Document 2NBLL1VgNrRwM5w1Kz1VnrgLg

July 15, 1987 THE DOW CHEMICAL COMPANY MIDLAND. MICHIGAN 48674 Mr. Tom Grumbles Vista Chemical Company P. 0. Box 19029 Houston, Texas 77224 Mr. Mark Stenzel Celanese Chemical 1250 W. Mockingbird Lane Dallas, Texas 75247 EMERGENCY RESPONSE PLANNING GUIDELINES As a follow up of our cab conversation, on July 10, please find the attached information about Emergency Response Planning Guidelines (ERPGs). Protocol for Developing ERPGs (Background Information, Philosophy, and Definitions) Procedures and Format for ERPG Documents t Example of an ERPG Document : HF 9 Some Visual Aids from our ERPG Awareness Package Since the ORC-AIHA process is step up and functioning, our collective efforts are now focused on approving as many scientifically dependable ERPGs as we can as fast as we can. That is why it was pleasing tc hear of your possible interest in ERPGs for methyl acrylate, vinyl chloride, and benzene. If you really are able to generate an inhouse commitment to prepare a draft document, please call Becky Daiss at ORC (202-737-6330) with a target date. If you have any questions, please do not hesitate to call. Dean R. Branson Health & Environmental Sciences 1803 Building 517-636-2730 rim attachments CTL017858 ERPG Page 1 I. Introduction The tragic incident in Bhopal, India heightened concern about potential adverse health effects-which might result from an accidental chemical release to a neighboring community and the r suiting short-term, or acute exposures. This concern has led many companies to re-evaluate possible "worst case" situations which might occur as a result of process or human failures. To fully evaluate the potential for release, and to do proper planning, there is a need for certain emergency response planning guidelines for these acute incidents. These guidelines are for use as a planning tool for evaluating the adequacy of precautions and containment measures at chemical manufacturing or using facilities or for transportation purposes. When an actual emergency occurs there is usually not time to measure airborne concentrations and then take action. Emergency Response Planning Guidelines (ERPGs) can be used as one piece of data together with information such as volatility, storage volumes, etc., in a computer for predicting the extent of actions necessary in case of a release. The actions may vary depending on such things as population density, type of population (e.g. schools), terrain, the nature of the release etc. The numbers may also be useful in evaluating whether engin ring controls are necessary to diminish or eliminate the potential for release. II. PRC's Role It was recognized that an ORC Task Force could serve as the vehicle to develop an industry-wide protocol and documentation format for development of emergency exposure guidance levels. This group could serve best in developing a protocol, not as a "number consensus" group. It could serve as a the vehicle to help spread the task of preparation over a number of companies if the preparation were all done according to an agreed upon protocol. The Task Force could also serve as the vehicle to exchange levels and their documentation with specific company identifiers removed. The participants in the Task Force agreed to develop their emergency response planning guidelines according to the protocol developed by the group, and then exchange those numbers and their documenta tion. The group also agreed to collectively develop a list of materials needing emergency response planning guidelines, and distribute them among the companies developing those guidelines. III. Long Term Goal Participation in the ERPG effort is voluntary, and participants are in no wav obligated to adhere to the numbers produced via the ERPG protocol. If, after several companies have compiled data CTL017859 ERPG Page 3 P nnsylvania D partment of Health. Guidelines from these organi zations are either very limited in scope* directed only to occupa tional exposure, and/or no longer being generated. Others, such as the World Bank and the European Community (EEC) provide guidance in terms of acutely hazardous quantities which are based on LC50 values. These are inappropriate since lethality is the only h alth effect considered. Human experience data, escape-impairing ffects, and serious nonlethal effects, such as lung of liver injury, are not considered. The National Fire Protection Association (NFPA) has developed a list of acute health hazard ratings on a one to four scale for use as an indicator to emergency service personnel and relative rankings, and do not meet the needs for airborne concentrations to be used in planning for emergency situations. Although "emergency numbers" have been put together by several organizations as indicated above, none of them have been specifically developed for use by industry for potential emergency releases. Because of the various short- comings in their development, only the NRC EEGLs appear to be of some value for present purposes. V. Background None of those values cited above, with the exception of some of the NRC EEGLs, are applicable in whole or in part for present purposes. For this reason, several companies, responding to internal needs, undertook development of these emergency planning numbers themselves. Each had separately agreed on several principals 1. The numbers are useful primarily for emergency planning and response. 2. The numbers are suitable for protection from acute effects due to short term exposures. They are not suitable for effects due to repeated exposures, nor as ambient air quality guidelines. 3. The numbers are guidelines. They are not absolute levels demarcating safe from hazardous conditions. 4. The numbers do not necessarily indicate levels at which certain actions must be taken. 5. The numbers are only one element of the planning activities which must be done to develop a program to protect and involve the neighboring community. In discussions among personnel in companies carrying out these guideline development efforts, it became evident that there was a definite need for consistency through a uniform procedure. Consistent procedures would allow for exchange of information among companies with a resulting utility to all participants. CTL017860 ERPG Page 5 In developing the ERPG rationale, it is important to primarily use acute or short-term exposure data. When evaluating the adverse health effects, both immediate and delayed health effects should be considered. When it is believed that adverse reproductive, developmental, and/or carcinogenic effects might be caused by an acute exposure, and therefore are relevant, the data should be included in the derivation of the ERPG's. If it is desired that carcinogenicity data be used, the National Research Council has developed mathematical approaches which may be useful for the desired purpose. Selection of ERPG values may include use of judgemental factors based on uncertainties about the data or its extrapolation. VII Limitations ERPGs are general reference levels that are intended to be used as part of an overall emergency planning program. The application and use of ERPG values requires a careful evaluation of a number of factors for any given situation. These may include how the on hour ERPG values might relate to exposures of several minutes or several hours, whether potential adverse effects on special risk groups, including the elderly, the young, and those individuals with underlying medical illnesses need further consideration, as w 11 as other factors such as volatilities, storage quantities, w ather conditions, etc. Assessment of these factors is needed to determine what actions should be taken in planning for and responding to a given emergency. The levels are not to be used as safe limits for routine operations. The ERPGs are general reference levels, the best judgement of specialists using the best available data? they are not to be taken as definitive delineators between safe and unsafe exposure conditions. CTL017861 EMERGENCY RESPONSE PLANNING GUIDELINES . 4 Range in which severe, permanent, life-threatening health effects are expected. Range in which serious health effects - target organ effects - are expected. DC h* LLI oOz o Range in which transient effects, increased irritation and odor (if relevant) effects are expected. RANGE 3 RANGE 2 RANGE 1 ERPG-3 Maximum airborne cone ntration below which, it is believed, nearly all in dividuals could be exposed for up to one hour without experiencing or developing life threatening health effects. ERPG-2 Maximum airborne concentration below which it is believed, nearly all in dividuals could be exposed for up to one hour without experiencing or developing irreversible adverse health ef fects or symptoms which could impair an individual ability to take protective action. ERPG-1 Maximum airborne concen tration to which nearly all in dividuals could be exposed for up to an hour without ex periencing or developing health effects more severe than mild od r percepti n or irritation, if relevant. CTL017862 INSTRUCTIONS FOR PREPARING EMERGENCY RESPONSE PLANNING GUIDELINE (ERPG) 1. ERPG Procedure 2. ERPG Format The following procedure and format are quite close to the WEEL procedure and format developed by the AIHA Workplace Environmental Exposure Level (WEEL) committee. In addition, the following is consistent with that used by Dow, NAS, and other organizations developing workplace or environmental guidelines. CTL017863 1 RECOMMENDED ERPG PROCEDURE 1. Establish, if appropriate, a committee composed of toxicology, medicine, industrial hygiene, and other health professionals to gather, review and draft ERPG. 2. Identify producers and users of the material and associations if appropriate and request information on unpublished toxicology, medical, industrial hygiene, and epidemiologic information. 3. Conduct a literature search including the appropriate on line databases. (For examples MEDLINE, TOXLINE, CHEMLINE, etc.) 4. Prepare a draft ERPG document using the attached format while following these additional guidelines: (a). Give physical properties at 760 mmHg and 20-25 C centigrade whenever possible. (b). Use consistent units. Use mg/kg for LDSO's and use ppm and mg/m 3 for LC50's. (c). When no information is available, retain the heading and state no data available. (d). Include negative findings as well as positive. (e). Always identify the meaning of any abbreviations the first time they appear. e.g. MCA (monochloroacetic acid) is.... SC (subcutaneous) dose... 5. Send copies of the draft through the appropriate review channels within your company in order to obtain approval for release. 6. Once your company has approved the ERPGs, the document nd copies of all supporting references, including translations, should be appended if possible so that a complete package could be made available for review. If the references are too numerous and can not be reproduced then effort should be given to attaching only those references which provide the most support for the ERPGs. 7. If your company prefers to remain anonymous, you may do so by specifying this intention at the outset. CTL017864 3 III. Toxicity Data A. Acute Toxicity (1-5 days) 1. Oral (ex. LD50, rats: 100 xng/kg) 2. Eye 3. Skin a) Irritation b) Absorption 4. Inhalation (State exposure duration if giving LC50. e.g. 4-hr. LC50, rats: 325 ppm) 5. Other (Include subcutaneous, intraperitoneal, intravenous etc.) B.* Mutagenicity (specify tests relevant to ERPG only) C.* Reproductive/Developmental Toxicity (Include teratology and reproduction studies) D.* Metabolism and Pharmacokinetics E.* Subacute (5-14 days) F.* Subchronic Toxicity (15 days to 6 months) (List each study separately in order of duration rather than route. Give duration, route, species, all doses tested and the effects observed at each dose.) G.* Chronic Toxicity and Carcinogenicity 06 month) (Present in same manner as subchronic studies.) Only if data are useful in establishing an ERPG. IV. Human Experience (Summarize data if appropriate) A. Acute (1-5 days) B. Subacute (5-14 days) CTL017865 5 C. Emergency Response Planning Guid line-1 (Valu , unite, time, and definition of ERPG-1) Rationale (Summarize the data which most appropriately supports the value and the effects which are to be avoided.) VII. Summary Tables/Plots A. Table Concentration/Effect (Develop a table of concentrations in descending order vs. effects in animals and humans. For example: Concentration Species Route/ Duration Effect Comments/Reference 400 ppm 50 ppm 25 PPm rat man man inhal/ 6 hours inhal/ 4 hours inhal/ 4 hours Death Irritation to URS... None observed Author B. Summary Plot (Optional) VIII. References Cite references following the procedure and format found in the AIHA's "Guidelines for Authors" (see attached copy). Identify which on-line databases were searched at the beginning of the references - "Literature searches performed". Include the date the literature search was performed. Always cite primary references where possible, e.g.. Cite primary references not NIOSH RTECS. "Company name, unpublished data, date..." referenced if hard copy is obtained. CTL017866 AIHA Ref rence Procedure and Format* Reference Designations in Text References are to be cited in text using superscript Arabic numericals, numbered sequentially in order of citation. Reference superscript numerals must appear outside punctuation to the right of any punctuation marks. Enclose all single groups of references in parentheses. If references "1,2,3,4,5,8/9 & 10" are cited at one point use "(1-3,5,8-10)". Do not include any author's names, publication titles, or dates in body of text. Refer only by superscript number to listing at end of article. Reference Listing Following Text References must be numbered and listed in the same order they are cited in text. Type (double spaced) on separate pages. Follow arrangement, order, capitalization and punctuation shown in examples exactly. Manuscripts not adhering to instructions regarding reference listing will be returned for correction. In the listing, references to journals or sources should show: author(s) name(s) typed in initial capitals, with first author's name presented with last name then first name or initials; other authors, name(s). Next title of article (with initial capitals on major words only and no quotation marks) followed by a period. Finally, name of publication (abbreviate journal names according to Bibliographic Guide for Editors & Authors. American Chemical Society (1974) plus volume no., colon(:) first and last pages, plus year (in parenthese) and final period. Review example b fore preparing reference listing. Correct Reference Format... (capitalization, punctuation, spacing) 1. Fulwiler, R.D., J.C. Abbott and F.J. Darcy: The Evaluation of Detergent Enzymes in Air. Am. Ind Hyg. Assoc. J. 33:231236 (1972. 2. Drinker, P. and T. Hatch: Industrial Dust. 2nd Ed. pp. 4043. McGraw-Hill, New York (1964). Reproduced from "Guidelines for Authors," periodically published in the American Industrial Hygiene Association Journal. CTL017867 EMERGENCY RESPONSE PLANNING GUIDELINES (ERPGs): RECOMMENDED PROCEDURES AND DOCUMENTATION FORMAT JUNE 15, 1987 AMERICAN INDUSTRIAL HYGIENE ASSOCIATION ERPG COMMITTEE cTLoi786g RECOMMENDED ERPG PROCEDURE 1. The authoring company should use a multi-disciplinary team (including toxicology, medical, industrial hygiene and other health professionals) to collect and review data and to develop draft ERPG documentations. 2. The author should identify producers, major users and industry associa tions having a significant interest in the chemical and should request information from then (especially unpublished data giving observed effects in humans or animals at known airborne concentrations). 3. A literature search should be conducted and should Include appropriate on-line databases such as MEDLINE and TOXLINE. 4. The draft ERPG documentation should follow the attached format and these additional guidelines: a. Give physical properties at 760 mm Hg and 20-25C whenever passible. b. Use consistent units. ex. Use mg/kg for all LDSO's; ppm and/or mg/m3 for all LC50's. Convert mg/m3 to ppm for all vapors. c. When no information is available, retain the subject heading and state "No data available". Several headings may be combined for this purpose. d. Include negative findings as well as positive. e. Identify the meaning of abbreviations the first time they appear in the document. Abbreviations used for the chemical name should be included in the synonyms. f. Whenever possible, obtain the original reference for all data as there are frequently errors or significant omissions in secondary references. 5. The authoring company should submit the draft ERPG document, marked "ORC Preliminary Draft* to the Organization Resources Councellors (ORC) ERPG Task Force. 6. When the preliminary draft is ready for review by the AIHA ERPG Connittee, it should be marked "Final ORC Oraft". 7. The author's final draft should be sent to the Chairman of the AIHA ERPG Connittee along with copies of the reference documents. a. For very lengthy reports, such as NTP chronic studies, the full report is not needed. CTL017869 b. For company reports which are considered confidential, an abstract which gives some details of methods, results and conclusions of the study should be provided. c. For lengthy review articles covering many chemicals, some irrelevant pages may be omitted from the copy. 8. If the authoring company does not wish to be identified on the document, they may omit that information. 9. The AIHA Committee will assign a primary and secondary reviewer for each ERPG submitted to them. 10. The primary reviewer will work directly with the author when addressing any questions or modifications regarding the draft document. 11. Only after this preliminary review and possible revision, should the document be presented to the full AIHA ERPG Committee for discussion. The author will be invited to attend the meeting. 12. A majority vote of members in attendance is needed before sending the draft to all members for ballot. (If all members are present, balloting may be done verbally at the meeting.) Members may vote "yes", "no" or "abstain". "No" votes must be accompanied by a specific explanation. Two-thirds of the non-abstaining votes received are needed for final approval of the ERPG. 13. Following approval, the documentation will be sent to the AIHA Akron office for publication. 14. Following publication, the documentation will be filed at Akron along with any references which would be difficult to replace. CTL017870 Author (optional) Draft Number ____ Date EMERGENCY RESPONSE PLANNING GUIDaiNE (ERPG) CHEMICAL NAME ERPG-1 ERPG-2 ERPG-3 I. Identification Chemical Name: Synonyms: (separate by semi-colon) CAS Number: Molecular Formula: Structural Formula: II. Chemical and Physical Properties Physical State and Appearance: (at ambient conditions) Odor Description: (not thresholds, etc.) Molecular Weight: Conversion Factors: I mg/m3 3ppm v/v 1 ppm v/v mg/m3 Boiling Point: C ( F) aturn Hg Vapor Pressure: ______ran Hg atC ( _____ F) (May include for several temperatures, if available, but especially for ambient conditions.) Saturated Vapor Concentration: ppm atC ( F) Vapor Oensity: Flash Point (closed cup): *C ( F) Flammability Limits: LEL ________ UEL Autoignition Temperature: "C ( F) CTL017871 Stability and Reactivity: Solubility in Water: III. Animal Toxicology Data (NOTE: Sunmarize each study separately. Give duration, route, species, and the effects at each dose, not just the no-effect level. Lengthy detail is unnecessary for some studies judged to be of minimal relevance for establishing an ERPG.) A. Acute Toxicity (include studies of <5 days exposure) 1. Oral (ex: LD50, rats: 100 mg/kg/day) 2. Eye 3. Skin Irritation 4. Skin Absorption 5. Inhalation (NOTE: State exposure duration for all LC50s; state whether nominal or actual concentration; include pathology if available; give mortalities at individual doses, not just the LC50, if available; give lowest lethal concentrations and highest non-lethal concentrations when available) B. Subacute Toxicity (5 to 14-day studies) C. Subchronic Toxicity (15-day to 6-months studies) D. Chronic Toxicity and Carcinogenicity (>6-months studies) E. Reproductive and Developmental Toxicity (include teratology and reproduction studies) F. Genotoxicity/Mutagenicity G. Other IV. Human Experience A. Toxicity and Odor Test Data (NOTE: Include only actual test data; that is, where humans were exposed to controlled concentrations. Do not include accidental exposures or estimates of human effects based only on animal data.) B. Workplace Experience (NOTE: Include subjective response information, such as vapor concentrations which caused eye or respiratory discomfort or produced objectionable odors.) CTL017872 C. Epidemiology (NOTE: A brief summary is sufficient.) 0. Other (NOTE: May include opinions or estimates of human effects which are based only on animal data.) V. Current Occupational and Emergency Exposure Guidelines (Give the source or organization, the guideline number, and a brief state ment about the rationale used. Rationales for STELs or other short-term guidelines are of particular interest.) A. ACGIH TLV or AIHA WEEL B. OSHA PEL C. NRC EEGL D. Others VI. Recommended ERPGs and Rationales (Although three ERPG levels are preferred for each chemical, occasionally only one or two ERPG levels will be judged appropriate. For instance, if the odor and irritancy concentrations are higher than the ERPG-2 level, an ERPG-1 value is inappropriate. This section should include an explanation for any ERPG level omitted.) A. ERPG-3: ________ ppm ( mg/ma) It is believed that nearly all individuals could be exposed to ppm for up to one hour without experiencing or developing life-threatening health effects. (Add basis for number selected -- ex. most important studies/data, expected effects.) B. ERPG-2: ppm ( mg/ma) It is believed that ppm Is the maximum airborne concentration below which nearly alt individuals could be exposed for up to one hour without experiencing or developing irreversible or other serious adverse health effects or symptoms which could impair an individual's ability to take protective action. (Add basis for number selected.) C. ERPG-I: ________ ppm ( mg/ma) It is believed that ppm Is the maximum airborne concentration below which nearly alt individuals could be exposed for up to an hour without experiencing or developing effects more serious than mild irritation, other mild transient health effects or perception of a clearly objectionable odor. (Add basis for number selected.) CTL017873 VII. References - Use the format shown in the attached "AIHA Reference Procedure and Format11. - Always review and cite primary references whenever possible. - When secondary references must be used, state as follows: "(primary reference), as cited in (secondary reference)." - If a company submitting unpublished data gives permission to identify them, cite as follows: "(Company name), unpublished data, (date). - If a company does not want to be identified, cite as follows: "Confidential unpublished data, (date).* VIII. Suwnary Tables or Plots (optional) (Summary 'tables giving species, concentration, duration, effects and references may be included. Tables are generally most useful when there is a lot of acute data. Plots may be useful for "visualizing" the more important data. These tables and/or plots may be helpful during the ERP6 development and review stages.) CTL017874 AZHA Ref erase a Procedure and Format-* Reference Designations Is Text References are Co be cited in text using superscript Arabic nunericais, numbered sequentially in order of citation. Reference superscript numerals must appear outside punctuation to tie right of any punctuation marks. Enclose all single groups of references in parentheses. If references *1,2,3,4,5,8,3 & 10* are cited at one point use *(1-3,5,3-10)". Do not -tnr-inr^ aBy author4 s names, publication titles, or in body of text. Refer .only by superscript nuaber to listing at end of article. Reference Listing Following Text References must be numbered and listed in the same order they are cited in text. Type (double spaced} on separate pages. Follow arrangement, order, capitalization and punctuation shewn -'in examples exactly. `'Manuscripts not adhering to instructions regarding reference listing will be returned for correction. In the listing, references to journals or sources should show: author(s) name(s) typed in initial capitals, with first author's name presented with last name then first name or initials; other authors, name (a) . Next, title of article (with initial capitals on major words only and no quotation marks) followed by a period. Finally, name of publication (abbreviate journal names according to Bibliographic Guide for Editors & Authors. American Chemical Society (1374)y plus volume so., colon(:) first and last pages, plus year (in parentheseij and final period. Review examples before preparing reference listing. Correct Reference Format... (capitalization, punctuation, spacing) 1. Fulwiler, R.D., J.C. Abbott and F.J. Darcy: The Evaluation of Detergent Ehrymes in Air. An. Ind Kvg. Assoc. J. 33:231236 (13721. 2. Drinker, P. and T. Hatch; Industrial Dust. 2nd Ed. pp. 4043. McGraw-Hill, Hew York (1364). Reproduced frea "Guidelines for Authors," periodically published in the American Industrial Hygiene Association Journal. CTL017875 DEFINITIONS FOR EMERGENCY RESPONSE PUNNING GUIDELINES (ERPGs) ERPG-3 Maximum airborne concentration below which, it is believed, nearly all individuals could be exposed for up to one hour without experiencing or developing life-threatening health effects. ERPG-2 Maximum airborne concentration below which, it is believed, nearly all individuals could be exposed for up to one hour without experiencing or developing irreversible or other serious adverse health effects, or symptoms which could impair an individual's ability to take protective action. ERPG-1 Maximum airborne concentration below which, it is believed, nearly all individuals could be exposed for up to one hour without experiencing or develop ing effects more serious than mild irritation, other mild transient health effects, or perception of a clearly objectionable odor. CTL017876 f EMERGENCY RESPONSE PLANNING GUIDELINE HYDROGEN FLUORIDE ERPG 3-20 ppa *ERPG 2-8 ppa ERPG 1 - 2 ppa I. Identification Chemical Name: Hydrogen Fluoride Synonyms: Hydrogen Fluoride anhydrous. HF. Hydrofluoric Acid. Hydrofluoric Acid, anhydrous. Hydroflouride. UN1052. Antisol 2B. CAS Number: 7664-39-3 Structure: HF II. Cheaical and Physical Properties Physical State: HF is a colorless, fuming, mobile liquid or gas vith strong irritating vapors. Molecular Veight: 20.01 Conversion: 1 ppm - 0.82 mg/m3 , 1 mg/m3 > 1.22 ppm Boiling Point: 67F, 19.4C Solubility: miscible in vater Flammability: not combustible Vapor Pressure: 60 ma Hg at 20C Specific Gravity: 0.991 at 67F Vapor Density: 0.7 Odor Threshold: 0.04 - 0.13 ppa Incompatibilities: Metals, concrete, glass and ceramics Reactivity: HP's corrosive action on metals can result in formation of hydrogen in containers and piping to create an explosion hazard. Vill react vith vater or steam to produce toxic and corrosive fumes. Violent reactions occur vith AS2O.J, P25' acetic anhydride, 2-aminoethanol, Hydrogen Fluoride 1 BGC:aeb-r/0287-84 3/11/87 CTL017877 -2- r NH.OH, HBiO-j, CaO, chlorosulfonic acid, ethylene diamine, ethylene inline, Pj, (HNO, + lactic acid), oleum, beta propiolactone, propylene oxide, Na, NaOH, I^SO^, and vinyl acetate. III. Animal Toxicity Data A. Acute Inhalation Toxicity 1. Inhalation a. Species: guinea pigs and rabbits Reference: Hachle, et al^ (1) 30 ppm 41 hour no deaths, subsequent weight loss 122 ppm 5 hour no deaths 610 ppm 15 min. weakness and ill health 1220 ppm 30 min. no deaths, damage to tissues 1830 ppm 5 min. death 1002 Species: guinea pigs and rabbits Reference: Ronzanl (2) 600 ppm 0.5 -1.1 h all animals, death betveen 0.5 -1.5 h. 250 ppm 1-3h all animals^ death betveen 1- 3 h 50 ppm 0-2h all guinea pigs died. Rabbits shoved severe distress 30 ppm 1 - 3 day guinea pigs died. Rabbits in poor condition 10 ppm 0-5 day no deaths At 2S0 and 600 ppm, all animals shoved severe signs of irrita tion vith labored breathing> ulcerations of upper respiratory tract and eye corneas and pulmonary edema. Hydrogen Fluoride 2 BGC:aeb-r/0287-84 3/11/87 CTL017878 -3- r c. Species: rats Reference: Higgins, et al. (3) LC100! 25,690 ppm 18,580 ppm 5 min. 5 min. toCOo LC50: 18,200 ppm 5 min. (calculated) LC30: LC10: lc0; 17,615 ppm 12,440 ppm 11,550 ppm + 25X CO 5 min. 5 min. 5 min. Species: mice Reference: Higgins, et al. (3) LC100: LC67: LC53: LC50s 11,010 ppm 7,615 ppm 8,140 ppm 6,247 ppm (calculated) 5 min. 5 min. 5 min. LC33: LCq: 4,500 ppm 2,430 ppm 5 min 5 min 2. Dermal Species: rabbits Reference: Derelanko et al. (4) 2X HP solution 1 hour Necrotic lesions of ear 2Z HP solution 4 hours Increased number of lesions over 1 hour exposure, transient total serum fluoride increase^(dose dependent) reduction in testicu lar weight. Hydrogen Fluoride 3 BGC:aeb-r/0287-84 3/11/87 CTL017879 r 2X HF solution >15 min. Produced greater number of lesions at increased size over IX HF for 5 min. or 0.5% at any exposure period. Neutralized solution (2%) HF produced no visible lesions after 1 hour. B. Subchronic Toxicity Guinea pigs, rabbits and monkeys vere exposed to 18.5 ppm HF for 2 months (5). Tvo of three guinea pigs died, one vith pulmonary hemorrhage, the other vith a lov grade inflammatory reaction in the alveolar vails. Focal necroses vith fatty changes in livers and necroses in the renal cortex vere also observed. Both animals lost considerable veight. In rabbits leukocytic infiltration of the alveolar vail vith and vithout edema vas found although the sacrifice occurred 7-8 months after exposure. Tvo rabbits of the five had lobular pneumonia and kidney damage vas observed in all rabbits. Monkeys shoved kidney damage only. Dogs vere subjected to 8.5 ppm HF for 6 hours a day, 6 days a veek for 5 veeks(6). Minor pulmonary changes vere noted. Existing Exposure Guidelines A. ACGIH TLV: 3 ppm ceiling B. OSHA PEL: 3 ppm C. NIOSH/OSHA IDLH: 20 ppm D. NIOSH RECOMMENDED TVA: 2.5 mg/m3, 3.0 ppm NIOSH RECOMMENDED CEILING (15 min): 5.0 mg/m3, 6.1 ppm E. NAS - Atmospheric Limits in Submarines (1 hour): 10 ppm CTL017880 Hydrogen Fluoride A BGC:aeb-r/0287-84 3/11/87 -5- r Human Toxicity Data A. Inhalation 1. Braun, et al.(7) revealed the case histories of four workers exposed to a mixture of sulfuric and hydrofluoric acid, liquid and fumes. One worker was hit by a few drops and was t'eated only for minor acid burns. The second died unexpectedly a few hours after the accident. No autopsy was done. The third and fourth victims were treated in the hospital showing signs and symptoms of liver and kidney damage. Victim #3 died after four weeks from respiratory insufficiency. The fourth worker recovered, yet still complains of coughing and hoarse ness one year after the accident. Hydrofluoric acid was reported to be the main toxic agent. 2. Mayer & Gruelich (8) reported two deaths from pulmonary edema after an exposure of only minutes to greater than 10,000 ppm HP (calculated). 3. Largent (9) reported no noticeable effects observed after exposure to average concentrations of 1.42 - 4.74 ppm for 6 hours a day, 5 days a veek and continuing from - 10 to SO days. At ranges up to 8.1 ppm, slight eye and face irritation and cutaneous erythema were found. Redness of the skin was noted at 3.39 ppm which also resulted in some flaking of the skin after 11 days of exposure. Five subjects were studied. 4. Machle, et al^ (1) found irritation of the larger airways at 30.5 ppm. but no coughing or sneezing. Exposure was for several minutes. At 61 ppm for 1 minute they noted discomfort of the large air passages but no skin irritation, 122 ppm was the highest tolerable concentra tion for 1 minute and smarting of the skin was experienced along with conjunctival and respiratory irritation. 5. Kleinfield (10) related a fatal case of exposure resulting in severe tracheobronchitis with hemorrhagic pulmonary edema after a chemist was splashed with hydrofluoric acid from a broken vat. The workman died 10 hours later. 6. The American Petroleum Institute (11) reports that 50 ppm HP, for 30-60 minutes, may be fatal. B. Dermal 1. A splashing incident was reported with 602 solution of HP leading to mild erythema and some tissue destruction. Healing was complete in 2-6 weeks. (12) 2. A fatality was reported from cardiac arrythemia. The victim suffered a third degree facial burn from anhydrous HF on the skin less than 10 Hydrogen Fluoride BGC:aeb-r/0287-84 3/11/87 CTL017881 minutes after the incident. Profound hypocalcemia was noted. Expo sure vas attributed to skin absorption. (13) Epidemiology Machle & Evans (14) reported on workmen exposed to levels of BF for nine years. Although initial exposure may have been "high", improved ventilation reduced the concentration after one year. Average concentrations during later years were measured in the range of 13-26 ppm. No skeletal fluorosis vas found after prolonged exposure at these levels. Others have reported ostereosclerosis after chronic worker exposure at unreported levels. (15) Hodge & Smith (16) describe the effects of long term vorker inhalation as chronic irritation and congestion of the nose, throat, and bronchi. This does not seem, however, to cause lung alterations since in a study of 74 men exposed to HF for an average of 2.7 years, Evans (17) reported cases of upper respiratory tract infection but no evidence of lung change or increased death from pulmonary infection. The concentrations vere, at times, severe enough to etch glass. Summary Exposure to hydrogen fluoride has proved fatal to humans in documented cases from both dermal and inhalation routes. The intensely painful skin bums have been treated effectively vlth injections or topical use of calcium gluconate. Dermal exposure, has also resulted in lung pathology although some inhalation cannot be excluded from the case histories. Pulmonary edema may be delayed for hours or days after the initial exposure. Hypocalcemia has been a finding in patients who died of cardiac arrythmias. Recommended ERPGs and Rationale A. ERPG-3: 20 ppm for one hour ERPG-3 is the maximum airborne concentration below vhich, it is believed, nearly all individuals could be exposed for up to one hour without experi encing or developing life threatening health effects. The value vas based on both the animal and human studies by Machle et al., (1) vho observed mild eye and nose irritation in humans exposed to 32 ppm HF for several minutes and vorker exposure in the range of 13-26 ppm withstood for 9 years (17). This guideline also corresponds to the IDLH value for occupa tional exposure (NI0SH/0SHA). B. ERPG-2: 8 ppm for one hour ERPG-2 is the maximum airborne concentration belov vhich, it is believed, nearly all individuals could be exposed for up to one hour without experi encing or developing irreversible adverse health effects or symptoms vhich could impair an individual's ability to take protective action. The value is based on human data from Largent (9) where approximately 4 ppm for 10 Hydrogen Fluoride BGC:aeb-r/0287-84 3/11/87 CTL017882 -7- r days yielded minor irritation. This ERPG is also consistent vith the NAS limit of 10 ppm (1 hour) for atmospheric limits in submarines vhich is applicable to (healthy vorker) crew performance in emergencies and the avoidance of permanent injury. ERPG-1: 2 ppm for one hour ERPG-1 is the maximum airborne concentration belov vhich nearly all indi viduals could be exposed for up to one hour without experiencing or developing health effects more severe than mild odor perception or irri tation, if relevant. The value is based on human data from Largent (9) vho observed no noticeable effects after exposure of healthy volunteers to average concentrations of 1.4 - 4.7 ppm for 6 hours a day, 5 days a week for 10 to 50 days. Bydrogen Fluoride BGC:aeb-r/0287-84 3/11/87 CTL017883 -8- HYDROGEN FLUORIDE REFERENCES - 1. Machle, W., F. Thamann, K. Kitzmiller, and J. Cholak: Effects of the Inhalation of Hydrogen Fluoride. J. Ind. Hyg. Toxicol. 16:129-145 (1934). 2. Ronzani, E., Experimental Studies on the Effect of Inhaling Irritant Industrial Gases Upon the Organism's Defense Mechanisms Against Infec tious Disease. Arch. Hyg. 70:217-69 (1909). (German), as cited in NIOSH 3. Higgins, E.A., V. Fiorca, A.A. Thomas, and H.V. Davis. Acute Toxicity of Brief Exposures to HF, HC1, NO. and HCN With and Without CO. Fire Technol. 8:120-130 (1972). i 4. Derelanko, M.J., S.C. Gad, F. Gavigan, and B.J. Dunn. Acute Dermal Toxicity of Dilute Hydrofluoric Acid. J. Toxicol. Cutan. & Ocul. Toxicol. 4:73-85 (1985). 5. Machle, V. and K. Kitzmiller. The Effects of the Inhalation of Hydrogen Fluoride: Response Folloving Exposure to Lov Level Concentration. J. Ind. Hyg. Toxicol. 17:223-229 (1935). ~ 6. Stokinger, H.E. Patty's Industrial Hygiene & Toxicology. 3rd. Ed. pp. 2945-2954. John Wiley & Sons (1981). 7. Braun, J., H. Stob, and A. Zober. Intoxication Folloving the Inhalation of Hydrogen Fluoride. Arch Toxicol. 56:50-54 (1984). 8. Mayer, L. and J. Geulich. Hydrogen Fluoride (HF) Inhalation and Burns. Arch. Environ. Health 7:445-447 (1963). 9. Largent, E.J. Fluorosis - The Health Aspects of Fluorine Compounds. Ohio State University Press (1961). 10. Kleinfield, M. Acute Pulmonary Edema of Chemical Origin. Arch. Envir n. Health 10:942-946 (1965). 11. API. Medical Management of Chemical Exposures in the Petroleum Industry (1982). 12. Jones, A.T. Treatment of Hydrofluoric Acid Burns. J. Ind. Hyg. Toxicol. 21:205-212 (1939). BGC:aeb-r/0287-84 3/11/87 CTL017884 -9- f HYDROGEN FLUORIDE REFERENCES (Continued) 13. Tepperman, P.B. Fatality Due to Acute Systemic Fluoride Poisoning Following a Hydrofluoric Skin Burn. J. Occup. Med. 22:691-692 (1980). 14. Machle, V. and E.E. Evans. Exposure to Fluorine in Industry. J. Ind. Hyg. Toxicol. 22:213-17 (1940). 15. Peperkorn, K. Intoxication. (German). Osteosclerosis as Consequence of a Chronic Fluorine Relchsarbeitsblatt Teil III No. 14/15:64-67 (1944) 16. Hodge, H.C., and F.A. Smith. Fluorine Chemistry. Vol. IV. Academic Press, New York (1965). 17. Evans, E.E. An X-ray Study of Effects of Industrial Gases Upon the Human Lung. Radiology 34:411-424 (1940). 18. Rosenholtz, M.J., T.R. Carson, H.H. Veeks, F. Vilinski, D.F. Ford, F.V. Oberst. A Toxicopathologic Study in Animals After Brief Single Exposures to Hydrogen Fluoride. Am. Ind. Hyg. Assoc. J. 24:253-261 (1963). 19. Dousset, J.C., C. Rioufol, R. Feliste, P. Levy and P. Bourbon. Effects of Inhaled HF on Lipid Metabolism in Guinea Pigs. Fund. Appl. Toxicol. 4:618-623 (1984). 20. Morris, J.B. and F.A. Smith. Regional Deposition and Absorption of Inhaled Hydrogen Fluoride in the Rat. Toxicol. Appl. Pharmacol. 62:82-89 (1982). 21. ACGIH. Threshold Limit Values and Biological Exposure Indices for 1986-87. 22. NIOSH Criteria for a Recommended Standard. Occupational Exposure to Hydrogen Fluoride. U.S. Dept H.E.V. (1976). 23. Medline Search. January, 1987. BGC:aeb-r/0287-84 3/11/87 CTL017885 HYDROGEN FLUORIDE Concentration ppa Duration Species Comments >10,000 Minutes Man Death from pulmonary edema, 2 hours after exposure 4953 4319 2684 2037 1830 1342 1305 1220 660 610 250 180 5 Min. 15 Min. 15 Min. 30 Min. 5 Min. 1 Hour 1 Hour 30 Min. 0.5-1.5 Hours 15 Min. 1-3 Hours 6 Hours Rat Guinea Pig Rat Rat Guinea Pigs, Rabbits Rat Rat Guinea Pigs, Rabbits Guinea Pigs, Rabbits Guinea Pigs, Rabbits Guinea Pigs, Rabbits Rat LC50 LC50 "50 LC50 LC100 LC50 "50 No deaths Death betveen 0.5 - 1.5 Hours Weakness and ill health Death in 1-3 Hours 1002 lethality, no sign of pulmonary danage or cyanosis prior to death Reference Mayer & Geulich,(8) Rosenholtz, et al.(18) Rosenholtz, et al.(18) Rosenholtz, et " al.1(18) Rosenholtz, et al.(18) Hachle, et al.(l) Morris & Smith(20) Rosenholtz, et al.(18) Machle, et al.(1) Ronzani(2) Machle, et al.^ Ronzani(2) Morris & Saith(20) BGC:aeb-r/0287-84 3/11/87 CTL017886 HYDROGEN FLUORIDB (Continued) Concentration ppm Duration 122 5 Hours 122 1 Hin. 61 1 Hin. 50 50 50 36-214 31.7 29.3 20 18.5 1 Day 1 Day 30-60 Min. 6 Hours Several Min. 41 Hours 30 Min. 6 Hours/Day 50 Days Species Comments Reference Guinea Pigs, Rabbits Man Han Rats Guinea Pigs Man Rat Man ' Guinea Pigs, Rabbits Han Guinea Pigs, Rabbits, Monkey No deaths Highest tolerable concentration. Smarting of exposed skin, conjunc tival and respiratory irritation Conjunctival and respiratory irri tation, discomfort of large air passages, no skin irritation Poor condition Death Hay be fatal Virtually all inhaled HP deposited in upper respiratory tract Mild eye and nose irritation, no cough or sneezing No deaths, but a subsequent veight loss Immediately dangeous to life & health Two guinea pigs died, one rabbit became pregnant and gave birth to 3 normal offspring. Necropsy revealed damage to lung, liver and kidney in all aninals except in the one exposed monkey who had kidney damage only. Machle, et al.(l) Machle, et al.(1) Machle, et al.(l) Ronzani(2) Ronzani(2) API(ll) Morris & Smith(20) Machle(l) Machle(l) OSHA Hachle and Kitzailler(5) BGCsaeb-r/0287-84 3/11/87 CTL017887 HYDROGEN FLUORIDE (Continued) Concentration ppa Duration 12.2 84 Hours 10 5 Days 8.5 3.39 Aver. 6 Hours/Day, 6 Days/Week 5 Weeks 10 Days 3 30 Days 3 3 2.59-4.74 1.42-4.74 0.04-0.13 8 Hours/Day 8 Hours/Day 6 Hours/Day, 5 Days/Week 50 Days 6 Hours/Day, 5 Days/Week 50 Days Species Consents Guinea Pigs Guinea Pigs, Rats Dogs Altered lipid netabolism in liver and plasna. Not fatal, guinea pigs shoved labored breathing and eye irritation. Hinor pulmonary changes 1 Han Rabbits, Guinea Pigs, Pigeons Man Han Man Flaking of epithliun resembling mild sunburn No effect level ACGIH - TLV-TWA PEL Slight irritation of face and eyes, cutaneous erythema. Man No noticeable effect. Man Odor Thresholds (detection & recognition) Reference Dousset, et al.(19) Ronzani(2) Stoklnger(6) Largent(9) Ronzani(2) ACGIH(21) NIOSH(22) Largent(9) Largent(9) BGC:aeb-r/0287-84 3/11/87 CTL017888