meet the monitoring criteria in Section 16 of the WHC Chemical Hygiene Plan (Sant 1995). chemicals be evaluated and that appropriate monitoring and/or sampling be conducted as required.
aggressively controlled through the use of ventilation hoods, general ventilation, and work practices. As a result, chemical concentrations at these facilities are generally considered as low as reasonably achievable (ALARA) .
This evaluation was performed to
The plan requires that potential employee exposures to hazardous
Chemical airborne concentrations at the 222-S Laboratory complex are
1.2 REPORT ORGANIZATION
This report was designed to review several factors that affect potential elevated airborne chemical concentrations. The scope of this report is described in Section 2. Section 3 provides a general discussion of the Chemical Hygiene Plan. Section 4 describes the facility, including the ventilation and chemical storage systems. Work practices, which often have the largest influence on airborne concentrations, are reviewed in Section 5. Frequently used chemicals are more likely to result in elevated airborne concentrations, and chemicals with high vapor pressures and molecular weights will typically result in greater airborne concentrations; these chemicals are discussed in Section 6 with additional information in Appendix A. Past monitoring history can also be an indicator of current exposures. current monitoring efforts are described in Section 7. the exposure assessment models used to estimate exposures and Section 9 presents the results of using these models. additional information on modeling results. Model validation is presented in
Past and
Appendixes B through F provide
Section 8 discusses
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Section 10. Section 13 contains the general conclusions o f this evaluation.
Monitoring recommendations are included in Sections 11 and 12.
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2.0 SCOPE
The scope o f t h i s r e p o r t was l imi ted t o t h e 222-S Laboratory complex including t h e 222-SA Standards Laboratory and chemical s torage u n i t (CSU). All labora tory chemicals were i d e n t i f i e d and evaluated. Maintenance chemicals were not included because they a r e beyond the scope of t h e Chemical Hygiene Plan. Airborne chemical p o t e n t i a l s were l imi ted t o normal a c t i v i t i e s . Poten t ia l concent ra t ions from s p i l l s , f i r e s , o r s i m i l a r emergencies were not incl uded.
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3.0 CHEMICAL HYGIENE PLAN
The 222-S Laboratory complex is operated in accordance with several sets This plan was written in of requirements including the Chemical Hygiene Plan.
accordance with the Occupational Safety and Health Administration (OSHA) requirements conkained in Title 29 of the Code of Federal Regulations (CFR) Part 1910.1450, Occupational Exposures to Hazardous Chemicals in Laboratories." The Chemical Hygiene Plan includes a general requirements section applicable to all laboratories under Fluor Daniel Hanford, Inc. control; information specific to each facility is included as an attachment to the plan.
usage including procurement, storage, protective apparel, handl ing precautions, monitoring, spills and emergency actions, and disposal. Most important to this evaluation were the handling precautions, which are based on chemical categories and monitoring requirements.
chemicals in the 222-S Laboratory are discussed in Section 3.1. requirements are discussed in Section 3.2. 3.2 is from the Chemical Hygiene Plan. discussed in Section 5.4.
This plan is reviewed and updated annually.
The Chemical Hygiene Plan encompasses all phases of laboratory chemical
The chemical categories and associated handling requirements for
Implementation of this plan is
Monitoring The information in Section 3.1 and
3.1 CHEMICAL CATEGORIES
Three general chemical categories (A, B, and C) are used in the Chemical Hygiene Plan. Category C chemicals are considered the least hazardous category of materials to work with and include some irritants and corrosives. Category B chemicals are substances of moderate chronic toxicity or high acute toxicity and include sensitizers and reproductive toxins. chemicals include substances of known high chronic toxicity, materials regulated by OSHA, and materials regulated by the U.S. Department of Energy (DOE). category to ensure health hazard control are described in the following text.
hazardous chemicals (Category A, B, and C) by following approved procedures or work plans. work plans require prejob planning and use of the Job Safety Analys;,s program, as required by WHC-CM-4-3, Industrial Safety Manual, Standard A-3, Prejob Planning , and the new WHC-CM-4;lO or the equivalent (WHC-CM-6-1, Standard Engineering Practices, EP-4.2, Testing Practices").
devices, personal protective equipment, proper storage, and waste handl ing procedures. In general, radiation work permit (RWP) precautions, where applicable, satisfy the chemical hygiene requirements for this class of chemicals. Category B chemicals are handled only by trained, designated, and approved personnel following approved procedures. Materials that cannot become airborne (i.e., are not fine powders, are not volatile, or are present at less than 1% in solution) may be worked with outside of a hood.
Category A
Administrative controls that must be implemented for each chemical
Laboratory personnel are required to perform all activities involving
New laboratory operations not covered by approved procedures or
Additional precautions for Category B chemicals include containment
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Substances of known high chronic t o x i c i t y a r e handled only by t r a i n e d , des igna ted , and approved personnel who a r e fol lowing procedures f o r handl ing Category A m a t e r i a l s . s p e c i f i c Chemical Hygiene L i s t s a s Category A hazardous chemicals , and include: ( 1 ) substances of known high chronic t o x i c i t y , ( 2 ) OSHA-regulated m a t e r i a l s , and (3) DOE-regulated mater ia l s (e .g . , beryl l ium compounds).
Each f a c i l i t y has designated a c o n t r o l l e d a rea o r a r e a s f o r work involving Category A m a t e r i a l s . Only t r a i n e d , approved personnel , w i t h c u r r e n t t r a i n i n g records , handle these m a t e r i a l s . Personnel must work w i t h these chemicals i n a physical containment device . Managers and s u p e r v i s o r s must be n o t i f i e d of each use and a r e required t o record t h e fol lowing f o r Category A mater ia l s : (1) amounts s t o r e d , ( 2 ) amounts used, (3) d a t e s of use, and (4) t h e names of employees using these m a t e r i a l s .
Category B m a t e r i a l s . l imi ted key d i s t r i b u t i o n f o r Category B and r e q u i r e s t h a t only small q u a n t i t i e s of Category A m a t e r i a l s be s tored i n room 4L and room 1G-C f o r use a s s tandards and re ference m a t e r i a l s . Hood 1 and the hood i n room 1 G - C a r e t h e designated Category A hoods. Special c lo th ing , inc luding two p a i r s of gloves and Tyvek (Tyvek i s a trademark of E . I . du Pont d e Nemours and Company) l a b c o a t s a r e requi red f o r Category A work. "Cancer hazard" pos t ings a r e a l s o requi red .
The 222-SA Standards Laboratory has i d e n t i f i e d Hoods 1 , 2, 3, and 4 f o r Category B chemicals and Hood 1 f o r Category A chemicals. and o t h e r c o n t r o l s a r e s i m i l a r t o those used i n t h e 222-S Laboratory complex.
These chemicals and m a t e r i a l s a r e shown on the f a c i l i t y
F a c i l i t y s p e c i f i c procedures vary f o r t h e handling of Category A and The 222-S Laboratory complex r e q u i r e s locked doors w i t h
P r o t e c t i v e c l o t h i n g
The Chemistry S t a t i s t i c s Laboratory requirements a r e the most r e s t r i c t i v e and r e q u i r e (1) a t e s t plan, (2) consul ta t ion w i t h the Chemical Hygiene O f f i c e r , and (3) pos t ing of t h e area f o r both Category A and B chemicals p r i o r t o working with any chemical.
3.2 MONITORING REQUIREMENTS
This eva lua t ion i s designed t o i d e n t i f y t h e monitor ing requirements i n accordance w i t h t h e Chemical Hygiene Plan. The monitor ing requirements f o r t h e 222-S Laboratory a r e descr ibed i n t h e Chemical Hygiene Plan a s fo l lows:
An employee's exposure t o any hazardous chemical regula ted by an OSHA standard s h a l l be evaluated. The fol lowing procedures must be implemented by 1 i n e management.
1. I d e n t i f y t h e monitoring t h a t must be conducted.
a . Survey t h e raw mater ia l s and determine whether p o t e n t i a l l y harmful mater ia l s a r e being used.
I d e n t i f y t h e condi t ions under which t h e s e m a t e r i a l s a r e being used and the processes t h a t genera te physical hazards.
b.
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c. Determine whether the materials or processes may present a potentially harmful exposure to employees.
2. Contact Industrial Hygiene Representative for determination of whether area monitoring or personnel sampling are required.
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4.0 FACILITY INFORMATION
An actively maintained and monitored ventilation hood configuration is the foundation of the 222-S Laboratory complex airborne contaminant control system. Although radiological controls are the principal driver for hood requirements, the same controls are equally effective for controlling chemical concentrations. Nearly all work is performed either in hoods or in totally contained hot cells. This section describes the engineering aspects of the ventilation system. storage system.
Also included is a brief description of the chemical
4.1 VENTILATION
The ventilation hoods in the 222-S Laboratory complex are designed to meet the criteria from the DOE General Design Criteria, DOE Order 6430.1A (DOE 1989), the Radiological Design Guide (Evans 1994), and the 222-5 Laboratory Interim Safety Basis (Weaver 1996). 125 linear feet per minute (lfm). or 725 cubic feet per minute (cfm), depending upon the hood style (Drawing H-299485). All hoods are verified monthly in accordance with procedure 3-PL-016. All hoods are fed into a common header which is exhausted through high-efficiency particulate air (HEPA) filters above building level to properly disperse nonradiological components.
222-S Laboratory complex and an average of approximately seven air changes per hour for the entire complex. Because of differences in the number and type of hoods in each room, there can be significantly greater air changes on a per room basis. The monthly measured air flow rates for each hood in the room combined with the measurements of exhaust air are used to determine the air change rate for each room.
Ventilation studies were performed to confirm air flow patterns and removal capabilities (Stoetzel and Hickey 1990; Stoetzel and Cicotte 1992). Smoke tubes, smoke bombs, and anemometers were used in these studies. In most laboratory rooms, the air flow was generally 10 to 30 lfm with localized higher flow areas, particularly at the hood openings. generally measured as "less than 15 minutes."
exposure from the few operations performed outside of hoods or other controlled areas (Section 5).
the laboratory rooms. these upgrades.
The minimum flow rate in each hood is This corresponds to a minimum flow of 195
There are a minimum of five air changes per hour in each room in the
Air clearances were
The high air exchange rate is effective at controlling the potential
The 222-S Laboratory complex is in the process of upgrading several of Continued future use of the hoods is a requirement of
4.2 CHEMICAL STORAGE
Bulk chemicals are primarily stored in separate specially designed buildings with individual venti 1 at ion systems. are stored in laboratory cabinets within the 222-S Laboratory complex. Some flammables are also stored inside in flammable cabinets. One item noted was
Small er chemical quanti ties
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t h a t no s torage cab ine ts appeared t o be vented. Hand l i ng Hazardous Chemicals i n Labora to r ies (Nat ional Research Counci l 1981), c i t e d i n OSHA l a b o r a t o r y standard 29 CFR 1910.1452, recommends t h a t t o x i c substances be s to red i n cab ine ts f i t t e d w i t h a u x i l i a r y v e n t i l a t i o n systems. Vent ing o f flammable s torage cab ine ts must be done i n accordance wi th Na t iona l F i r e P r o t e c t i o n Assoc ia t i on (NFPA) 30, Flammable and Combustible L i q u i d s Code, (NFPA 1991) and approval o f t h e l o c a l f i r e p r o t e c t i o n rep resen ta t i ve .
Prudent P r a c t i c e s f o r
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5.0 WORK PRACTICES
Work p r a c t i c e s i n t h e 222-S Laboratory complex were eva lua ted t o determine p laces and a c t i v i t i e s t h a t may r e s u l t i n increased chemical a i r b o r n e concentrat ions. 24, 1996, p rev ious exper ience w i t h t h i s f a c i l i t y , and worker d i scuss ions . Observat ions i n each l a b o r a t o r y room where exposures cou ld occur a re summarized i n Sec t i on 5.1, 222-SA Standards Laboratory p r a c t i c e s a re desc r ibed i n Sec t i on 5.2, Insta-Gel ( Insta-Gel i s a trademark o f Packard Inst ruments) usage i s d iscussed i n Sec t i on 5.3, and implementat ion o f t h e Chemical Hygiene Plan i s descr ibed i n Sec t i on 5.4.
These work p r a c t i c e s were i d e n t i f i e d d u r i n g a t o u r on J u l y
5 .1 LABORATORY ROOM PRACTICES
Th is s e c t i o n i d e n t i f i e s each room a t t h e 222-S Laboratory and desc r ibes t h e p r a c t i c e s performed i n t h e room. p r a c t i c e s and are n o t i n c l u s i v e o f a l l l a b o r a t o r y a c t i v i t i e s .
The p r a c t i c e s desc r ibed a re genera l work
5 .1 .1 Room 4L
Room 4L i s p r i m a r i l y used t o s t o r e and package m a t e r i a l s f o r d i s p o s a l . I n a d d i t i o n t o fume hoods, t h i s room con ta ins f o u r flammable m a t e r i a l s cab ine ts and a mercury d i s t i l l a t i o n u n i t . i n Room 4E. Workers r e p o r t t h a t t he re i s an o rgan ic smel l when some o f t h e cab ine ts a re opened. These cab ine ts con ta in severa l o rgan ic m a t e r i a l s t h a t have been s to red f o r an extended p e r i o d o f t i m e awa i t i ng d i sposa l . When i n Room 4E, cab ine t 2 was equipped w i t h charcoal adso rp t i on c a n i s t e r s t h a t were l i k e l y i n s t a l l e d t o adsorb o rgan ic vapors. These c a n i s t e r s a re e f f e c t i v e o n l y i f they are changed f r e q u e n t l y .
(Ted la r i s a trademark o f E . I . du Pont de Nemours and Company) bag sampling k i t t o r e t r i e v e a gas sample from Cabinet 2. f o u r i e r t rans fo rmer based a n a l y t i c a l equipment t o at tempt t o i d e n t i f y t h e o rgan ics present . Th i s mon i to r i ng was n o t successfu l . A d d i t i o n a l screening i s underway. was unsuccessful, a conserva t i ve model was used t o es t ima te t h e p o t e n t i a l chemical a i r b o r n e concen t ra t i ons . The model used i s desc r ibed i n Sec t i on 8.2 and t h e concen t ra t i ons est imates r e s u l t i n g f rom t h e model are presented i n Sec t i on 9.1.
These u n i t s were p r e v i o u s l y s t o r e d
The 222-S Laboratory complex personnel were p rov ided w i t h a Ted la r
The l a b o r a t o r y used i n f r a r e d
Because mon i to r i ng the a i rbo rne concen t ra t i ons f rom Cabinet 2
The mercury d i s t i l l a t i o n u n i t , t h a t was p r e v i o u s l y i n room 4E, i s n o t c u r r e n t l y i n ope ra t i on . mercury d i s t i l l a t i o n u n i t .
It i s unknown i f t h e r e have been any s p i l l s f rom t h e
5.1.2 Room 28
Room 2B con ta ins t h e decontamination s t a t i o n . Most decontaminat ion i s performed i n s i d e o f hoods. and l e a d s h i e l d i n g . concentrated n i t r i c ac id . E t h y l a lcohol was a l s o p resen t i n t h e room, o u t s i d e o f t h e hood, i n a small s q u i r t b o t t l e .
I tems decontaminated i n c l u d e l a b o r a t o r y g lassware The chemical used most o f t e n f o r decontaminat ion i s
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In addition, this room receives decontamination waste from the Waste Sampling and Characterization Facility (WSCF). During the tour there was a 55-gal drum from WSCF in room 28. Understandably, this drum cannot be opened inside of a hood. However, according to personnel at the 222-S Laboratory, this waste must have less than 2% organic content to be put into the 222-S Laboratory complex system. airborne chemical concentrations are considered very low.
Because o f this restriction, the potential
The greatest potential for airborne chemical concentrations in this room is likely from acid splashing in the hoods during the decontamination of lead. This exposure was evaluated based on the Industrial Hygiene Ventilation Manual (ACGIH 1988) (see Sections 8.3 and 9.2).
5.1.3 Room 4P Organic Laboratory
room 4P organic laboratory. of WSCF; however, airborne chemical concentrations are still possible. Previous monitoring in this room indicated that chemical airborne concentration levels are generally low (Section 7). Modeling has also been performed to determine the potential chemical airborne concentrations that could result if normal laboratory practices and procedures are not followed (see Sections 8.5 and 9.4).
Several organic materials, including methylene chloride, are used in the Use of this room has decreased with the opening
5.1.4 Room 4A Environmental Laboratory
In this room there are several large (approximately 5-gal) bottles containing various acids outside of hoods. spigot, to beakers. These beakers are transferred to hoods for chemical evaluations. are plans to remove these acid bottles. Modeling has been performed t o determine the potential airborne concentrations that could result from general chemical transfers, including activities performed in room 4A (see Sections 8.5 and 9.4).
Liquids are poured, through a
The highest concentration liquid is 9 molar nitric acid. There
5.1.5 Room 1J ICP Room
Five percent nitric acid is used in this room outside of hoods. acid is pipetted in small quantities as an analysis step. small volumes and low vapor pressure of this concentration of nitric acid, airborne chemical concentrations exceeding applicable limits is not considered an issue. this activity.
This Because of the
In addition, the modeling performed in Sections 8 and 9 includes
5.2 222-SA STANDARDS LABORATORY PRACTICES
Most analysis chemicals are mixed in the 222-SA Standards Laboratory. As a result, this lab contains the most solids (for weighing) and has the most operations performed outside of hoods. The solids used are nonradioactive and typically weighed in quantities of 10 g or less. solid is weighed approximately one to two times each year.
Up to approximately 1 kg of
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S o l i d s genera t i on i s n o t n e a r l y as g r e a t a concern as vapor genera t i on . Unless t h e p a r t i c l e s i z e i s ext remely smal l and t h e r e i s some a g i t a t i o n mechanism, t h e genera t i on r a t e s f o r s o l i d s a re much sma l le r than genera t i on r a t e s f o r v o l a t i l e o rgan ic l i q u i d s . a c t i v i t i e s performed i n t h e 222-SA Standards Laboratory . Th i s p o s i t i o n i s supported by references, which p rov ide l i t t l e d i scuss ion o f c a p t u r i n g d u s t un less t h e r e i s some a c t i v e mechanism t o generate t h e dus t (Na t iona l Research Counci l 1981, ACGIH 1988). However, t h e p o t e n t i a l f o r increased a i r b o r n e concen t ra t i ons has been r a i s e d and was evaluated as p a r t o f t h i s s tudy (Sect ions 8.4 and 9.3).
Th is i s p a r t i c u l a r l y t r u e f o r t h e
5.3 INSTA-GEL USAGE
I ns ta -Ge l i s one o f t h e most f r e q u e n t l y procured chemicals. T h i s chemical i s used as a s c i n t i l l a t i o n c o c k t a i l f o r rad iochemical eva lua t i ons . The p r imary component i n Insta-Gel i s 1 ,2,4- t r imethy l benzene. Each usage o f Insta-Gel i s approx imate ly 20 mL. A i rbo rne l e v e l s , based upon p rev ious mon i to r i ng , are l ow (Sect ion 6) . Insta-Gel i s i nc luded i n t h e a i r b o r n e chemical e v a l u a t i o n (Sect ions 8.5 and 9.4).
5.4 CHEMICAL HYGIENE PLAN IMPLEMENTATION
The Chemical Hygiene Plan i s r e l a t i v e l y new and i s s t i l l i n t h e process o f be ing implemented. Ca tegor i za t i on o f a l l chemicals was j u s t r e c e n t l y completed. I n i t i a l e f f o r t s t o implement t h e c a t e g o r i z a t i o n system i n t o procedures revealed s i g n i f i c a n t l i m i t a t i o n s w i t h t h e approach as w r i t t e n . E f f o r t s are ongoing t o modi fy t h e Chemical Hygiene Plan t o be c o n s i s t e n t w i t h newer l a b o r a t o r y guidance documents. Consequently, t h e r e was l i t t l e evidence o f work p r a c t i c e s i n v o l v i n g the c a t e g o r i z a t i o n system. However, carcinogens, which make up t h e b u l k o f t h e most r e s t r i c t e d chemicals, are c o n t r o l l e d .
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6.0 CHEMICAL INFORMATION
The 222-S Laboratory complex c u r r e n t l y ma in ta ins an i nven to ry o f over 400 chemicals. q u a n t i t i e s . Other chemicals are used f o r maintenance a c t i v i t i e s (e.g., p a i n t s ) . A d d i t i o n a l i n f o r m a t i o n on t h e l a b o r a t o r y chemicals, n o t i n c l u d i n g maintenance chemicals, i s prov ided i n Appendix A and inc ludes t h e chemical name, Chemical Abs t rac t Se rv i ce (CAS) number, and q u a n t i t y present as o f J u l y 15, 1996. pressure, molecular weight , and app l i cab le a i rbo rne concen t ra t i on l i m i t s . Th i s l a t t e r i n f o r m a t i o n was used f o r modeling i n Sect ions 8 and 9.
Th is s e c t i o n i d e n t i f i e s those chemicals most f r e q u e n t l y ordered and those t h a t have t h e g r e a t e s t p o t e n t i a l t o exceed a i rbo rne l i m i t s based on phys i ca l p r o p e r t i e s . Sect ions 8.5 and 9.4.
Most o f these chemicals are used i n r e l a t i v e l y small
A lso i nc luded i n Appendix A are i n f o r m a t i o n on vapor
These chemicals form t h e l i s t t h a t i s modeled i n
6.1 FREQUENTLY ORDERED CHEMICALS
The t o t a l q u a n t i t y o f chemicals ordered each year i s impor tant as an i n d i c a t o r o f p o t e n t i a l e leva ted a i rbo rne concentrat ions. The 10 chemicals most f r e q u e n t l y ordered between January 1994 and June 1996, accord ing t o o rde r ing records, are prov ided i n Table 6-1. Table 6-1, w i t h t h e except ion o f standards and isotopes, were evaluated f o r p o t e n t i a l a i rbo rne chemical concentrat ions. Standards and i so topes a re u s u a l l y used o n l y i n small q u a n t i t i e s and are o f t e n i n s o l u t i o n s o f methylene c h l o r i d e o r n i t r i c ac id , both o f which are evaluated f o r p o t e n t i a l a i rbo rne concen t ra t i ons .
A l l o f t h e chemicals on
6.2 HIGH POTENTIAL AIRBORNE CONCENTRATION CHEMICALS
A i rbo rne chemical concen t ra t i ons are o f t e n r e l a t e d t o t h e phys i ca l p r o p e r t i e s o f t h e chemicals. The two pr imary phys i ca l p r o p e r t i e s a f f e c t i n g a i rbo rne concen t ra t i ons are molecular weight and vapor pressure. These two phys i ca l p r o p e r t i e s , a long w i t h a i rbo rne l i m i t s , can be used t o d e r i v e an a i rbo rne f a c t o r t o screen chemicals f o r a d d i t i o n a l eva lua t i on . The a i rbo rne f a c t o r i s based on Equation 6-1.
Equat ion 6-1:
(VP)(MW) Airborne Factor = ~
Where:
MW = Molecular weight
AL
VP = Vapor pressure (mmHg)
AL = Airborne limit (mglm3)
6-1
m N
Chemical
Methylene Chloride Ni t r i c Acid
Table 6-1. Most Frequently Ordered Chemicals a t 222-S Laborator ies .
Quantity Ordered from January 1994 t o
56 b o t t l e s , 4 L/bot t le 273 b o t t l e s , most 250 mL/bottle; some 500 mL/bottle
June 1996’ Notes
Ethyl alcohol
Hydrochloric acid
Single element l i qu id s tandards Organic s tandards
348 b o t t l e s i s es t imated usage (volume o f b o t t l e s unknown) 112 b o t t l e s , mostly 2,500 mL/bottle
Ins t a Gel
Isotopes Mu1 t i -el ement 1 iquid s tandards
157 b o t t l e s , mostly 100 mL/bottle I Most s tandards in 2% n i t r i c acid
157 ampoules o f 1 mL/ampoule
84 in 5-L con ta ine r s
57 in mostly 5-mL ampoules
48, mostly i n two 500-mL bo t t l e s /o rde r
Most s tandards i n methylene ch lo r ide so lu t ion . Some in methanol o r toluene. Standard t y p i c a l l y <l%/vol ume. Pr incipal compound in Insta-Gel i s 1 ,2 ,4- t r imethyl benzene Most in <IO% n i t r i c ac id so lu t ion Most in <5% n i t r i c acid so lu t ion
1 Eased on information provided by 222-S Laboratory chemical ordering personnel
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Based on t h i s a i r b o r n e f a c t o r concept, t h e chemicals a t t h e 2 2 2 - S Laboratory complex w i t h t h e h ighes t p o t e n t i a l f o r a i rbo rne concen t ra t i ons g r e a t e r t han t h e l i m i t s are p rov ided i n Table 6 - 2 . a i rbo rne l i m i t s used on t h e Hanford S i t e are t h e most r e s t r i c t i v e o f e i t h e r the OSHA Perm iss ib le Exposure L i m i t s (PELS) from 2 9 CFR 1910 Subpart Z o r t h e American Conference o f Governmental I n d u s t r i a l Hyg ien i s t s (ACGIH) Threshold L i m i t Values (TLVs). concen t ra t i ons are assumed i f gas i s released. P o t e n t i a l concen t ra t i ons f rom these chemicals are evaluated i n Sect ion 9.4. V a l i d a t i o n o f t h i s method i s prov ided i n Sect ion 10.1.
O f t h e 10 h igh a i r b o r n e p o t e n t i a l chemicals i d e n t i f i e d , o n l y two are known t o be used ou ts ide o f hoods: n-hexane and methylene c h l o r i d e . N-hexane use o u t s i d e o f hoods i s f r e q u e n t l y performed d u r i n g o rgan ic a n a l y s i s f o r d i l u t i o n o f standards and sample ex t racs us ing 1 t o lOmL n-hexane volumes.
The
Gases are omi t ted from t h i s l i s t because h i g h
Methylene c h l o r i d e i s used as fo l l ows :
A 1-L aqueous sample i s t r a n s f e r r e d t o a continuous l i q u i d - l i q u i d e x t r a c t o r . and conta ined w i t h i n t h e e x t r a c t o r . A f t e r t h e e x t r a c t i o n i s completed (18 t o 24 hours), t he b o i l i n g f l a s k c o n t a i n i n g t h e methylene c h l o r i d e i s removed and t r a n s f e r r e d t o a fume hood f o r c o n t i n u i n g work.
A I - L aqueous sample i s t r a n s f e r r e d t o a separatory funne l . A f t e r a pH adjustment, 60 mL o f methylene c h l o r i d e i s added t o t h e separatory funne l . The separatory funnel i s sealed and v i g o r o u s l y shaken f o r 1 t o 2 minutes w i t h p e r i o d i c ven t ing t o re lease excess pressure. Th is ven t ing i s performed i n a fume hood t o avoid exposure o f t h e ana lys t t o so l ven t vapors. The organic l a y e r i s a l lowed t o separate from t h e water phase f o r a minimum o f 10 minutes. The so l ven t e x t r a c t i s then c o l l e c t e d i n a Kuderna- Danish concen t ra to r .
The e x t r a c t i o n process i s then repeated two more t imes us ing f r e s h p o r t i o n s o f methylene c h l o r i d e . The Kuderna-Danish concen t ra to r , c o n t a i n i n g t h e combined e x t r a c t s , i s t r a n s f e r r e d t o a fume hood f o r c o n t i n u i n g work.
Approximately 300 mL o f methylene c h l o r i d e i s added
Each methylene c h l o r i d e procedure was performed approx imate ly 16 t o 2 0 t imes i n t h e l a s t 12 months.
6-3
Table 6-2. Chemicals w i t h Potent ia l f o r Elevated Airborne Concentrations.
Methylene Chloride
a? P
TLV = threshold limn value
(1 I From $945 MSAReJponse Resprator Seledor and OSHAZOCFR1010 Subpan2
( 2 ) From 1996MSA Response Rerplralar Selector an5ACGIH TLVfor ChemiCal Subrisnces and PhyscaIAgenfs (3) (VP)(MW)I(Eip Level] Exposure level used 13 m001 reatrlalve of OSHAor ACGlH 14) Hydmdllonc w d results highly dependent on mn~8ntration See Section 9 4 3 1
( 5 ) Ammonium Hydroxide as ammonia
(6) PELandTLVlaiHFasF
19%- 1995 3 z 7 wl
wl c -0
r
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7.0 PREVIOUS AND CURRENT MONITORING EFFORTS
In recent years, most industrial hygiene monitoring has been for asbestos, accounting for over 90% of the monitoring since 1989. the asbestos work at the 222-S Laboratory complex can be considered well characterized. Lead has also received additional attention and lead concentrations are part of an ongoing review. fairly well characterized and asbestos work is not a laboratory function, this section will focus on chemicals other than asbestos and lead. However, lead concentrations are still an area of potential concern (Section 9.2). The source of information for this review is the Hanford Industrial Hygiene Exposure Database, accessed July 9, 1996.
Since 1989, monitoring has been performed for 57 chemicals during 17 sampling events. less than detectable concentrations and none were greater than permissible airborne concentration limits. monitored were rooms 4E and 4P. parts per million (ppm) (208.8 mg/m3) methylene chloride in room 4P. a short-term exposure that resulted in an 8-hour time weighted average (TWA) of 6.5 ppm (22.6 mg/m3). exposure models described in Section 8 (see also Section 10.1). chemicals monitored, methylene chloride concentrations in room 4P were generally the highest. 222-S Laboratory complex since 1989 is provided in Table 7-1.
As a result,
Because these materials are
In all of this monitoring, 27 chemicals were indicated at
The highest concentration indicated was 60 The rooms and activities most frequently
This was
This monitoring event was used to validate the Of all the
A summary of the chemical monitoring performed in the
7-1
REff chemical Date R a n Result Monitored (m)
U
N
8hr Tw. PEL Activity (pp) (ppa)
v)
v) c -0
r
0 0
0
w
c
0
Table 7-1. 2 2 2 4 Exposure Monitoring. Sheet 2 o f 2
Activity
c V
r W
0 0 c
W (0
5
. -. _ _ _ . . . . . available to establish actual length of activiiy.
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T h i s page i n t e n t i o n a l l y l e f t b l a n k .
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8.0 ASSESSMENT MODELS
The models chosen for this evaluation were designed to predict airborne chemical concentrations and were based on U . S . Environmental Protection Agency (EPA), ACGIH, and American Industrial Hygiene Association (AIHA) Guidelines (EPA 1991; ACGIH 1988; AIHA and ACGIH 1996). Different models are used but all are based on a two-stage approach: (1) predict the generation rate of the component and (2) predict the dispersion. for each are provided in this section.
The information in these appendixes is generally presented as problem statements with subsequent assumptions, calculation data, and results.
The models used and justification
Additional modeling information is provided in Appendixes E through F .
8.1 SCENARIOS
identified that could result in elevated airborne chemical concentrations. These scenarios are as follows:
As a result of site tours and personnel interviews, four scenarios were
Room 4L Storage Cabinet Work. material storage cabinets. An organic odor is detected when at least one of these cabinets is opened. distribution of chemicals from this cabinet would help determine potential airborne concentrations and recommended actions.
and lead could result in elevated airborne levels. than permissible limits are considered highly unlikely due to the chemicals used and the use of hoods. Modeling of decontamination is difficult because solids, liquids, and vapors are involved. However, available data could indicate the potential for elevated levels of chemical airborne concentrations.
Standard Lab Solids Weighing. Most solids in the 222-S Laboratory complex are used in the 222-SA Standards Laboratory. The weighing of these solids outside of a hood may result in increased airborne levels. Modeling of the potential for increased airborne levels would indicate if monitoring was needed.
in hoods, periodically there may be a condition in which liquids are used or transferred outside of a hood then placed into a hood. Modeling of this activity for the chemicals identified in Section 6 will provide a general indication of the potential for elevated airborne concentrations.
In Room 4L there are four flammable
Modeling of the
Room 28 Decontamination Station Work. Decontamination of glass Levels greater
General Liquid Transfers. Although most operations are performed
8.2 STORAGE CABINET MODELS
For this evaluation, it was assumed that only one chemical contributes to the airborne concentrations released when the storage cabinets are opened. This was done to simplify the estimates and also to maximize the potential concentration. Both xylene and methylene chloride were modeled, xylene
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because i t i s present i n t h e cab ine t and methylene c h l o r i d e because it i s a common chemical used and s to red i n t h i s t ype o f cabinet . i n f o r m a t i o n on t h e s torage cab ine t models, see Appendix B.
For a d d i t i o n a l
8.2 .1 Storage Cabinet Generat ion Model
The genera t i on r a t e model (Equation 8-1) was adapted from t h e EPA drum f i l l i n g model (EPA 1991). Th i s model i s f r e q u e n t l y used t o est imate a i r b o r n e concen t ra t i ons d u r i n g tank t r u c k o r t ank ca r l o a d i n g and drumming operat ions. The concept behind t h i s model i s t h a t when a substance i s added t o a con ta ine r , an equal amount o f volume w i l l be d isp laced. I n most cases t h e m a t e r i a l added i s l i q u i d . I n t h i s s torage cab ine t case, t h e m a t e r i a l added i s a i r ( i . e . , when t h e cab ine t i s opened, a i r d i sp laces t h e chemical u n t i l t h e odor f u l l y d i s s i p a t e s ) . The f i l l r a t e was assumed t o be t h e t ime necessary t o remove a l l o f t h e odor, e i t h e r 5 o r 15 minutes, based on worker est imates f o r odor d i s s i p a t i o n . Because t h e r e were no obvious s p i l l s o r open b o t t l e s i n t h e cab ine t , i t was considered h i g h l y u n l i k e l y t h a t t h e chemicals would reach s a t u r a t i o n concen t ra t i ons . The s a t u r a t i o n f a c t o r i s a m o d i f i e r no rma l l y used t o compensate f o r sp lashing l i q u i d s . For t h i s a c t i v i t y i t w i l l be used t o compensate f o r a nonsaturated atmosphere and i s assumed t o be 10%. A d d i t i o n a l i n f o r m a t i o n on t h e use o f t h i s model i s prov ided i n Appendix 8.
Equat ion 8-1:
G, = mass rate of contaminate released, glmin r =filling rate, m i d v = volume of cabinet = 0.75 m3
f =factor accounting for nonsaturated air = 10% Papq = vapor pressure of contaminate, atm
mw, = molecular weight of contaminate, glg-mole
R = 8.205 x
T = temp, K (assumed room) = 298 K g -mole K
8.2.2 Storage Cabinet D ispe rs ion Model
f o r a constant genera t i on r a t e , w e l l mixed room (A IHA and ACGIH 1996) and (2) r a t e o f pu rg ing (ACGIH 1988). Both models are needed t o p r o p e r l y address t h e a i r b o r n e contaminat ion l e v e l s .
The models used f o r d i s p e r s i o n were: (1) t he general v e n t i l a t i o n model
The constant genera t i on r a t e , w e l l mixed room model (Equat ion 8-2) i s a p p l i c a b l e u n t i l t h e t ime t h e vapors have been removed from the cab ine t , e i t h e r 5 o r 15 minutes. The i n i t i a l room concen t ra t i on was assumed t o be zero. Based on room 4E, where t h e cab ine ts were p r e v i o u s l y s tored, t h e room volume was c a l c u l a t e d t o be approximately 147 m3. The v e n t i l a t i o n r a t e was
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calculated to be 37.1 m3/min based upon facility drawings. Per the Industrial Ventilation Manual (ACGIH 1988), an effective ventilation rate of 12.4 m3/min was used.
Equation 8-2: Q'(t-I> G, GX -7 C = - + (C,--)e
Q' Q'
G, = generation rate of contaminate, glmin Q' = effective volumetric airflow rate, m'lmin C, = initial room concentration = 0
t = time of concern = 5 , 15 minutes to = initial time = 0 v = room volume = 147 m'
After the initial 5- or 15-minute time for the contaminate vapor to be removed from the cabinet, the concentration will be exponentially reduced as a purge based on ventilation rate and room volume (Equation 8 - 3 ) .
Equation 8-3 :
Cf =
Cr= cx =
t - t o =
Target concentration = 1.0 mglm' Initial concentration, mglm' Time for reaching target concentration
A target concentration of 1.0 mg/m3 was chosen as a conservative value, To determine the time necessary to meet the target not as an airborne limit.
concentration the purge equation was solved for t (Equation 8 - 4 ) .
Equation 8-4 :
The results o f this modeling are described in Section 9 . 1 .
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8.3 DECONTAMINATION MODEL
The decontamination in the hoods in Room 2B is often performed for extended periods. Chemicals (frequently nitric acid) are used to decontaminate materials (frequently lead). There is no known acceptable modeling for decontamination activities due to the difficulties in predicting generation rates of lead and nitric acid under these conditions and the airborne distribution opposite the direction of air flow. However, the Industrial Hygiene Ventilation Manual (ACGIH 1988) indicates exposures are likely acceptable based upon empirical data. is described in Section 9.2.
The basis for this acceptability
8.4 222-SA STANDARDS LABORATORY SOLIDS WEIGHING MODEL
By comparing the airborne concentrations measured under a control led study with conditions similar to those in the 222-SA Standards Laboratory, potential laboratory specific airborne concentrations can be predicted. A study was funded by the EPA to provide a model to estimate typical airborne particulate concentrations in the vicinity of industrial operations involving the handling of small volumes of solids (grams to kilograms of powders, granules, and flakes) (Cowherd et al. 1989). The materials evaluated were talc, sodium chloride, portland cement, and direct yellow 4 dye. These materials where chosen based upon their ability to create dust and were viewed as covering a wide range of "dust potential." 50 and 125 kg of each compound were transferred from one container to another. Each test split the original quantity to 28 to 43 different transfers. airborne concentration was monitored for one hour. The average drop height of the chemicals was between 7.5 and 32 cm, depending on the test and material. The air exchange rate was 4.5 air changes per hour. Additional information on this model is provided in Appendix C.
determined that the conditions for each critical parameter (e.g., drop height and air flow) were either more conservative in the 222-SA Laboratory complex or similar. The major difference was the weight. By comparing the weights, a rough order of magnitude airborne concentration potential could be determined using Equation 8-5.
In l/Z-hour tests, between
The
Comparing the EPA tests with the 222-SA Standards Laboratory, it was
Equation 8-5: Assumed Airborne Concentration =
Average airborne concentration measured ~ Assumed weight tramferred Average total transfer weight measured
8.5 GENERAL CHEMICAL TRANSFER MODELS
The airborne concentrations from pouring a chemical and leaving it outside o f a hood could be significant. results of methylene chloride usage (Section 7 ) , indicate that there has been usage of some chemicals with measurable concentrations outside of hoods. The
Past history, including monitoring
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models used for this evaluation assume use outside of hoods. fumes inside of hoods is not modeled because the hoods are designed to prevent high levels of airborne chemical concentration and are tested monthly to ensure that design parameters are met (Section 4.1). two generation rate models and dispersion/exposure models were used. approach assumed that airborne generation is primarily due to displaced vapors and the distribution follows a Gausian model to the person pouring the chemical. driver and the general room ventilation model is the distribution path. When developing both approaches, methylene chloride was used as a test condition. Additional information on these models, using methylene chloride, is provided in Appendix D.
In both approaches, the following general parameters were assumed:
Exposure to
For these evaluations, One
The other approach assumed that evaporation is the generation
The material of concern is poured from a container to a beaker, outside of the fume hood
The material is allowed to remain outside of the hood for a period a time (e.g., 5 minutes)
The room is similar in size to room 4E (approximately 150 m3)
The design ventilation rate is seven air changes per hour and the effective rate is 1/3 of this based on ACGIH guidance (ACGIH 1988)
Air flow is generally 30 ft/min based upon previous Pacific Northwest National Laboratory (PNL) studies (Stoetzel and Hickey 1990; Stoetzel and Cicotte 1992)
Ideal gas laws are acceptable when other more specific data i s not avai 1 ab1 e.
These assumptions were chosen because they are either conservative measurements or common occurrences in most laboratories and provide quantifiable values for determining potential exposures.
8.5.1 Displacement Vapors Generation Rate
saturation mole fraction of the chemical of concern, then determining the volume and mass released. into a beaker containing residual liquid, displacing 200 mL of saturated volume. This model utilized Equations 8-6 through 8-8.
The displacement vapor generation model is based upon determining the
In this case it was assumed that 200 mL was poured
Equation 8-6:
m3 chemical m3 total
Ideal gas assumed, y. =
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y, = Saturation mole fraction of chemical Pa Ya = - P a h
Pressure of chemical a 760mm
moles chemical toral moles
Y . =
Y . =
Equat ion 8-7:
Volume released, = (200ml)(-)Cye) m3 106ml
Equat ion 8-8:
Mass released = (Volume released)(rnolecular weight) molar volume
8.5.2 Displacement Vapors D i s p e r s i o n
plume, as m o d i f i e d by de vevers (1995) and the A I H A and A C G I H (1996) (Equat ion 8 - 9 ) .
The displacement vapor d i s p e r s i o n model i s based upon the Gaussian
Equat ion 8-9: r'
M -w Ca = -e 8(7rtD,)'
C, = Airborne concentration of chemical ut time t , distance r m = mass released, kg
D, = Turbulent dispersion coeficient = 1.67 x t = time, seconds
based on AIHA h ACGIH (1996) g
r = radius, assumed 1 m
8.5.3 Evaporat ion Generat ion Model
The evapora t ion genera t ion model i s a general equat ion developed by t h e EPA (EPA 1991) f o r s p i l l s t h a t can be used t o p r e d i c t t h e evapora t ion r a t e o f a l i q u i d i n a f l o w i n g a i r stream (Equat ion 8-10). takes i n t o account t h e e f f e c t o f changes i n temperature, pressure, pool s ize , and a i r v e l o c i t y . I n general , t h e €PA equat ion assumes low concent ra t ions o f t h e evapora t ing so lvent , as compared t o t h e a i r c o n c e n t r a t i o n i n t h e room.
I n add i t i on , t h e model
As
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a result, this equation may begin to show errors for strongly evaporating solvents, long pool lengths, or slow air wind velocities (EPA 1991).
acceptable due to the relatively short times that the material would be outside of the hood. negligible.
Equation 8-10:
For this evaluation, -the 1 imitations of the equation were considered
In addition, lip effects from the beaker were assumed This also is a conservative estimate.
Evap. Rate(mg/min)
(2.79~10 -3) ( 1 . W . ) 0 . 8 3 5 ( V . P . ) ( A ) 7- ~ 0 . 0 5
= (7560)
where: 7,560 = M.W. = P = a = T = V.P. = A = v, =
conversion from lb/hr to mg/min molecular weight of evaporating liquid A overall pressure, atmospheres length of pool along air flow, feet surface temperature of pool, Kelvin vapor pressure of substance A (in.Hg) liquid surface area, ft2 velocity of air, ft/min
This equation was tested by the EPA (1991) by comparing it to experimental data provided by Pace Laboratories (EPA 1991). In an extensive study using a specially-built apparatus, Pace Laboratories measured the evaporation rate of 15 different compounds at several different temperatures and air velocities, and fit the data against "power law" regression against molecular weight, vapor pressure, and air velocity, with generally good results. Pace Laboratories performed an overall regression analysis for all chemicals except the "low vapor pressure" alcohols (1-hexanol, 1-heptanol, and 2-octanol) and obtained the following equation (Equation 8-11).
Equation 8-11:
Evap. Rate (mghin) = (7,560) (0.000237) (MW) (VP) (V,""") ( A )
where: 7,560 = M.W. = molecular weight of evaporating liquid A V.P. = vapor pressure of substance A (in.Hg) A = liquid surface area, ft2 v, = velocity of air, ft/min
conversion from lb/hr to mg/min
8.5.4 Evaporation Dispersion Model
used for the storage cabinet (Section 8.2.2), i.e., a constant generation The dispersion model for this analysis was considered the same as that
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r a t e , we l l mixed room. had t o account f o r bo th t h e t ime o u t s i d e o f t h e hood (genera t ion) and t h e purge t ime a f t e r t h e m a t e r i a l was placed i n s i d e o f t he hood over v a r y i n g t imes. The same equat ions were used (Equations 8-2 and 8-3) w i t h t h e f o l l o w i n g except ions: o f t h e hood and t h e purge t ime was t h e t ime t h e person was present i n t h e room (maximum o f 8 hours).
As i n t h e s to rage cab ine t model, t he d i s p e r s i o n model
t h e bu i l dup t ime was t h e t ime the chemical was o u t s i d e
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9.0 AIRBORNE CHEMICAL CONCENTRATION ESTIMATES
T h i s s e c t i o n descr ibes t h e a i r b o r n e chemical c o n c e n t r a t i o n es t imates based upon t h e scenar ios and models descr ibed i n Sec t ion 8. i n f o r m a t i o n on these es t imates i s p rov ided i n Appendixes 8 th rough F.
A d d i t i o n a l
9.1 STORAGE CABINET ESTIMATE
For t h i s est imate, t h e s to rage cab ine t i n room 4L was assumed t o c o n t a i n t h e vapors o f e i t h e r xy lene o r methylene c h l o r i d e . t he vapors were re leased i n e i t h e r 5 o r 15 minutes. s to rage c a b i n e t a i r b o r n e chemical c o n c e n t r a t i o n modeling, based on i n f o r m a t i o n prov ided i n Appendix 6, i s presented i n Table 9-1. room a i r b o r n e c o n c e n t r a t i o n can be h igh and t h e t ime t o decrease concent ra t ions t o 1 mg/m3 c o u l d take up t o 90 minutes. sho r t exposure t imes, 8-hour TWA l i m i t s w i l l l i k e l y n o t be exceeded. exposures and purge t imes are expected t o be c l o s e r t o t y p i c a l va lues than wors t case, b u t t h i s cannot be conf i rmed u n t i l m o n i t o r i n g i s completed. model assumes good m i x i n g i n t h e e n t i r e room. i n f r o n t o f t h e c a b i n e t w h i l e i t i s v e n t i n g w i l l be h igher . i s a good p r a c t i c e t o min imize exposures.
When t h e door was opened,
As ind ica ted , t h e maximum
The r e s u l t s o f t h e
However, due t o t h e Ac tua l
T h i s
Leaving t h e room Exposures t o personnel s t a n d i n g
Tab le 9-1. Storage Cabinet A i rborne Chemical Concent ra t ion Est imates.
Worst Case' Typ ica l ' Chemical Evaluated Generat ion
Xylene w i t h a 15 min 0.26 15 re lease t ime Methylene c h l o r i d e 8.02 464 w i t h a 15 min r e l e a s e t ime Methylene c h l o r i d e 23.9 663 w i t h a 5 min re lease t ime
I 5 air changes per hour estimated per ACGlH criteria 15 air changes per hour calculated for room 4 E
Time t o Reach
(minutes) 47
1. m9/m3
88
Conc. Reach
(minutes)
9.2 DECONTAMINATION ESTIMATES
Est imates o f l ead and n i t r i c a c i d a i rborne concent ra t ions i n t h e room 28
Because
decontaminat ion s t a t i o n can be assumed low due t o t h e s t r i c t eng ineer ing design requirements (Sec t ion 4.1), b u t t he re are no known models a v a i l a b l e t o adequately p r e d i c t t h e genera t ion r a t e and subsequent concent ra t ions . t he re are no adequate models, p e r i o d i c m o n i t o r i n g f o r l ead and n i t r i c a c i d should be performed i n room 28. This m o n i t o r i n g i s scheduled.
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HNF-SD-SUP-LB-001, Rev. 0
A i rbo rne concen t ra t i ons ou ts ide o f hoods are a func t i on o f b o t h t h e a i r f l o w i n t o t h e hood and t h e general v e n t i l a t i o n p a t t e r n . The ACGIH V e n t i l a t i o n Manual (ACGIH 1988) c i t e s a study performed by Caplan and Knutson (1978) t h a t demonstrated concentrat ions ou ts ide o f hoods can be mainta ined l o w i f hoods are adequately designed. hood and o u t s i d e the hood, a t r a c e r gas re lease i n s i d e o f t h e hood o f a t l e a s t 8 L/min r e s u l t e d i n concen t ra t i ons ou ts ide o f t h e hood below 0.1 ppm and u s u a l l y below 0.01 ppm. These r e s u l t s were w i t h an a i r f l o w i n t o t h e hood o f 50 l f m . I f t h e a i r f l o w ou ts ide o f t h e hood was poor, concen t ra t i ons o u t s i d e o f t h e hood were h ighe r , even i f t h e face v e l o c i t y was increased t o 150 l f m . Th i s r e l a t i o n s h i p between the general room a i r and t h e a i r f l o w cannot be r e a d i l y modeled.
hoods i n room 2B may re lease p a r t i c l e s g rea te r than fume s i ze , which w i l l have a g r e a t e r p o t e n t i a l f o r escaping t h e hood. Laboratory hoods are designed p r i m a r i l y t o capture fumes. Larger p a r t i c l e s could be re leased f rom t h e a c t i o n o f scrubbing m a t e r i a l s . However, i t i s l i k e l y t h a t these m a t e r i a l s a re captured. t h a t re lease m a t e r i a l s a t low v e l o c i t y , such as i n t e r m i t t e n t con ta ine r f i l l i n g ( A C G I H 1988). Pe r iod i c a i rbo rne chemical mon i to r i ng would he lp demonstrate adequate des ign and proper decontamination methods.
Wi th a good a i r supply system i n s i d e t h e
Decontamination o f glassware and lead s h i e l d i n g performed i n s i d e o f t h e
A capture v e l o c i t y o f 100 t o 200 l f m i s recommended f o r a c t i v i t i e s
9.3 222-SA STANDARDS LABORATORY SOLIDS WEIGHING ESTIMATES
Exposures t o s o l i d s i n t h e 222-SA Standards Laboratory are minimal and should n o t be f u r t h e r evaluated. A study funded by t h e EPA p rov ided a model t o est imate a i r b o r n e concen t ra t i ons o f a v a r i e t y o f m a t e r i a l s when small volumes o f these m a t e r i a l s were t r a n s f e r r e d over a 30-minute t ime (Cowherd e t a l . 1989). As i n d i c a t e d i n Sect ion 8.4 and Appendix C, t h e c o n d i t i o n s i n t h e 222-SA Standards Laboratory are a t l e a s t equal, i f n o t more conservat ive, t han t h e t e s t cond i t i ons .
Resul ts o f t h e comparison o f t h e 222-SA Laboratory complex and t h e EPA s tudy i n d i c a t e t h a t t h e worst case maximum est imated 1-hour a i rbo rne concen t ra t i on i s 1 mg/m3 and t h e l a r g e m a j o r i t y o f weighing a c t i v i t i e s would r e s u l t i n concen t ra t i ons equal t o o r l e s s than 0.01 mg/m3 (Table 9-2) . chemicals t h a t cou ld be weighed have exposure l i m i t s o f 0.01 mg/m3. compound w i t h t h e l owes t known exposure l e v e l i s cadmium s u l f i d e (0.1 mg/m3). Th is product i s never weighed i n l a r g e q u a n t i t i e s . I n a d d i t i o n , t h e l i m i t s are f o r an 8-hour exposure, t hus the 8-hour concen t ra t i on would be s i g n i f i c a n t l y lower than those i d e n t i f i e d i n Table 9-2.
No The
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Avg. A i rborne Concent ra t ion
(Assume
Tab le 9-2. E v a l u a t i o n o f 222-SA Standards Labora tory P o t e n t i a l A i rborne Concentrat ion.
Average A i rborne Concent ra t ion
I Assume
Cowherd e t a1 . (1989) Data’
T rans fer 1 kg) (ms/m3)
T r a i s f e r 10 g) (ms/m’)
Ta lc
Sodium C h l o r i d e
P o r t l a n d Cement
D i r e c t Yel low 4 Dve
87.27 48.4 t 13.7
99.60 106 f 24
124.8 36.8 f 19.7
54.30 9.96 f 5.67
0.003
0.002
Dust I n h a l a t i o n Exposures f rom the Hand l ing o f Smal l Volumes o f Powders (Cowherd e t a l . 1989) A l l measurements w i t h i n 1% o f average. *
9.4 GENERAL CHEMICAL TRANSFER ESTIMATES
I f c e r t a i n chemicals a re used o u t s i d e of hoods, t h e a i r b o r n e concent ra t ions cou ld be s i g n i f i c a n t and exceed exposure l i m i t s . some o f these chemicals i n d i c a t e s t h a t exposure w i l l occur i f the chemicals are p resent o u t s i d e of a hood (Sec t ion 7 ) . Because most chemicals, i n c l u d i n g a l l chemicals t h a t have been i d e n t i f i e d as having a h igh a i r b o r n e c o n c e n t r a t i o n p o t e n t i a l , a re r e p o r t e d l y used on ly i n s i d e o f hoods, t h e r e s u l t s i n t h i s s e c t i o n should be used p r i m a r i l y t o i n d i c a t e p o t e n t i a l concent ra t ions i f normal l a b o r a t o r y p r a c t i c e s and procedures are no t fo l lowed.
Past usage of
9.4.1 Chemicals Evaluated
The chemicals eva lua ted were those t h a t i n d i c a t e d h igh a i r b o r n e c o n c e n t r a t i o n p o t e n t i a l based upon comparing: (1) t h e molecu la r weight, vapor pressure, and a p p l i c a b l e a i r b o r n e l i m i t s (Sec t ion 6.2) and (2) many o f t h e f r e q u e n t l y used chemicals (Sec t ion 6.1) (Table 9-3). I n some cases, chemicals f i t i n t o bo th ca tegor ies . A i rborne l i m i t s f o r these chemicals are p rov ided i n Table 9-3. I n some cases a i rborne l i m i t s were d e r i v e d from ACGIH C r i t e r i a (ACGIH 1996).
9-3
Table 9-3. Chemicals o f Concern - Airborne L imi ts .
W
P
(1) 8-hourTime Weighted Average (2) 15mnute Averaged Shar lTen Exposure Limit (3) Ceiling Value that should never be exceeded
(4) Ammnium Hydroxide as ammonia (5) OSHA (6) Based on 3 times 8-hr TWA Value. per. ACGIH Guidance
(7) Based on 5 times 8-hr TWA value. pr ACGlH Guidance (8) ACGlH (9) 5 minute STEL IS available but not panicable for lab Situation
I z n
v)
? v) c 73
r
0
m
W 4
0
HNF-SD-SUP-LB-001, Rev. 0
Methylene C h l o r i d e
High P o t e n t i a l A i rborne Bromine
9.4.2 Displacement Vapors A i rborne Concent ra t ion Est imates
f rom a displacement o f sa tura ted vapor and subsequent d i s p e r s i o n based on Gaussian d i s t r i b u t i o n was low, was s i g n i f i c a n t l y l e s s than t h a t p r e d i c t e d by evaporat ion, and was no l o n g e r considered a major c o n t r i b u t o r t o a i r b o r n e concent ra t ions . However, f o r chemicals w i t h low a i r b o r n e l i m i t s (e.g., benzene, bromine, and h y d r o f l u o r i c ac id ) , p a r t i c u l a r l y i f s h o r t - t e r m exposure l i m i t s (STELs) o r c e i l i n g l e v e l s a re invo lved, even t h i s r e l e a s e i s s u f f i c i e n t t o cause p o t e n t i a l exceedance o f t h e l i m i t . I f volumes s i g n i f i c a n t l y g r e a t e r than 200 mL a re poured, t h i s pathway c o u l d be reeva lua ted . pressure chemicals w i t h extremely low exposure l i m i t s such as mercury.
d i sp l acement .
The a i r b o r n e c o n c e n t r a t i o n es t imates f rom c a l c u l a t i n g t h e mass r e s u l t i n g
I n add i t i on , t h i s may be a pr ime pathway f o r v e r y low vapor
Table 9-4 prov ides t h e maximum concent ra t ion r e s u l t s es t imated from
Chemical Name Maximum Concentration Due to Displacement"'
High Potential AirbornelFrequent Use
H y d r o c h l o r i c Ac id (38 wt%)"'
23.6
71 - 8
Ammonium Hydroxide (27 wt%)I3'
H y d r o f l u o r i c Ac id (51 w t % )
Ammonium Hydroxide (11 wt%)I3'
E p i c h l o r o h y d r i n
Hydrogen perox ide (30 w t % )
Pyr i d i ne
n-Hexane
Frequent Use
N i t r i c Ac id (70 wt%)
I n s t a Gel (1,2,4-trimethylbenzene)
I Benzene I 4 . 6 5 I 13.27
6.09
2.46
0.95
0.13
1.01
8.49
0.15
0.29
Ethy l a lcoho l 1.61
(2) Hydrochloric acid results highly dependent on concentration. See Section 9.4.3.1, (3) Ammonium Hydroxide as Ammonia.
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HNF-SD-SUP-LB-001, Rev. 0
Figure 9 - 1 provides the concentration curve for methylene chloride. All other concentration curves are similar. These maximum values are achieved within seconds of pouring. The average levels would be much lower.
9.4.3 Evaporation Airborne Concentration Estimates
model and Pace Laboratories empirical model (EPA 1991). As indicated in Table 9-5, the EPA model is typically a factor of approximately two higher than the Pace Laboratories model. by EPA for airborne concentration assessments, it is also the value used in this evaluation.
9.4.3.1 Results. rise until the chemical is placed in a hood. This is demonstrated for methylene chloride in Figure 9-2. As expected, the longer the chemical is outside of the hood, the higher the maximum (Figure 9 - 3 ) and average concentrations (Figure 9 - 4 ) . Figures for each of the chemicals of concern for typical ventilation rate (seven air changes per hour) are provided in Appendix E (maximum concentrations) and F (average concentrations). Table 9-6 indicates the times necessary for concentrations to reach airborne limits. Table 9-7 provides equilibrium concentrations and times to reach equilibrium concentrations.
Exposure to hydrochloric acid is highly dependent on the solution
The evaporation rates can be significant, based on the EPA theoretical
Because this higher value is the value used
The airborne concentration profile is indicated by a sharp
concentration of the hydrochloric acid solution. Calculations of the maximum airborne concentration of hydrochloric acid in the room were performed for solution concentrations of 30 wt% through 38 wt% HC1 (9.4M through 12.4M). The results of these calculations, shown in Figure 9-5, indicate that a solution concentration of 38 wt% will cause the airborne concentration of airborne HC1 in the room to exceed the immediately dangerous to life or health (IDLH) level in a very short time, whereas a solution concentration of 30 wt% will cause the airborne concentration in the room to never reach the ceiling exposure (CEIL) level.
relatively short time periods for many of the chemicals of concern. This evidence supports the laboratory practice of using most chemicals only in hoods.
As can be seen from Table 9-6 , airborne limits can be exceeded within
Actual concentrations, and times to reach airborne limits, will vary from those predicted. that actual exposures will likely be closer to the typical values than the worst case values.
9.4.3.2 Minimum Volumes. Activities that use very small liquid quantities outside of hoods may never exceed airborne limits due to lack o f available material. By multiplying the shortest time necessary to reach an airborne limit by the evaporation rate, a minimum volume required to reach the limit is identified (Table 9-8) . monitoring unless usage conditions change. small volumes of several chemicals could result in exceeding limits if left outside of hoods.
The model validation provided in Section 1 0 . 1 indicates
Use of volumes less than this should not require Table 9-8 indicates that only
Large volumes are necessary for methylene chloride.
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HNF-SD-SUP-LB-001, Rev. 0
In N 0 N
P
N
0 In 0
N
0 r
OD
c, E a,
I s - n ul
a E 0 Q 3
.u al v)
m 0 .u L
c 0
Q E 0
h c c, Q 3E
Y- O
E 0 c,
L c, E 0 u E
V
0 E. L
0 n L U
-
m
.- - -
.r
m
.-
.-I I m al L z
U
in .r
9-7
Table 9-5. Chemicals of Concern Evaporation Rates.
ln W
Chemical Name
(1) Based on EPA 1991 equatlOnS as described In SeCtlOn 8 5 3
(2) Assuming
5 5 in dcameler container
30 Wmin aimow over container
(3) Hydmchlonc acld results hlghly dependent on mnCentratiOn See SeCtlOn 9 4 3 1
(4) Ammonium Hydroxide as Ammonia
I z n
m
m c V
7
r m 0 0 c.
W 4
0
250
lo
lo
0
G. = 5.52 x lo3 mg / min = release rate Q = 17.5 m3 / min = 7 air changes/hr V = 150 m3 = room volume to = 0 min t, = 10 min = assumed time chemical is outside of hood t = time from chemical being placed in room
140 20 40 60 80
Time (min)
100 120
Figure 9-2. Instantaneous Concentration o f Methylene Chlor ide i n Room.
r m 0 0 w
P rD <
0
9000.00
8000.00
7000.00
6000.00 0
E
5000.00
. -. .
I- Maximum Concentration CElL ' - - - - IDLH
- _ _ _ _ . ~-
2000.00
1000.00
0.00 0 50 100 150 200 250 300 350 400 450
(1) Maximum concentration is that ConCentratlon seen at time 1. ifthe chemical is placed in a hood at time 1. (2) Average wncentration is cumulative average concentration if the chemical IS placed in a hood at timet. and the person remains in the area for 4 hours (3) Exposure limit is the most restrictive from OSHA or ACGlH
t, (min)
I z -n
VI
VI c V
r-
0 0
0
w - W c
Figure 9-3. Maximum Concentration o f Methylene Chloride in Room. 0
200.00
180.00
160.00
140.00
E .c 100.00 g g 80.00
E
0
40.00
20.00 ~- ~~~~ ~ ~
-Average Concentration
8-hr TWA Limit - ~
0.00
0 50 100 150 200 250 300 1, (min)
(1) Maximum wncentration is that concentration seen at time 1. if the chemical is placed in a hood at timet. (2) Average concentration is cumulative average concentration If the chemical is placed in a hood at tlme 1, and the person remains in the area for 4 hours. (3) Exposure limit is the most reStriCtive from OSHA or ACGlH
Figure 9-4. Averaged Concentrat ion o f Methylene Chloride i n Room.
v) D
v) c P r W
0 0
W <
0
Table 9-6 . Chemicals o f Concern - Times t o Reach Airborne L imi ts .
(1) R w m ventillati~n relo of 5 83 m'lmm (2 3 air changer I hour).
(2) R w m ventiliation relo Ot 17.5 m'lmln (7 air Changer I hour).
(3) Time Rqured lo madl airborne limn See Table C 3 for limns
(4) Using estimated limn bared on ACGlH guidance (See Table $3)
(5) Hydmchlonc acld resub hlghly dependent an concentrillBn. See SedlOo 9 4 3 1
(6) Ammonium Hydroxide as Ammonia
W <
0
Table 9-7. Chemicals o f Concern - Equi l ibr ium Concentrations.
W
W l-a
Worst Case Ventillation ‘’I I Typical Ventillation ‘*I Chemical Name I I
II I I
Hydrogen Peroxide (30 wt%) 7 185 2 47 Pyndine 41 215 14 75 n-Hexane 340 280 113 85
( 1 ) R w m ventillation rate of 5 83 m’lmin (2 3 air changes I hour)
(2) Rwm ventillation rate of 17 5 m’imin (7 air changes i hour)
(3) Hydmchlonc acid results highly dependent on concentralion See Seaion 9 4 3 1
(4) Ammonium Hydroxide as Ammonia
W C
0
HNF-SD-SUP-LB-001, Rev. 0
0 m 0 0 7
u s 2 I
r -
0 N 0 w 0 W 0
0 0 In
0 Ln P
0 0 m
0 0 N
0 In T
0 z
0 In
0
VI E 0
c,
L c, S
0 S
V VI T3 0 L
w c,
.- m
.r
m
m
8 p: C .r
2 s 0 L 0 c 0 L -0 * I 'c 0
S 0
c, L c, E al u S 0 V
.r
F
.r
m
5 2 E .r
r
Y)
m Q L T3
Y
m .r
T a b l e 9-8. Chemicals o f Concern - Volumes o f Chemical Required.
Chemical Name
(1) R w m ventillatinn rate of 5.83 m’lmin (2.3 air changes I hour).
(2) Room ventillatinn rate of 17 5 m’lmln (7 air changes I hour)
(3) No limits exceeded
(4) Hydrochloric acid resuI1s highly dependent on mncentratlon See Section 9 4 3 2
(5) Ammonium Hydroxideas Ammonia
P m <
0
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T h i s page intentionally left blank.
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10.0 MODEL VALIDATION
Because o f a l a c k o f comparative data, l i t t l e 222-S Labora to ry -spec i f i c model v a l i d a t i o n i s poss ib le . Th i s s e c t i o n p rov ides i n f o r m a t i o n t h a t q u a l i t a t i v e l y v a l i d a t e s t h e evaporat ion and subsequent constant generat ion, good m ix ing model used f o r general chemical t r a n s f e r s (Sect ion 9.4). These models a re v a l i d a t e d based upon prev ious mon i to r i ng r e s u l t s (Sect ion 7 ) . s e c t i o n a l s o p rov ides a v a l i d a t i o n o f t h e screening model based on vapor pressure, molecular weight, and exposure l e v e l (Sect ion 6.2).
Th i s
10.1 EXPOSURE MODEL VALIDATION
The bes t p rev ious mon i to r i ng f o r comparison and v a l i d a t i o n o f t h e evaporat ion and subsequent constant generat ion, good m ix ing model was performed February 4, 1992 f o r methylene c h l o r i d e a i r b o r n e mon i to r i ng r e s u l t s i n room 4P (Table 7-1) . t h e o n l y methylene c h l o r i d e opera t i on t h a t c l e a r l y i nc luded some work on t h e benchtop o u t s i d e o f a hood. The measured concen t ra t i on o f methylene c h l o r i d e was 60 ppm (208.8 mg/m3) and t h e 8-hour TWA was 6.5 ppm (22.6 mg/m3). Based on t h i s i n fo rma t ion , t h e p e r i o d moni tored was approx imate ly 52 minutes.
The average concen t ra t i on f o r a 52-minute exposure, based on averaging values, i s approx imate ly 270 mg/m3, which i s g r e a t e r than 208.8 mg/m3, b u t w i t h i n 25%. The 8-hour TWA f o r a 52-minute i n i t i a l exposure i s 34 mg/m3, which i s g r e a t e r than 22.6 mg/m3, b u t w i t h i n 35%. Agreement w i t h i n 35% i s ve ry good. Most modeling f o r t h i s t ype o f a c t i v i t y i s considered r e l i a b l e i f w i t h i n a f a c t o r o f 10 (1,000%). Based on t h i s , i t can be assumed t h a t t h e model can conserva t i ve l y , b u t r e a l i s t i c a l l y , es t ima te exposures.
Th is v a l i d a t i o n i s cons idered q u a l i t a t i v e . q u a n t i t a t i v e because o n l y one sample was a v a i l a b l e f o r comparison, t h e a c t i v i t i e s were n o t i d e n t i c a l , and t h e values measured d i d n o t necessa r i l y i n c l u d e t h e t ime t h a t t h e i n d i v i d u a l was i n t h e l a b o r a t o r y bu t t h e chemical was i n t h e hood.
The a c t i v i t y i nvo l ved r i n s i n g glassware. Th is was
The maximum concen t ra t i on a t 52 minutes i s approx imate ly 300 mg/m3.
It cannot be considered
10.2 SCREENING MODEL VALIDATION
I n Sec t i on 6.2, a screening model was used t o determine t a r g e t chemicals o f concern based upon molecular weight, vapor pressure, and a i rbo rne l i m i t s . Th i s screening method was demonstrated i n Sect ion 9.4 t o be e f f e c t i v e a t i n d i c a t i n g chemical concen t ra t i ons t h a t may exceed a i rbo rne l i m i t s . The chemicals o f concern were g e n e r a l l y presented i n terms o f usage categor ies, n o t s e q u e n t i a l l y by a i rbo rne screening f a c t o r . p o i n t s f o r t h e chemicals o f concern: i n decreas ing numerical va lue (Sect ion 6.2) and (2) t h e t ime the chemical must be l e f t ou t o f t h e hood t o reach t h e 8-hour TWA a i rbo rne l i m i t (Sect ion 9.4.3). Appendix F.
Table 10-1 p rov ides two da ta (1) a i rbo rne screening f a c t o r s arranged
These t imes are presented g r a p h i c a l l y f o r each chemical i n
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Table 10-1. Comparison o f Screening Fac to rs and Exposures.
1 Based on molecular weight. vapor pres6ure. and exposur~ limit. as described in Section 6.2 2 Time tho chemical must bo left Out of tho hood far tho total OXPOSUIO. averaped over 8 hours.
t o reach the exposure limit under typical ventilation conditions (See Tabla 9-31.
As can be seen i n Table 10-1, t h e two values are i n v e r s e l y p r o p o r t i o n a l ; t h e h ighe r t h e a i r b o r n e f a c t o r , t he s h o r t e r t h e t ime t o reach t h e a i r b o r n e l i m i t . chemical s o f concern.
Th is data i n d i c a t e s t h a t us ing t h i s model w i l l e f f e c t i v e l y i n d i c a t e
Based on these values, an approximate a i rbo rne screening va lue equal t o o r g r e a t e r t han 170 cou ld be used t o i n d i c a t e chemicals o f concern under t h e c o n d i t i o n s modeled. Th is va lue i s based upon a 4-hour t i m e w i t h t h e chemical ou ts ide o f t h e hood causing exceedance o f t h e 8-hour TWA l i m i t and t h e f o l l o w i n g equat ion de r i ved from the data i n Table 10-1.
Equat ion 10-1: log (Airborne Factor) = - 0.9638 [ log rime (min) ] + 4.53
Note: Equat ion c o r r e l a t i o n equals 0.90
A f t e r t h i s i n i t i a l screening, t h e i n d i v i d u a l chemicals can be eva lua ted t o determine i f s u f f i c i e n t volume i s used t o a l l o w exceedance o f l i m i t s (Sect ion 9.4.3.2).
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HNF-SO-SUP-LB-001, Rev. 0
11.0 AIRBORNE CHEMICAL MONITORING RECOMMENDED
T h i s s e c t i o n i d e n t i f i e s t h e recommended mon i to r i ng f o r t h e 222-S Laboratory complex based on the a i rbo rne chemical concen t ra t i on est imates i n Sec t i on 9.
11.1 ROOM 4L FLAMMABLE STORAGE CABINET
Ai rbo rne chemical concentrat ion est imates i n d i c a t e t h a t maximum concen t ra t i ons i n room 4L r e s u l t i n g from opening one o r more s torage c a b i n e t s cou ld be h igh, b u t average concentrat ions would n o t l i k e l y exceed a i r b o r n e l i m i t s (Sec t i on 9.1). moni tored d u r i n g opening as l o n g as chemicals and odors are p resen t . recommended t h a t an annual mon i to r i ng frequency be used. should i n i t i a l l y be performed t o a s s i s t i n i d e n t i f y i n g chemicals and e s t a b l i s h a i rbo rne concen t ra t i ons . i n i t i a1 mon i to r i ng .
As a precaut ion, Cabinet 2 should be p e r i o d i c a l l y It i s
A c t i v e m o n i t o r i n g
Passive badges may be evaluated f o r use a f t e r
11.2 ROOM 2B DECONTAMINATION STATION
Exposure est imates could no t be adequately made f o r t h i s exposure. Because o f t h e a c t i v i t i e s performed and the presence o f lead, decontaminat ion a c t i v i t i e s i n room 26 should be p e r i o d i c a l l y monitored. An annual m o n i t o r i n g frequency i s recommended unless decontamination methods change. n i t r i c a c i d should be i n i t i a l l y evaluated. demonstrated t o be low, then on ly one compound should be evaluated each year ; most l i k e l y l ead .
Both l e a d and I f n i t r i c a c i d l e v e l s are
11.3 CHEMICAL USAGE OUTSIDE OF HOODS
As s t a t e d i n Sect ion 10, t he general chemical t r a n s f e r models a re Based on p r e d i c t e d e f f e c t i v e a t p r e d i c t i n g exposures ou ts ide o f hoods.
exposures, t h e f o l l o w i n g chemicals should be monitored any t ime they a re used ou ts ide o f hoods u n t i l use -spec i f i c pa t te rns can be developed o r concen t ra t i ons l ower than those t y p i c a l i n the 222-SA Laboratory are used.
Bromine Benzene H y d r o f l u o r i c Ac id (51 wt%) Ammonium Hydroxide (> 11 wt%) Hydroch lo r i c Ac id (> 30 w t % )
New chemicals, chemicals w i t h s i m i l a r p r o p e r t i e s b u t no e s t a b l i s h e d exposure l i m i t s , and d i l u t e d forms o f t h e above chemicals should be eva lua ted by i n d u s t r i a l hygiene personnel based on molecular weight , vapor p ressu re ( i n mmHg), and e i t h e r known o r est imated exposure l i m i t s ( i n mg/m ) us ing t h e exposure f a c t o r f o rmu la (Sect ion 10.2) t o determine i f s i m i l a r exposure l e v e l s are l i k e l y i f used ou ts ide o f hoods. An exposure f a c t o r o f 170 cou ld be used t o i d e n t i f y chemicals o f concern (Sect ion 10.2).
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In addition, if organic chemicals are used outside of hoods it is recommended that monitoring be periodically performed as a demonstration of acceptable exposure levels. An annual monitoring frequency is recommended. This is particularly true of methylene chloride in light of current regulatory efforts (60 FR 54462 and 60 FR 62360) to reduce exposure levels. badges may be used for this monitoring.
Passive
11.4 MERCURY DISTILLATION
According to laboratory personnel, the mercury distillation unit, previously in room 4E, has not been used for some time. monitoring available for this operation. ventilation path. the fact that materials will be heated, any future mercury distillation with this equipment should include monitoring. Engineering controls should first be instituted to remove any residual mercury vapor. Surface contamination surveys should also be performed in room 4E to determine if there have been previous spills.
There is no In addition there was no clear local
Because of the extremely low airborne limit of mercury and
11.5 MAINTENANCE CHEMICALS
The 222-S Laboratory complex contains several maintenance chemicals. These chemicals include paints and solvents that may result in significant exposure depending on usage. It is recommended that airborne monitoring of these activities be performed as controlled through the Job Control System. Monitoring during subcontractor activities is also recommended.
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1 2 . 0 MONITORING NOT RECOMMENDED
Th is s e c t i o n descr ibes t h e mon i to r i ng t h a t i s n o t cons idered necessary based on t h i s eva lua t i on .
1 2 . 1 SOLIDS MONITORING I N THE 222-SA STANDARDS LABORATORY
Th is eva lua t i on has demonstrated t h a t exposure t o s o l i d s i n t h e 222-S Standards Laboratory are l i k e l y very l ow and should n o t be f u r t h e r evaluated.
12.2 MOST CHEMICALS
With t h e except ion o f t he chemicals l i s t e d i n Sec t i on 11.3, a i r b o r n e concen t ra t i ons from most chemicals should be low and should n o t be f u r t h e r evaluated unless t h e r e i s some mechanism ou ts ide o f hoods t h a t would c rea te e leva ted a i rbo rne concen t ra t i ons such as hea t ing ma te r ia l s , v igorous s t i r r i n g , o r t r a n s f e r o f l a r g e q u a n t i t i e s o f m a t e r i a l . commitment t o per form most operat ions i n s i d e o f hoods minimizes t h e p o t e n t i a l f o r increased chemical a i rbo rne concentrat ions.
The 222-S Laboratory complex’s
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13.0 CONCLUSIONS AND OTHER RECOMMENDATIONS
The 222-S Laboratory complex has an e s t a b l i s h e d system o f eng inee r ing c o n t r o l s (i .e., hoods), procedures, and q u a l i f i e d personnel t o c o n t r o l exposures t o p o t e n t i a l l y harmful ma te r ia l s , i n c l u d i n g chemicals and rad ionuc l i des . request on l y . c o n d i t i o n s where exposures could occur b u t exceedance o f e s t a b l i s h e d l i m i t s i s h i g h l y u n l i k e l y due t o e x i s t i n g c o n t r o l s . recommendations are prov ided.
modeling r e s u l t s f o r p o t e n t i a l h igh a i rbo rne concen t ra t i on chemicals and f r e q u e n t l y used chemicals i s summarized i n Table 13-1.
Mon i to r i ng has been performed i n t h e pas t b u t has been by Based on t h e i n fo rma t ion i n t h i s eva lua t i on , t h e r e a re some
The f o l l o w i n g general
Modeling has been performed t o est imate a i rbo rne concen t ra t i ons . The
13.1 PERFORM PERIODIC AND TASK SPECIFIC MONITORING
A p e r i o d i c mon i to r i ng schedule should be e s t a b l i s h e d i n accordance w i t h Sec t i on 11. w i t h Sec t i on 11.5, Job Contro l System requirements, and i n d u s t r i a l hygiene requirements, i n c l u d i n g asbestos and l e a d mon i to r i ng .
Task s p e c i f i c mon i to r i ng should a l s o be performed i n accordance
13.2 EVALUATE HOOD USAGE
The pr imary means f o r chemical exposure c o n t r o l i s t h e hoods. Managers should be v i g i l a n t i n ensur ing hoods are used whenever necessary. emphasis o f t h i s i n t r a i n i n g , and poss ib le a d d i t i o n o f t h i s i t em t o month ly i nspec t i ons would a s s i s t i n t h i s emphasis.
Continued
13.3 FURTHER EVALUATE AND MODIFY MERCURY DISTILLATION
The mercury d i s t i l l a t i o n u n i t should n o t be operated u n t i l su r face mon i to r i ng i s performed and engineer ing c o n t r o l s a re implemented t o remove mercury vapors.
13.4 UTILIZE AIRBORNE SCREENING FACTOR AND VOLUME COMPARISON
Th is eva lua t i on demonstrated t h e e f f e c t i v e n e s s o f t h e a i r b o r n e screening f a c t o r f o r chemical use ou ts ide o f hoods (Sect ions 6.2 and 10.2). Use o f t h i s f a c t o r cou ld be i nco rpo ra ted i n t o t h e Chemical Hygiene Plan. chemicals o f concern, t hen determin ing i f volumes used can cause l i m i t s t o be exceeded, c o n t r o l s can be es tab l i shed f o r t h e minimum number o f chemicals.
13.5
By i d e n t i f y i n g
MONITOR STORAGE CABINETS AND EITHER REMOVE CHEMICALS OR EVALUATE VENTING STORAGE CABINETS I F NEEDED
The cab ine ts i n room 4L should be moni tored f o r a i rbo rne chemical concentrat ions. I f l e v e l s i n d i c a t e t h a t employee exposures are e leva ted and approaching l i m i t s , t h e changes recommended i n t h e s e c t i o n should be f u r t h e r eval uated.
13-1
c W
N
Chemical Name
Table 13-1. Chemicals o f Concern - Summary In format ion.
L i m i t i n g Ai rborne
L i m i t
n-Hexane
High Po ten t i a l Exposure (Frequent Use) Hydrochlor ic Ac id (38%) Hydrochlor ic Ac id (30%) Methvlene Chlor ide
NONE
CEIL NONE
8 -h r TWAI3’
High Po ten t i a l Exposure Bromine Benzene Ammonium Hydroxide (14.5) Ammonium Hydroxide (6m) Hydro f l uo r i c Ac id Epich lorohydr in Hydrogen Peroxide 30% P v r i d i ne
Frequent Use N i t r i c Ac id I n s t a Gel (1,2,4-tr imethyl benzene) Ethv l Alcohol
STELI4’ STEL STEL STEL CEIL
8 -h r TWA 8 -h r TWA
NONEI5’
NONE NONE NONE
L i m i t i n g Concentrat ion
(mg/m31
7 NA 174
1.3 16 35 35 2.5 7.6 1.4
NONE
NONE NONE NONE NONE
Time t o Reach L i m i t (min)
1 NA 260
1 2 1 16 2
290 295
NONE
NONE NONE NONE NONE
~~
Volume t o Reach L i m i t (mL)
2.2 NA 755
1.2 1.3 5 7
0.8 31 15
NONE
NONE NONE NONE NONE I z n
VI
VI c -U
r
0 0
7
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Condi t ions i n which employees are advised t o l eave a work area f o r ven t ing (e.g., when Cabinet 2 i s opened i n room 4L) should be avoided. I f exposure i s an issue, removal o f t h e chemicals i s t h e p r e f e r r e d s o l u t i o n . I f t h i s cannot be done, cab ine t ven t ing should be evaluated i n accordance w i t h OSHA recommended p r a c t i c e s (Sect ion 5.1.1) and NFPA 30 (NFPA 1991).
The NFPA 30, Flammable and Combustible L i q u i d s Code, g e n e r a l l y recommends n o t ven t ing flammable ma te r ia l cabinets . I f v e n t i n g i s needed, t h e c o n s t r u c t i o n m a t e r i a l should be s i m i l a r (e.g., schedule 40 p ipe ) and ven t ing must be done t o an ou ts ide l o c a t i o n . I f a i r movement i s necessary, e i t h e r a Class 1 D i v i s i o n 1 motor and fan s h a l l be used i n s i d e t h e system o r an e x t e r n a l motor and an A i r Movers Contract Assoc ia t i on (AMCA) Class A non- spa rk ing f a n i s needed.
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14.0 REFERENCES
AIHA and ACGIH, 1996, P ro fess iona l Development Course 402, A Tool Box of Mathematical Models f o r Occupational Exposure Assessment, American I n d u s t r i a l Hygiene Assoc ia t i on and t h e American Conference o f Governmental I n d u s t r i a l Hyg ien i s t s , Course Manual, 1996, American I n d u s t r i a l Hygiene Conference and Exposi t ion, Washington, D.C.
Agents, 1996, American Conference o f Governmental I n d u s t r i a l Hyg ien i s t s , C i n c i n n a t i , Ohio.
E d i t i o n , American Conference o f Governmental I n d u s t r i a l Hyg ien i s t s , C i n c i n n a t i , Ohio.
AMCA, 1986, Standards Handbook, P u b l i c a t i o n 99-86, A i r Movement and Con t ro l Associat ion, Inc., A r l i n g t o n Heights , I l l i n o i s .
Caplan, K.J. and Knutson, G.W., 1978, Laboratory Fume Hoods: I n f l u e n c e o f Room A i r Supply, ASHRAE Transact ion, Vol . 84, Pa r t 2, 1978
Cowherd, C. Jr, Gre l i nge r , M. A., and Wong, K. F., 1989, Dust I n h a l a t i o n Exposures f rom the Handl ing o f Small Volumes o f Powders, American I n d u s t r i a l Hygiene Assoc ia t i on Journal 50(3):131-138, March, 1989.
New York.
ACGIH, 1996, Threshold L i m i t Values f o r Chemical Substances and Phys ica l
ACGIH, 1988, I n d u s t r i a l V e n t i l a t i o n , A Manual o f Recommended Prac t i ce , 2 0 t h
de Nevers, N . ,
DOE, 1989, General Design C r i t e r i a , DOE Order 6430.1A, U.S. Department o f
EPA, 1991, P repara t i on o f Engineer ing Assessments, Volume 1 CEB Eng ineer ing
1995, A i r P o l l u t i o n Con t ro l Engineering, McGraw H i l l , Inc. ,
Energy, Washington, D.C.
Manual D r a f t , U.S . Environmental P r o t e c t i o n Agency O f f i c e o f Tox ic Substances, Washington D.C.
Westinghouse Hanford Company, R ich l and, Washington.
Pennsylvania.
Chemicals i n Laborator ies, Na t iona l Academy Press, Washington D.C.
P r o t e c t i o n Associat ion, Quincy, Massachusetts.
Occupational Sa fe ty and Health, U.S. Department o f Hea l th and Human Serv ices, NIOSH Pub l i ca t i ons , C inc inna t i , Ohio.
WHC-SD-CP-HSP-001, Westinghouse Hanford Company, R i c h l and, Washington.
Evans, R. A., 1994, R a d i o l o g i c a l Design Guide, WHC-SD-GN-DGS-30011, Rev. 0,
MSA, 1996, Response R e s p i r a t o r Selector , Mine Safety, P i t t sbu rgh ,
Na t iona l Research Counci l , 1981, Prudent P r a c t i c e s f o r Hand l i ng Hazardous
NFPA, 1991, Flammable and Combustible L i q u i d s Code, 30, Na t iona l F i r e
NIOSH; 1994, NIOSH Pocket Guide to Chemical Hazards, Na t iona l I n s t i t u t e f o r
Sant, W., 1995, Westinghouse Hanford Company Chemical Hygiene Plan,
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S toe tze l , G. A. and C ico t te , G. R., 1992, E v a l u a t i o n o f A i r F low P a t t e r n s i n Se lec ted Areas o f t he 222-5 Laboratory Complex, P a c i f i c Northwest Laborator ies, R i c h l and, Washington.
S toe tze l , G. A. and Hickey, E. E., 1990, Eva lua t i on o f A i r Sampling and M o n i t o r i n g Loca t ions i n the 2225 F a c i l i t y D r a f t , P a c i f i c Northwest Laborator ies, R i c h l and, Washington.
Rev. 1, Westinghouse Hanford Company, Richland, Washington. Weaver, L. L., 1996, 222-5 Laboratory I n t e r i m S a f e t y Basis , WHC-SD-CP-ISB-002,
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APPENDIX A LABORATORY CHEMICAL INVENTORY INFORMATION
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Non-Maintenance Chemicals
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Non-Maintenance Chemicals
I I I I I I I I
I I I I I I II Carbon anode solution I 1.50E+W liters I 11 Carbon cathode solution I 8.WE+W liters I r^_*^^^.L I"Q~.E.II I 3 M E A - litDrc I
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Non-Maintenance Chemicals
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APPENDIX B STORAGE CABINET MODEL INFORMATION
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STORAGE CABINET MODEL INFORMATION
PROBLEM STATEMENT
When opening doors, s t r o n g o rgan ic smell i s present f o r approximately 15 minutes. under va r ious scenarios?
When t h e doors are opened, what i s t h e concen t ra t i on i n Room 4L
DATA There are no open con ta ine rs
I n i t i a l Room Concentrat ion = 0 mg/m3
Room volume and a i r f l o w based on prev ious s torage room, Room 4E - Room 4L very s i m i l a r .
Room volume = ( l e n g t h ) ( w i d t h ) ( h e i g h t ) = 2 6 f t x 2 0 f t x loft 1m3
= 5 , 2 0 0 f t 3 (- 35 .31 f t 3 ,
= 147m3
Cabinet Volume
1 ) (- I N 1// f t 3 m 3 4 4 1728inches 35 .31 f t
65” x 31- x 31- =6.35 x 104inches3(
= 1.04m3 = i m 3
Assume cab ine t 1 / 4 f u l l o f g lass
E f f e c t i v e volume = 0.75 m 3
Q = Vo lumet r i c Air Flow Rate Based upon P r i n t s m 3
3 5 . 3 1 f t 3 mi n ) = 37.1- 1m
= (13lOcfm)(-
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Air Changes per hour = 4 roomvo lume
= 15hr-’
4’ =Effective ventilation = - Q K
K = 3 Based on ACGIH Ventilation Manual m 3 37.1- min - 12.4m3 q / = ~ - ~
3 min
PROBLEM STATEMENT A
What is the generation rate if assuming xylene?
ASSUMPTIONS
Cabinet a i r l / l O t h sa tu ra ted w i t h xylene. open/broken con ta ine rs . process. Cabinet a i r changed o u t i n 15 minutes
l / l O t h chosen because t h e r e a re no Any leakage i s through d i f f u s i o n , a ve ry slow
Contaminate i s P-xylene Molecular weight : 106.2 g/g-mole Vapor pressure: 9 mm L i q u i d dens i t y : 0.86 g/mL OSHA PEL: Source: N I O S H Pocket Guide
100 ppm (435 mg/m3)
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STORAGE CABINET MODEL INFORMATION
F i l l i n g r a t e :
- 1 - - I
= 0.067mi n-'
r15 = t ank f i l l r a t e = a i r changeout t i m e 15min
G, = mass r a t e o f xy lene re leased r15v Pavap f (MWJ
RT r15 = f i l l i n g r a t e = 0.067min"
-
v = volume o f cab ine t = 0.75m3 l a t m
760mm Pavap = vapor pressure o f contaminate = (9mm)(-) = 1.18 x 10-'atm
f = f a c t o r account ing f o r nonsaturated volume = 0.1
mo 1 ecul a r we igh t o f xy lene 106 9 .2- g m o 1 e
m3atm g m o l e k
R = 8.205 x 10-5-
T = temp€ " K (assumed room) = 298.15k
(0.067mi n-' ( 0 . 75m3) (1 .18 x lO-'atm) ( 0 . 1 ) ( 1 0 6 . 2 9 )
m3atm (8.205 x 10-5-)(298.15"k) g m o l e k
g-mole G, =
= 0.258 9 mi n
Volume o f Xylene re leased
1 G 1 = (0.258 -) (15 min) (
min 0.86 g/ml = 4.5 m l
PROBLEM STATEMENT B
What i s t h e maximum room concen t ra t i on?
ASSUMPTIONS
Cabinet a i r change o u t i n 15 minutes Instantaneous room mix ing Xylene
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Q' =
cxo =
to = t =
v = *
cx.m.x=
HNF-SD-SUP-LB-001, Rev. 0
STORAGE CABINET MODEL INFORMATION
generat ion r a t e o f xy lene = 0 . 2 5 8 2 m i n
e f f e c t i v e vo lumetr ic a i r f l o w r a t e = 1 2 . 4 m " m i n
i n i t i a l room concen t ra t i on = 0 t ime o f concern = 15 min i n i t i a l t ime = 0 room volume = 147m3
0 . 2 5 8 9 0 . 2 5 8 9 1~4"115rnin1 min
m i n min ) e - 147m3
m 3 12.4- m 3 12.4- m i n m i n
+ (0 -
= 0 . 0 1 5 x m 3
= 1 5 2 (3 ppm) m
PROBLEM STATEMENT C
What i s t he maximum room concen t ra t i on i f t h e contaminate i s methylene ch 1 o r i d e ?
ASSUMPTIONS
A l l o the rs as s t a t e d above
DATA Contaminate i s methylene c h l o r i d e Molecular weight : 84.9 Vapor pressure: 350 mm
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L i q u i d dens i t y : 1.33 OSHA PEL: A C G I H TLV: Source: NIOSH Pocket gu ide
ACGIH TLV handbook
From prev ious c a l c u l a t i o n :
500 ppm (1739 mg/m3) 50 ppm (174 mg/m3)
GmC = Generation r a t e methylene c h l o r i d e G, = Generation r a t e xy lene P = Vapour pressure
mw = M o l e c u l a r weight
1 Volume Released = (8.02 9) (15 min) ( m i n 1.33 g/ml)
= 90.4 ml
A l l u n i t s p r e v i o u s l y descr ibed
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Cmcmax = 0 . 4 6 4 9 m3
= 4 6 4 2 (135 ppm) m
PROBLEM STATEMENT 0
What i s the maximum concentration i f methylene chlor ide i s the contaminate and the Cabinet a i r change is reduced f r o m 15 minutes t o 5 minutes?
ASSUMPTIONS
As above except new Cabinet a i r change out t i m e
1 5 min
New f i l l i n g ra te = r5 = - = 0.2 min-'
1 0.2 min-' = 8 . 0 2 9 (
min 0.067 min-' 9
min GmCnew = 23 .9-
A l l un i t s previously described t = 5 minutes
CmCmn- = 6 6 3 2 (194 ppm) m
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STORAGE CABINET MODEL INFORMATION
PROBLEM STATEMENT E
How long w i l l i t take f o r t he a i r concen t ra t i on t o be reduced t o 1 . 0 mg/m" wi th a 5 minute Cabinet a i r change out?
ASSUMPTIONS
Methylene c h l o r i d e i s contaminate Cabinet a i r change o u t i n 5 minutes Maximum a i r concen t ra t i on i s 663 mg/m3
DATA To ta l t ime = t ime t o maximum concen t ra t i on t t ime f rom maximum t o t a r g e t concen t ra t i on Time t o maximum concen t ra t i on = 5 minutes as c a l c u l a t e d above Time from maximum t o t a r g e t concen t ra t i on = purge t ime
0'lt-tol ~
C, = C,e " C,= Target concen t ra t i on = 1.0%
m 3
C, = I n i t i a l concen t ra t i on = 6 6 3 7 m
t - to =Time reach t a r g e t concen t ra t i on
Other u n i t s as p r e v i o u s l y descr ibed
So lv ing f o r t - to
147m3 1.0 = -- ln-
m 3 663 12.4- m i n
= 77 min
Time from maximum t o t a r g e t concen t ra t i on = 77 minutes To ta l t ime = 5 minutes t 77 minutes = 82 minutes
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PROBLEM STATEMENT F
How long w i l l i t take f o r t he a i r concen t ra t i on t o be reduced t o 1.0 mg/m” with a 15 minute Cabinet a i r change out?
ASSUMPTIONS
Methylene c h l o r i d e i s t h e contaminant Cabinet a i r change ou t i n 1 5 minutes Maximum a i r concen t ra t i on o f 464 mg/m3
A s p r e v i o u s l y descr ibed
Purge t ime = 73 minutes Purge r a t e c o n s i s t e n t l y = 75 min
T o t a l t ime more a f a c t o r o f cab ine t a i r change o u t t i m e
= 88 min To ta l t ime = 15 min + 73 min
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APPENDIX C 222-SA STANDARDS LABORATORY SOLIDS WEIGHING MODEL INFORMATION
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222-SA STANDARDS LABORATORY SOLIDS WEIGHING MODEL INFORMATION
PROBLEM STATEMENT
What is the potential exposure to airborne solids in the 222-SA Standards Laboratory?
ASSUMPTIONS
Exposure t o s o l i d s i n a l a b o r a t o r y - t y p e environment has been evaluated and p i e r reviewed (Cowherd e t a l . 1989). The i n f o r m a t i o n from t h a t r e p o r t w i l l be used as a bas i s f o r 222-SA Standards Laboratory exposures. Parameters from Cowherd e t a l . (1989) can be used as i d e n t i f i e d below.
DATA Per 1 aboratory personnel :
A l l s o l i d s a c t i v i t i e s ou ts ide o f hoods a re f o r weighing
On a ve ry i n f requen t bas i s (- 1 t o 2 t imes p e r yea r ) , chemicals up
>95% o f weighing i s 5 10 grams
t o -1 kg are poured
Most chemicals poured have l a r g e c r y s t a l 1 i n e s t r u c t u r e s
c-3
HNF-SD-SUP-LB-001, Rev.
222-SA STANDARDS LABORATORY SOLIDS WEIGHING MODEL INFORMATION
Table C-1. Conditions in Cowherd et al. (1989) and comparisons to 222-SA Standards Laboratory.
PARAMETER
Materials
Weight used
Monitoring performed Transfer methods
Ventilation
COWHERD ET AL. 1989
Talc, sodium chloride, Port1 and cement, direct Yellow 4 dye (chosen for wide size range and ability to cause airborne contamination) 50 to 125 kg transfers tested. Each transfer took 30 minutes, see below for further details 1 hour monitoring periods Poured or scooped from 14, 22, and 32 cm
Base air exchange rate 4.5 air changes per hour
222-SA STANDARDS LABORATORY
Wide variety of material, primarily large crystalline structure
5 10 grams usually infrequently up t o fi 1 kg
No monitoring data
Assumed simi 1 ar (conservation assumption, typical height closer to 1 to 5 cm) 7 air exchanges per hour typical, 5 minimum
0
As a result of comparing the conditions in Cowherd et al. (1989) and 222-SA Standards Laboratory, it is assumed that the Cowherd et al. (1989) data can be used to conservatively estimate 222-SA Standards Laboratory potential exposure as follows.
large majority of concentrations I 0.01 mg/m3. average would be approximately eight times lower.
As a result, maximum estimated 1 hour air concentration is 1 mg/m3 with Eight hour time weighted
c-4
Table C-2. Evaluat ion o f 222-SA Standards Laboratory Potent ia l Airborne Concentration.
Materi a1 Tested
Talc Sodium Chloride Por t l and Cement
COWHERD ET AL. (1989) DATA
Avg. Total A y .
(Kg) Transfers’ (Kg)
Transfer Avg. Number Weight/ Weight’ o f Transfer
87.27 42.33 2.06
99.60 28.67 3.47
124.8 29.00 4.30
54.30 36.50 1.48 9.96 t 5.67
48.4 t 13.7
106 f 24
36.8 f 19.7 0.30 P 0
v)
0 r
0 v)
H 0.18 .002
’ All numbers within 1 % of average AII transfers plus or minus 2 (Avg. airborne concentration measured)/(Avg. total transfer weight measuredl(Assurned weight transferred] x 0
0 m r
P <
0
HNF-SD-SUP-LE-001, Rev. 0
222-SA STANDARDS LABORATORY SOLIDS WEIGHING MODEL INFORMATION
This page intentionally left blank.
C-6
HNF-SD-SUP-LP-001, Rev. 0
APPENDIX D GENERAL CHEMICAL TRANSFER MODEL INFORMATION
D- 1
HNF-SD-SUP-LP-001, Rev. 0
This page intentionally left blank. ,
D-2
HNF-SD-SUP-LB-001, Rev. 0
GENERAL CHEMICAL TRANSFER MODEL INFORMATION
OVERALL PROBLEM STATEMENT
What i s the pe rsona l exposure t o methylene c h l o r i d e when p o u r i n g the chemical i n t o a beaker under va r ious c o n d i t i o n s u s i n g var ious model ing techniques?
ASSUMPTIONS
v = Room volume s i m i l a r t o Lab 4E e 150 m3 A i r changes p e r hour = 7 hr- ' based on minimum a i r change o u t des ign A i r f l o w g e n e r a l l y 10 - 30 f t / m i n (3.05 - 9.15 m/min)
Q = Volumetr ic a i r f l o w r a t e 7 h r hr 60 min
= (-)(-)150m2
m 3 m i n
Q = 17.5 -
Q Q' = E f f e c t i v e v e n t i l a t i o n = - K
K = 3 Based on ACGIH
Methylene c h l o r i d e molecular weight : 84.9 g/g-mole vapor pressure: 350 mm l i q u i d dens i t y : 1.33 OSHA PEL: 500 ppm (1739 mg/m3) N I O S H Pocket Guide
PROBLEM STATEMENT A
What i s t he vapor genera t i on volume i f assume genera t i on volume p r i m a r i l y due t o sa tu ra ted atmosphere displacement?
ASSUMPTIONS
L i q u i d volume poured equal s volume o f sa tu ra ted atmosphere d i sp laced Two hundred m i l l i l i t e r s o f methylene c h l o r i d e are poured Evaporation c o n t r i b u t i o n i s n e g l i g i b l e Standard Room Temperature Idea l Gas
D-3
HNF-SD-SUP-LB-001, Rev. 0
GENERAL CHEMICAL TRANSFER MODEL INFORMATION
Sa tu ra t i on mole f r a c t i o n
y, = S a t u r a t i o n mole f r a c t i o n o f methylene c h l o r i d e
PA "sp Y, = - Path 350mm
Y, = - 760mm
moles methylene c h l o r i d e t o t a 1 moles
ya = 0.46
m 3 methylene c h l o r i d e m 3 t o t a l
S ince I d e a l gas, ya = 0.46
Vol ume o f methylene c h l o r i d e re1 eased = volume o f headspace re1 eased (Vol ume f r a c t i o n methylene c h l o r i d e )
m 3 0.46m3 methylene c h l o r i d e Volume releasedmc = (200ml)(-) 10% 1 m 3 t o t a l
volume releasedmc = 9.2 x 10-5m3
PROBLEM STATEMENT B
What i s the a i r b o r n e concen t ra t i on assuming Gaussian puff wi th t h r e e d imensional spreading and un i fo rm d i spe rs ion?
ASSUMPTIONS
Methylene c h l o r i d e re leased i n sho r t t ime (==lo seconds) Gaussian p u f f Uni form d i s p e r s i o n Turbulent d i s p e r s i o n c o e f f i c i e n t (DT) = 1.0 m2/min(1.67 x l o - ' m'/s)
Worker == 1 meter from source
based upon AIHA/ACGIH i f guidance i n "A Tool Box o f mathematical models f o r Occupational Exposure Assessment" (AIHA 1996)
0-4
HNF-SD-SUP-LB-001, Rev. 0
GENERAL CHEMICAL TRANSFER MODEL INFORMATION
DATA The mass o f methylene c h l o r i d e re leased i s :
(Volume r e l e a s e d ) ( m o l e c u l a r w e i g h t ) molar volume
Mass r e l e a s e d =
(9.2 x 1 0 - 5 m 3 ) ( 8 4 . 9 k 9 )
m 3 (24.4 - kg+nole
kg-mole m = 1
in = 3.2 x 10-4kg
Cmc = Concentrat ion o f methylene c h l o r i d e a t t i m e f , d i s t a n c e r m = mass = 3 . 2 x w 4 k g t = t i m e = 10 seconds
0, = Turbulent d i s p e r i o n c o e f f i c i e n t = 1.67 x
r = r a d i u s = 1 m 10 mr
411 67 x 1 0 - 2 ~ 1 1 1 0 si (3.2 x 10-4kg) cmc = e
m 2 3
(8)((n)(1.67 x 10-2-)(10 s ) ) ~ S
= 23.6 % ( l i m i t i s 1 7 3 9 3 ) m 3 m 3
D-5
HNF-SD-SUP-LB-001, Rev. 0
GENERAL CHEMICAL TRANSFER MODEL INFORMATION
PROBLEM STATEMENT C
What i s t h e genera t i on r a t e i f evaporat ion i s t h e d r i v i n g re lease mechanism?
ASSUMPTIONS
Methylene c h l o r i d e i s l e f t i n a 5.5" diameter beaker No vapor displacement No l i p e f f e c t o f beaker Other assumptions as prev ious l y described
1 1 29 m
2.79 x P a ( - + - ) 0 2 5 ( v z ) 0 5 A
Gmc = 'j= 0 05Az 0 05p 0 5
where
lb GmC = Generat ion r a t e , - h r
l b lb mole
in = m o l e c u l a r we igh t , - = 84.9
inches 25.4 mm
P - = vapor pressure, inHg = (350 mm)(- ) = 13.8 inches
f t v, = a i r v e l o c i t y , - f t = 30 - (moreconservat ive) mi n m i n
5.5 inches A = area, f t 2 = n((
T = temperature, OK = 298'K
f t ) ) ' = 0.17 f t 2 2 ) ( 12 inches
AZ = p o o l l eng th along f l o w d i r e c t i o n , f t
= (5.5 i nches ) ( f t ) = 0.46 f t 12 inches
P, = o v e r a l l pressure, atm = 1 atm
D-6
HNF-SD-SUP-LB-001, Rev. 0
GENERAL CHEMICAL TRANSFER MODEL INFORMATION
1 1 29 84.9
2.79 x 1 0-3( 84. 9)0.835( 13.8) ( - + - ) 0.25( 30) 0.50. 17 -
( 298)0.05 (0. 46)0.5 ( 1)0.5 l b 454 g g-mole 24.41 103cm2 1 = (0.7522 -)(-)(- )(-I(- h r l b 84.9 g mole 7
cm h r
= 9,82 x 104-
l b hr 454 g lo3 mg hr 60 min 7b 9 m i n
= (0.7522 -)(- I(-)(-) = 5.69 x 103 2
PROBLEM STATEMENT D
What i s t he a i r b o r n e contaminat ion i f evaporat ion i s t h e d r i v i n g fo rce?
ASSUMPTIONS
From t h e t ime t h e methylene c h l o r i d e i s poured t o t h e t ime i t i s i n t h e hood i s 5 minutes Worker remains i n t h e l a b f o r 4 hours
D-7
HNF-SD-SUP-LE-001, Rev. 0
GENERAL CHEMICAL TRANSFER MODEL INFORMATION
_DATA
Use bas i c equat ions for b u i l d up and purge used i n s torage cab ine t model F ind t h e d e f i n i t e i n t e g r a l of t he f o l l o w i n g curve f o r t ime = to t o t,:
-$It -T,l ) for t < t, Cz,l = - ( I GA - e
Q GA -$ir, - tal -$ir - t5i
C,>, = -(1 -e Q
t ,
) f o r t t t , 1 (e
D-8
HNF-SD-SUP-LB-001, Rev. 0
APPENDIX E MAXIMUM AIRBORNE CONCENTRATIONS UNDER TYPICAL VENTILATION CONDITIONS
E- 1
HNF-SD-SUP-LB-001, Rev. 0
This page intentionally left blank.
E - 2
120.0000
100.0000
80.0000 0-
E ml E - - C
60.0000 e L E 0
0 0
40.0000
20.0000
0.0000
Maximum Concentration of Hydrochloric Acid in Room Typical Ventillation (7 air changeslhr)
0 10 20 30 40 50 60 70 80 90 100
(2) Average concentration IS cumulative average concentration if the chemical IS placed in a hood at time 1. and the person remains in the area for 4
0 0 t, (rnin) c. (1) Maximum concentration is that wncentration seen at time 1. if the chemical is placed in a hood at time 1.
hours. (3) Exposure limit is the most restnctive from OSHA or ACGIH.
W <
0
KlUSTID02~LISOMHYORCHLOXLS Mar I17 5 )
9000.00
8000.00
7000.00
6000.00 0-
3 5000.00
,E
3000.00
2000.00
1000.00
Maximum Concentration of Methylene Chloride in Room Typical Ventillation (7 air changeslhr)
~ M a x l m u m G G G , - - - - - . C E I L I
IDLH I
..-
0 50 100 150 200 250 300 350 400 450
(1) Maximum concentration is that concentration seen at time 1, if the chemical is placed in a hood at timet (2) Average concentration is cumulative average concentration if the chemical is placed in a hood at time t. and the person remains in the area for 4 hours (3) Exposure limit IS the most restrictive from OSHA or ACGIH.
t, (min)
c P r m
0 E W c
0
KIUSTIO0221ALISOMMECL XLS Max (11 51
50.0
45.0
40.0
35.0
30.0 - 2
15.0
10.0
5.0
0.0
Maximum Concentration of Bromine in Room Typical Ventillation (7 air changeslhr)
...... STEL ---
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 I t, (min)
(1) Maximum concentration is that concentration seen at timet. if the chemical is placed in a hood at time 1. (2) Average concentration is cumulatlve average concentration if the chemical is placed in a hood at time 1, and the person remains in the area for 4 hours. (3) Exposure limit IS the most restridive from OSHA or ACGIH.
0 0 c.
P (D 4
0
KIUSTIW22~LISOMBROMINE XLS Max (5 831
20.00
18.00
16.00
14.00
n- z 1200
g 10.00 m 2
g 8.00 s
- F E
t c m a
6.00
4.00
2.00
0.00
Maximum Concentration of Benzene in Room Typical Ventillation (7 air changeslhr)
Maximum Concentration STEL
, - - - - - .CEIL
0 0.5 1 1.5 2 2.5 3 t, (min)
(1) Maximum concentration is that concentration seen at time t, if the chemical is placed in a hood at time 1. (2) Average concentration IS cumulative average concentration if the chemical is placed in a hood at time 1, and the person remains in the area for 4 hours. (3) Exposure limit is the most restrictive from OSHA or ACGIH.
0 0 c
W C
0
KlVSTIOOZ2l4LISOMBENZENE XLS. Mar (5831
250.00
200.00
0-
5 150.00 - z? r : 5
C
u - s g 100.00 0
50.00
0.00
Maximum Concentration of 27 Wt% Ammonium Hydroxide (as Ammonia) in Room Typical Ventillation (7 air changeslhr)
------
Maximum Concentration
i v) c 0 -
0 10 20 30 40 50 60 70 80 90 100 1 0
tl (min) - (1) Maximum concentration is that concentration seen at time 1. if the chemical is placed in a hood at time 1. (2) Average concentration is cumulative average concentration If the chemical is placed in a hood at timet. and the person remains in the area for 4
(3) Exposure limit IS the most restrictive from OSHA or ACGlH hours P
0
K lUST10022iALISOMhMMONl~ XLS Mar (5 831
30.00
25.00
20.00
Maximum Concentration of Hydrofluoric Acid in Room Typical Ventillation (7 air changeslhr)
f 1-
5.00
0.00 0 50 100 150 200 250 300 350 400 450
(1) Maximum concentration is that concentration seen at time 1, if the chemical is placed in a hood at timet. (2) Average concentration is cumulative average concentration if the chemical is placed in a hood at time 1. and the person remains in the area for 4 hours (3) Exposure limit is the most restrictive from OSHA or ACGIH.
t, (min)
I z -ll
ln
ln c -0
r m
0 0
0
w
W <
0
KIUSTIDD22l4LISONlHF XLS. MBX I17 5)
250.00
200.00
1 1 150.00 E - 6
r : 2 W E : 100.00 s
2
50.00
0 00
Maximum Concentration of 11 Wt% Ammonium Hydroxide (as Ammonia) in Room Typical Ventillation (7 air changeslhr)
Maximum Concentration
L
3 z -rl
m 0
m c P r
0
0 10 20 30 40 50 60 70 80 90 100 m t, (min)
(1) Maximum concentration is that concentration seen at timet. if the chemical is placed in a hood at timet (2) Average concentration is cumulative average concentration if the chemical is placed in a hood at time 1, and the person remains in the area for 4 hours. (3) Exposure limit IS the most restnctive from OSHA or ACGlH
0 c
0
K \USTID02Z\ALISON\AMMON6 XLS Mar (5 831
HNF-SD-SUP-LB-001, Rev. 0
A 0 0 0 0
K 9 9 5! m 9
0 . - N
E - I O
HNF-SD-SUP-LB-001, Rev. 0
I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I
0 In 0
b
80.00
70.00
60.00
- “E 50.00 - - E E
m 2 40.00 L 2 ! N C
0
5 30.00
20.00
Maximum Concentration of Pyridine in Room Typical Ventillation (7 air changeslhr)
--
Maximum Concentration CElL
000 y 0 50 100 150 200 250 300 350
t, (min) 400 450
(1) Maximum concentration is that concentration seen at timet. if the chemical is placed in a hood at time 1. (2) Average concentration is cumulative average concentration if the chemical is placed in a hood at time 1. and the person remains in the area for4 hours. (3) Exposure iimlt is the most restridive from OSHA or ACGIH.
KlUSTID02Z~LlSOMPYRlOlNE XLS. Max 117 51
900.00
800.00
700.00
600.00 - E
E 500.00 C
m P n e 2 400.00 0
0 0
300.00
200.00
100.00
Maximum Concentration of n-Hexane in Room Typical Ventillation (7 air changeslhr)
Maximum Concentration 1 STEL
CElL
000 y 0 50 100 150 200 250 300 350 400 450
(1) Maximum concentration is that concentration seen at time 1. If the chemical is placed In a hood at timet (2) Average concentration is cumulative average concentration If the chemical IS placed in a hood at timet. and the person remains in the area for4 hours (3) Exposure limit is the most restrictive from OSHA or ACGlH
t, (min)
K\USTIDOZZV\LISOMHEXANMIE XLS Max (17 5)
I z 7 7
v)
v) c V
r m
0 0
Fl
c
W C
0
HNF-SD-SUP-LB-001, Rev. 0
0 0 0 0 0 0 0
8 K 7 8 7 K 8 N
K N
2 m (,u/Sru) uo!)eJ)uaDuo3
E-14
400.00
350.00
300.00
ny 250.00 - E
100.00
50.00
0.00 0
Maximum Concentration of lnsta Gel in Room Typical Ventillation (7 air changeslhr)
1- Maximum Concentration 1 STEL EL I
50 100 150 200 250 300 350 400 450 t, (min)
(1) Maximum concentration is that concentration seen at time 1, if the chemical 1s placed in a hood at time 1. (2) Average concentration is cumulative average concentration if the chemical is placed in a hood at timet. and the penon remains in the area for 4 hours. (3) Exposure limit IS the most restrictlve from OSHA or ACGlH
I z n
v)
lA c W
r
0 0
7
4" c
W 4
0
K\USTID022II\LISONIINSTA XLS Mar I17 51
30.00
25.00
20.00
E .... E"
I I
~~ -~ ~
-Maximum Concentration 1
Maximum Concentration of Ethyl Alcohol in Room Typical Ventillation (7 air changeslhr)
I z -n
wl
01 c 9
r
0 0
P
w
w
W <
0
5.00
0.00 0 50 100 150 200 250 300 350 400 450
t, (min)
(1) Maximum concentration is that concentration seen at timet. if the chemical is placed in a hood at time 1. (2) Average concentration is cumulative average concentration if the chemical is placed in a hood at time t. and the person remains in the area for 4 hours (3) Exposure limit is the most restrictive from OSHA or ACGIH.
K \USTIW22NLISON\ETHALC XLS Max I17 5 )
HNF-SD-SUP-LB-001, Rev. 0
APPENDIX F AVERAGE AIRBORNE CONCENTRATIONS UNDER TYPICAL VENTILATION CONDITIONS
F - l
HNF-SD-SUP-LE-001, Rev. 0
T h i s page intentionally left blank.
F - 2
100.0000
90.0000
80.0000
70.0000
- E 60.0000 1
C .e 50.0000 g E
40.0000 0
Averaged Concentration of Hydrochloric Acid in Room Typical Ventillation (7 air changeslhr)
I - IDLH l -Average Concentration ,
I
30.0000
20.0000
10.0000
0 0000 0 50 100 150 200 250 300 350 400 450
t, (min) (1) Maximum concentration is that concentration seen at time 1. if the chemical is placed in a hood at time t. (2) Average concentration is cumulative average wncentratlon If the chemical is placed in a hood at time 1. and the person remains in the area for 4 hours (3) Exposure limit is the most restridive from OSHA or ACGIH
K \USTID022\1\LISOMHYORCHLO XLS TWA (17 5)
200.00
180.00
160.00
140.00
- E 120.00 P
60.00
40.00
20.00
Averaged Concentration of Methylene Chloride in Room Typical Ventillation (7 air changeslhr)
Average Concentration I
8-hr TWA Limit
0.00 0 50 100 150 200 250 300
t, (min) (1) Maximum wncentration is that concentration seen at time 1, if the chemical is placed in a hood a1 time 1. (2) Average concentration is cumulative average wncentration if the chemical is placed in a hood at time t, and the person remains in the area for 4 hour?. (3) Exposure limit is the most reslriclive from OSHA or ACGIH.
m c TI
r 40 0 0 +8
W <
0
K\USTIW22I1\LISOMMECLXLS TWA 117 5)
1 .o
0.9
0.8
0.7
- E 0.6 E
0.3
0.2
Averaged Concentration of Bromine in Room Typical Ventillation (7 air changeslhr)
8-hr TWA Limit
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 I .8 2 4 (mW
(1) Maximum concentration is that wncentration seen at time 1, if the chemical is placed in a hood at time 1. (2) Average concentration is cumulative average concentration if the chemical is placed in a hood at time I, and the person remains in the area for 4 hours. (3) Exposure limit is the most restrictive from OSHA or ACGIH.
I z -n
v)
v) c V
r W
0 0
P
E C
0
K\USTID022WISOMBROMINE XLS. N Y A I5 831
n m
8.00
7.00
6.00
4.00
Averaged Concentration of Benzene in Room Typical Ventillation (7 air changeslhr)
/
i /
Average Concentration 8-hr TWA Limit
0 10 20 30 40 50 60 t, (min)
(1) Maximum concentration is that concentration seen at time 1. if the chemical is placed in a hood at time t. (2) Average concentration IS cumulative average concentration if the chemical is piaced in a hood at time 1. and the person remains in the area for 4 hours (3) Exposure limit is the most restnctive from OSHA or ACGIH.
0
K\USTIW22V\LISOMBENZENE XLS. TWA (5 831
Averaged Concentration of 27 Wt% Ammonium Hydroxide (as Ammonia) in Room Typical Ventillation (7 air changeslhr)
40.00
t 35.00
0 10 20 30 40 50
(1) Maximum concentration is that concentration seen at timet, it the chemical is placed in a hood at time 1. (2) Average wncentration IS cumulative average concentration if the chemical is placed in a hood at timet. and the person remains in the area for4 houn. (3) Exposure limit is the most restrictive from OSHA or ACGIH.
t, (min)
I z -n
m
m c V
u
W c
0
K \ U S T I W 2 Z \ 4 L I S O ~ M O N l 4 X L S TWA (5 83)
14.00
12.00
10.00 - E - I F 5 8.00
e 6.00 u
4.00
2.00
0.00 0 50 100 150 200 250 300 350 400 450
t, (min) (1) Maximum concentration is that wncentration seen at time t. if the chemical is piaced in a hood at time 1. (2) Average concentration is cumulative average wnentration if the chemical is placed in a h o d at time 1. and the person remains in the area for 4 hours (3) Exposure limit is the most restrictive from OSHA or ACGlH
Averaged Concentration of Hydrofluoric Acid in Room Typical Ventillation (7 air changeslhr)
KIUSTIWZZULISOMHF XLS TWA(I7 51
45.00
40.00
35.00
30.00
“E - m .k 25.00 C 0
; . f a E 20.00
2 0 0
15.00
10.00
5.00
0.00
Averaged Concentration of 11 Wt% Ammonium Hydroxide (as Ammonia) in Room Typical Ventillation (7 air changeslhr)
-8-hr TWA Limit
0 50 100 150 200 250 300 350 400 450
(1) Maximum concentralion is that concentration seen at time 1, if the chemical is placed in a h o d at time 1. (2) Average concentration is cumulative average concentration if the chemical is placed in a hood at time 1. and the person remains in the area for 4 hours (3) Exposure limit is the most restrictive from OSHA or ACGIH
t, (rnin)
P <
0
K I U S T I ~ I S O N W J M O W XLS TWA (5 g l l
10.00
9.00
8.00
7.00
3.00
2.00
1 .oo
0 00 0 50
Averaged Concentration of Epichlorohydrin in Room Typical Ventillation (7 air changeslhr)
100 150 200 250 300 350 t4 fminl 0 . . .
(1) Maximum concentration is that concentration seen at time t, If the chemical is placed in a hood at time 1. (2) Average concentration is cumulative average concentration if the chemical is placed in a hood at time t, and the person remains in the area for 4 houn. (3) Exposure limit 1s the most restrictive from OSHA or ACGIH.
E <
0
I(~USTID022U\LISONIEPlCtOR XLS W A (1 7 5 )
Averaged Concentration of Hydrogen Peroxide in Room Typical Ventillation (7 air changeslhr)
0 50 100 150 200 250 300 350 t, (min) 0
0 (1) Maximum concentration is that wncentration seen at time t. if the chemical is placed in a hood at timet.
(3) Exposure limit is the most restridive from OSHA or ACGIH.
c
(2) Average concentration is cumulative average concentration if the chemical is placed in a hood at time 1, and the person remains in the area for 4 hours. P
5 0
KVSTID022HLISONIH202 XLS TWA I17 51
Averaged Concentration of Pyridine in Room Typical Ventillation (7 air changeslhr)
14.00 ~-
(I) Maximum concentration is that wncentration seen at timet. if the chemical is placed in a hood at time I. (2) Average concentration is cumulative average concentration if the chemical is placed in a hood at time 1. and the person remains in the area for 4 hours (3) Exposure limit is the most restrictive from OSHA or ACGIH
I z 7
v)
v) c V
r W
0 0
P
w
W 4
0
K\USTIO022\1\LISOMPYRlDlNE XLS W A (17 51
180.00
160.00
140.00
120.00 - ,E P 100.00
t; g 80.00
C .- 7 - , e
0
0' 0
60.00
40.00
20.00
0.00
Averaged Concentration of n-Hexane in Room Typical Ventillation (7 air changeslhr)
I z n v)
?
0 50 100 150 200 250 300 350 400 450
(1) Maximum concentration is that COncentration seen at time t. if the chemical is placed in a hood at timet. (2) Average concentration is cumulative average concentration if the chemical is placed in a hood at time 1. and the person remains in the area for4 hours. (3) Exposure limit is the most restrictive from OSHA or ACGIH.
t, (min)
v) c P r m
0 0
W 4
0
KUJSTIW2MLISOMHEYANE XLS TWAI17 5 )
10.00
9.00
8.00
7.00
6.00
5.00
4.00
3.00
2.00
1 .oo
Averaged Concentration of (70 wt%) Nitric Acid in Room Typical Ventillation (7 air changeslhr)
-Average Concentration I -8-hr TWA Limit
0 00 0 50 100 150 200 250 300 350 400 450
(1) Average concentration is cumulatlve average concentration if the chemical IS placed In a hood at time 1. and the person remains in the area for 8 hours (2) Exposure limit is the most restrictive from OSHA or ACGlH (Table 9-3)
t, (rnin)
VI
VI c 73
r W
0
W m
0
K\USTID023U\LISOM/IPPnNiTRlC XLS W A (17 51
140.00
120.00
100.00
40.00
20.00
Averaged Concentration of lnsta Gel in Room Typical Ventillation (7 air changeslhr)
I -Average Concentratior
8-hr TWA Limit _ _ _ -
0.00 L 0 50 100 150 200 250 300 350 400 450
(1) Maximum concentration is that concentration seen at timet. if the chemical is placed in a hood at time 1. (2) Average concentration is cumulative average cOnCentratiOn if the chemical is placed in a hood at time 1. and the person remains in the area for 4 hours. (3) Exposure limit IS the most restrictive from OSHA or ACGlH
t, (min)
I z -n
r A
La c -0
r
0 0
7
cp c
P 4
0
K\USTlD02214tISOMINSTAXLS N V A I17 5 )
2000.00
Average Concentration -
1800.00
1600.00
1400.00
0-
1200.00 I E" - C
7l 2 1000.00
: e s
l e
e 800.00
600.00
400.00
t 200.00
Averaged Concentration of Ethyl Alcohol in Room Typical Ventillation (7 air changeslhr)
0.00 0 50 100 150 200 250 300 350 400 450
(1) Maximum concentration IS that concentration seen at time 1. if the chemical is placed in a hood at time 1. (2) Average concentration is cumulative average concentration if the chemical is placed in a hood at timet. and the penon remains in the area for4 hours. (3) Exposure limit is the most restrictive from OSHA or ACGlH
t, (min)
K\USTIO02ZU\LISOMETHALC XLS TWAi l7 51