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3. Melting point: -8.5<>C.
4. Boiling point: 130.2<>C.
5. Specific Gravity (H2O = 1): 2.16 at 20<>C.
6. Vapor pressure: 10mm Hg at 23.5<>C.
7. Solubility in Water: Decomposes in water.
II. Fire, Explosion and Reactivity Data.
A. Fire: Arsenic, Arsenic Trioxide and Arsenic Trichloride are nonflammable.
B. Reactivity:
1. Conditions Contributing to Instability: Heat.
2. Incompatibility: Hydrogen gas can react with inorganic arsenic to form the highly toxic gas arsine.
III. Monitoring and Measurement Procedures.
Samples collected should be full shift (at least 7-hour) samples. Sampling should be done using a personal sampling pump at a flow rate of 2 liters per minute. Samples should be collected on 0.8 micrometer pore size membrane filter (37mm diameter). Volatile arsenicals such as arsenic trichloride can be most easily collected in a midget bubbler filled with 15 ml of 0.1 N sodium hydroxide.
The method of sampling and analysis should have an accuracy of not less than plus or minus 25 percent (with a confidence limit of 95 percent) for 0.01 mg per cubic meter of air (10 <>g/m [FN3]) and plus or minus 35 percent (with a confidence limit of 95 percent) for concentrations of inorganic arsenic between 0.005 and 0.01 mg/m [FN3].
Appendix C
Medical Surveillance Guidelines
I. General
Medical examinations are to be provided for all employees exposed to levels of inorganic arsenic above the action level (0.005mg/m [FN3])for at least 30 days per year (which would include, among others, all employees who work in regulated areas). Examinations are also to be provided to all employees who have had 10 years or more exposure above the action level for more than 30 days per year while working for the present or predecessor employer though they may no longer be exposed above the level.
An initial medical examination is to be provided to all such employees within 4 months of the effective date of the standard. In addition, an initial medical examination is to be provided to all employees who are first assigned to areas in which worker exposure will probably exceed 0.005mg/m [FN3] at the time of initial assignment. In addition to its immediate-diagnostic usefulness, the initial examination will provide a baseline for comparing future test results. The initial examination must include as a minimum the following elements:
(1) A work and medical history, including a smoking history;
(2) A physical examination with special attention to skin, nose, respiratory tract, lymph nodes, nervous system, and liver;
(3) Posterior-anterior chest X-ray (14-inch x 17-inch);
(4) A sputum cytology examination; and
(5) Other examinations which the physician believes appropriate because of the employee's exposure to inorganic arsenic or because of required respirator use.
Periodic examinations are also to be provided to the employees listed above. The periodic examinations shall be given annually for those covered employees 45 years of age or less with fewer than 10 years employment in areas where employee exposure exceeds the action level (0.005mg/m [FN3]). Periodic examinations need not include sputum cytology and only an updated medical history is required.
Periodic examinations for other covered employees, shall be provided every six (6) months. These examinations shall include an updated medical history and all tests required in the initial examination, except for the chest X-ray, and that the medical history need only be updated.
The examination contents are minimum requirements. Additional tests such as pulmonary function tests may be useful.
II. Noncarcinogenic Effects
The standard is based on minimizing risk of exposed workers dying of lung cancer from exposure to inorganic arsenic. It will also minimize skin cancer from such exposure.
The following three sections quoted from "Occupational Diseases: A Guide to Their Recognition," Revised Edition, June 1977, National Institute for Occupational Safety and Health is included to provide information on the nonneoplastic effects of exposure to inorganic arsenic. Such effects should not occur if the OSHA standards are followed.
A. Local -Trivalent arsenic compounds are corrosive to the skin. Brief contact has no effect but prolonged contact results in a local hyperemia and later vesicular or pustular eruption. The moist mucous membranes are most sensitive to the irritant action. Conjunctiva, moist ad macerated areas of skin, the eyelids, the angles of the ears, nose, mouth, and respiratory mucosa are also vulnerable to the irritant effects. The wrists are common sites of dermatitis, as are the genitalia if personal hygiene is poor. Perforations of the nasal septum may occur. Arsenic trioxide and pentoxide are capable of producing skin sensitization and contact dermatitis. Arsenic is also capable of producing keratoses, especially of the palms and soles.
B. Systemic -The acute toxic effects of arsenic are generally seen following ingestion of inorganic arsenical compounds. This rarely occurs in an industrial setting. Symptoms develop within 1/2 to 4 hours following ingestion and are usually characterized by constriction of the throat followed by dysphagia, epigastric pain, vomiting, and watery diarrhea. Blood may appear in vomitus and stools. If the amount ingested is sufficiently high, shock may develop due to severe fluid loss, and death may ensue in 24 hours. If the acute effects are survived, exfoliative dermatitis and peripheral neuritis may develop.
Cases of acute arsenical poisoning due to inhalation are exceedingly rare in industry. When it does occur, respiratory tract symptoms -cough, chest pain, dyspnea-giddiness, headache, and extreme general weakness precede gastrointestinal symptoms. The acute toxic symptoms of trivalent arsenical poisoning are due to severe inflammation of the mucous membranes and greatly increased permeability of the blood capillaries.
Chronic arsenical poisoning due to ingestion is rare and generally confined to patients taking prescribed medications. However, it can be a concomitant of inhaled inorganic arsenic, from swallowed sputum, and improper eating habits. Symptoms are weight loss, nausea and diarrhea alternating with constipation, pigmentation and eruption of the skin, loss of hair, and peripheral neuritis. Chronic hepatitis and cirrhosis have been described. Polyneuritis may be the salient feature, but more frequently there are numbness and parasthenias of "glove and stocking" distribution. The skin lesions are usually melanotic and keratotic and may occasionally take the form of an intradermal cancer of the squamous cell type, but without infiltrative properties. Horizontal white lines (striations) on the fingernails and toenails are commonly seen in chronic arsenical poisoning and are considered to be a diagnostic accompaniment of arsenical polyneuritis.
Inhalation of inorganic arsenic compounds is the most common cause of chronic poisoning in the industrial situation. This condition is divided into three phases based on signs and symptoms.
First Phase: The worker complains of weakness, loss of appetite, some nausea, occasional vomiting, a sense of heaviness in the stomach, and some diarrhea.
Second Phase: The worker complains of conjunctivitis, a catarrhal state of the mucous membranes of the nose, larynx, and respiratory passage. Coryza, hoarseness, and mild tracheobronchitis may occur. Perforation of the nasal septum is common, and is probably the most typical lesion of the upper respiratory tract in occupational exposure to arsenical dust. Skin lesions, eczematoid and allergic in type, are common.
Third Phase: The worker complains of symptoms of peripheral neuritis, initially of hands and feet, which is essentially sensory. In more severe cases, motor paralyses occur; the first muscles affected are usually the toe extensors and the peronei. In only the most severe cases will paralysis of flexor muscles of the feet or of the extensor muscles of hands occur.
Liver damage from chronic arsenical poisoning is still debated, and as yet the question is unanswered. In cases of chronic and acute arsenical poisoning, toxic effects to the myocardium have been reported based on EKG changes. These findings, however, are now largely discounted and the EKG changes are ascribed to electrolyte disturbances concomitant with arsenicalism. Inhalation of arsenic trioxide and other inorganic arsenical dusts does not give rise to radiological evidence or pneumoconiosis. Arsenic does have a depressant effect upon the bone marrow, with disturbances of both erythropoiesis and myelopoiesis.
III. SPUTUM CYTOLOGY
Sputum can be collected by aerosol inhalation during the medical exam or by spontaneous early morning cough at home. Sputum is induced by transoral inhalation of an aerosolized solution of eight per cent (8 percent) sodium chloride in water. After inhaling as few as three to five breaths the subject usually yields an adequate sputum. All sputum should be collected directly into sixty percent (60 percent) alcohol.
Addendum to Section 5214 "Inorganic Arsenic"
Bibliography
Feldman, R.G., Niles, C.A., Kelly-Hayes, M. 1979. Peripheral neuropathy in arsenic smelter workers. Neurology 29:939-944.
Fowler, B.A., Ishiniski, N., Tsuchiya, K. 1979. Arsenic, in Handbook on the Toxicology of Metals. Friberg et al (Ed.). Elsevier, New York.
Haley, T.J. 1984. Arsenic. Dangerous Properties of Industrial Materials 4:9-17.
Hine, C.H., Pinto, S.S. and Nelson, K.W. 1977. Medical problems associated with arsenic exposure. J. Occup. Med. 19:391-396.
Landrigan, P.J. 1981. Arsenic - State of the art. Am. J. Indust. Med. 2:5-14.
Lauwerys, R.R. 1983. Arsenic, in Industrial Chemical Exposure: Guidelines for Biological Monitoring. Biomedical Publications, Davis, CA.
Leonard, A. and Lauwerys, R.R. 1980. Carcinogenicity, teratogenicity and mutagenicity of arsenic. Mut. Res. 75:49-62.
National Institute for Occupational Safety and Health. 1975. Occupational Exposure to Inorganic Arsenic. NIOSH/HEW 75-149.
National Research Council. 1977. Arsenic. National Academy of Sciences, Washington.
s 5215. 4,4'-Methylenebis(2-Chloroaniline).
(a) Scope and Application.
(1) This section establishes requirements for the control of employee exposure to 4,4'-methylenebis(2-chloroaniline), MBOCA, Chemical Abstracts Service Registry No. 101144.
(2) This section applies to the manufacture, packaging, repackaging, storage, handling and use of MBOCA, but does not apply to:
(A) Fabricated products; or
(B) The storage or transportation of MBOCA in sealed, unbroken containers except for labeling of containers under Section 5215(l)(4), reporting of use under Section 5215(n)(1) and preparation of emergency plan under Section 5215(h)(4).
(3) The requirements of this section are subject to the provisions of the Occupational Carcinogens Control Act of 1976 (Health and Safety Code, Division 20, Chapter 2).
(b) Definitions.
Authorized Person. Any person specifically authorized by the employer to handle or use MBOCA or to enter a controlled access area or any person entering such an area as a designated representative of employees for the purpose of exercising an opportunity to observe monitoring and measuring procedures.
Chief. The Chief of the Division of Occupational Safety and Health, P.O. Box 420603, San Francisco, CA 94142.
Controlled Access Area. An area where entry and exit are restricted and controlled for the purpose of limiting occupational exposure to MBOCA.
Engineering Controls. Methods of controlling occupational exposure to injurious materials or conditions by means of general or local exhaust ventilation, by process modification, or by isolation or enclosure of health hazard-producing operation or machinery. Engineering controls do not include employee personal protection.
Work Practice Controls. Methods of controlling occupational exposure to injurious materials or conditions by means of written procedures specifying handling, employee personal protection and personal hygiene.
Fabricated Products. Any elastomer or foam product processed so that the unreacted MBOCA is less than 1.0 percent by weight of polymer.
MBOCA. 4,4'-Methylenebis(2-chloroaniline), Chemical Abstracts Service Registry No. 101144. Appendix A contains other synonyms.
(c) Permissible Exposure Limit.
(1) Exposure to MBOCA shall be controlled such that no employee's urine contains more than 100 micrograms (mg) of MBOCA per liter of urine when the specific gravity of the urine is adjusted to 1.024.
(2) Where specific urine samples are not received as requested by the Chief or his authorized representatives:
(A) Employees shall not be exposed to an 8-hour time-weighted average concentration of MBOCA in excess of 10mg (micrograms) per cubic meter of air, and
(B) Employees shall not be exposed to a ceiling concentration in excess of 50mg per cubic meter of air during any 15-minute period, and
(C) Accessible surfaces which employees are likely to contact in controlled access areas or uncontrolled areas during their normal work shall not exceed 100 <>g MBOCA per 100 cm [FN2] of surface. For regulatory purposes, the average of at least five wipe samples shall be used; if one sample exceeds the mean by a factor of 10 or more, it will be rejected as not being representative.
(d) Monitoring.
(1) Within 30 days of the effective date of this standard, employers using more than one kilogram of MBOCA regardless of concentration, dilution or form, except frozen premix, in any 6-month period shall institute a program of monitoring of surface contamination and urine analysis.
(2) All authorized employees who enter a controlled access area shall have the urine analysis repeated quarterly. Samples are to be obtained near the end of the work shift.
(3)(A) Employees whose urinary levels of MBOCA exceed 100m<>>=/1 with specific gravity adjusted to 1.024 shall be tested at least monthly until 2 consecutive samples taken no less than 3 days apart have been reduced to below 100mg/liter.
(B) No later than 6 months from the effective date of this standard, employees whose urinary levels of MBOCA exceed 100mg/1 with specific gravity adjusted to 1.024 shall be tested at least monthly until 2 consecutive samples taken no less than 3 days apart have been reduced to below 30m/liter.
(4) The method of monitoring and measurement shall be accurate and precise so that 95% of the determinations are within 25% of the true value at the exposure limit.
(5) Employees or their designated representatives shall be afforded reasonable opportunity to observe the monitoring and measuring required by this paragraph.
(6) Within 10 working days following any monitoring and measuring which discloses that any employee has been exposed in excess of the permissible exposure limit, each such employee shall be notified in writing of the numerical results of the monitoring.
(e) Controlled Access Area.
(1) All areas outside of controlled access areas shall be maintained so that MBOCA contamination of surfaces does not exceed 100 <>g per 100 cm [FN2].
(2) All equipment and materials removed from a controlled access area shall be decontaminated so that MBOCA does not exceed 100 <>g per 100 cm [FN2] of surface.
(3) Entry to controlled access areas shall be limited to authorized personnel and escorted visitors. A daily roster shall be made of persons who enter the controlled access area.
(4) Storage, consumption or use of food, beverages, cosmetics, smoking or chewing materials are prohibited in controlled access areas, except for foot-operated drinking fountains.
(f) Methods of Control.
(1) Employee exposures which exceed the limits specified in Section 5215(c) shall be prevented by engineering controls whenever feasible.
(2) Written plans, including timetables for attaining compliance with this section, shall be developed and furnished on request for examination and copying by the Chief or his authorized representative. Such plans shall be updated at least every six months until compliance is achieved and maintained to reflect current methods of control.
(g) Respiratory Protection.
(1) Respiratory protective equipment shall be provided in accordance with this subsection and Section 5144. Records of face fit tests shall be maintained.
(2) Appropriate selection, provision, and use of respiratory protective equipment shall be based on the following table.
RESPIRATORY PROTECTION FOR MBOCA
Concentration of
Airborne
MBOCA Respiratory Type
1. Not greater than Air-purifying with high efficiency parti-
0.1 milligram
per cubic meter. culate filter [FNa1] and half-mask;
Any supplied air respirator
with half-mask.
2. Not greater than Air-purifying, with high efficiency partic-
0.5 milligrams
per cubic meter. ulate filter [FNa1] and full facepiece;
Any supplied air respirator
with full facepiece;
Any self-contained breathing
apparatus with full facepiece.
3. Not greater 10 Powered air-purifying, with high effici-
milligrams
per cubic meter ency particulate filter [FNa1], half-mask, full
facepiece, hood or helmet;
Supplied air, operated in
positive pressure mode, with
half-mask.
4. Not greater than Supplied air, operated in positive pressure
20 milligrams
per cubic meter mode, with full facepiece, hood, helmet,
or suit.
5. Firefighting Self-contained breathing apparatus with
and/or any high
or potentially high full facepiece operated in pressure demand
concentration
mode;
Combination breathing appar-
atus: supplied-air, positive
pressure, full facepiece
respirator with auxiliary
self-contained compressed air
supply with sufficient service
time for escape.
[FNa1] High efficiency filter -99.97 percent efficiency against 0.3 micrometer
monodisperse diethylhexyl phthalate (DOP) particles.
(3) Employee Options.
(A) Employees who wear respirators shall be allowed reasonable time to leave work areas to wash the face and respirator facepiece to prevent potential skin irritation associated with respirator use.
(B) Where air-purifying respirators are required for protection against MBOCA, the employee shall be permitted to change filter elements whenever an increase in breathing resistance is detected, a the employer shall maintain an adequate supply of filter elements for this purpose.
(C) Where compliance with this section requires employee use of an air-purifying respirator for a major portion of the work shift, the employer shall provide, at the option of each affected employee, a powered respirator within 120 days of the effective date of this order.
(h) Hazardous Operations and Emergencies.
(1) Employees engaged in hazardous operations, shall be provided with and required to use:
(A) Respiratory protection that is in accordance with Section 5215(g).
(B) Protective garments to prevent skin contact. The protective garments shall be selected for the operation and its possible exposure conditions.
(C) Eye and face protection where splash hazards from liquid or solution of MBOCA exist.
(2) Employees shall be decontaminated before removing protective garments.
(3) Protective garments shall be provided clean and dry for each use of the garments.
(4) A written operational plan for hazardous operations and emergency situations shall be developed for each facility manufacturing, processing, handling, packaging, repackaging, releasing, storing, selling, transferring, transporting, disposing, or using MBOCA. Appropriate portions of the plan shall be implemented in the event of an emergency. The plan shall specifically provide that:
(A) Employees engaged in hazardous operations or correcting situations of existing hazardous spills shall be equipped as required in this paragraph.
(B) Other employees not so equipped shall evacuate the area and not return until conditions are controlled by methods required in Section 5215(f) and the emergency is abated.
(C) Areas containing hazardous operations, or where the emergency currently exists, shall be posted in accordance with Section 5215(l)(2).
(D) Reports shall be made as required by Section 5215(n)(2).
(E) An employee with a known contact with MBOCA shall be required to shower and wash hair as soon as possible, unless prevented by physical injuries, and shall be given the option to provide a urine specimen for analysis of MBOCA content.
(i) Decontamination and Disposal. All waste contaminated with MBOCA shall be disposed of in accordance with Hazardous Waste Disposal Regulations, Title 22, California Administrative Code, Sections 60001 through 60283.
(1) All shipping containers shall be considered contaminated until decontaminated, or shown not to be contaminated.
(2) Contaminated surfaces may be decontaminated by:
(A) Removal of MBOCA by appropriate mechanical and chemical means; or
(B) Reacting and sealing the MBOCA with urethane or isocyanate solutions.
(3) Decontaminated surfaces shall be retested by wipe samples or fixed with a label showing date and method by which surface was decontaminated, and the label required by Section 5215(l)(4).
(j) Training.
(1) Each employee engaged in an operation or activity where MBOCA is used shall receive an Information and Training Program including the information or requirements of this subsection and precautions for its safe use.
(2) Instruction shall include all information in the Material Safety Data Sheets applicable to the specific MBOCA-containing product to which there is possible exposure. Such a program shall be provided without cost to the employee.
(3) The program shall include:
(A) The nature of the carcinogenic hazard, including local and systemic toxicity.
(B) The specific nature of the operation involving MBOCA which could result in exposure in excess of the permissible exposure limits and necessary protective steps.
(C) The purpose, proper use, and limitations of respiratory protective devices, gloves and protective garments.
(D) The purpose for, and application of, decontamination procedures.
(E) The purpose for, and significance of, emergency practices and procedures.
(F) The employee's specific role in prescribed emergency procedures.
(G) Employee familiarization with the prescribed emergency procedures and rehearsal in their application.
(H) Specific information to aid the employee in recognition of conditions which may result in exposure to MBOCA.
(I) The purpose for, and application of, specific first aid procedures and practices.
(J) The purpose for, and description of, the monitoring program.
(K) The purpose for, and description of, the medical surveillance program.
(L) Employee rights under this section and the CAL/OSHA program.
(M) A review of this section at the employee's first training and indoctrination program and annually thereafter.
(4) All materials relating to the program shall be provided on request to the Chief or his authorized representative.
(5) The employer shall make a copy of this section and its appendices readily available to all affected employees.
(k) Medical Surveillance. A program of medical surveillance shall be instituted for each authorized person. The employer shall provide each such employee with an opportunity for medical examinations and tests in accordance with this subsection. All medical examinations and procedures shall be performed by or under the supervision of a licensed physician, and shall be provided without cost to the employee.
(1) Frequency of medical examinations:
(A) Prior to time of initial assignment or within 90 days of the effective date of this order.
(B) At least every 3 years for the first 10 years of employment involving the use of MBOCA, and annually thereafter.
(2) Content of medical examinations:
(A) A comprehensive medical history with emphasis on pertinent medical, occupational, genetic, and environmental factors (employee and employee's family).
(B) A comprehensive physical examination with emphasis on detecting abnormalities of the liver, pulmonary system, urinary system, breasts, and hematologic system.
(C) Evaluation of the advisability of the employee using negative or positive pressure respirators.
(D) Laboratory tests shall include:
1. Chest X-ray (14-inch by 17-inch, posterior-anterior).
2. Serum total bilirubin.
3. Serum alkaline phosphatase.
4. Serum glutamic oxaloacetic transaminase (SGOT) or serum glutamic pyruvic transaminase (SGPT).
5. Complete blood count (CBC).
6. Complete urinalysis (UA).
(3) Information provided to the physician by the employer:
(A) A copy of this standard and its appendices.
(B) The results of the biological monitoring required by this section since the last medical examination.
(4) The examining physician's written opinion to the employer regarding each employee shall include:
(A) The results of the medical tests performed.
(B) Any medical condition that could place the employee at an increased risk of material impairment of health from his employment.
(5) The employer shall provide a copy of the written opinion to the affected employee.
(l) Signs and Labels.
(1) Entrances to controlled access areas shall be posted with legible signs bearing the legend:
CONTROLLED ACCESS AREA AUTHORIZED PERSONNEL ONLY 4,4'-Methylenebis(2-
chloroaniline)
(2) Areas containing hazardous operations or where an emergency currently exists shall be posted with legible signs bearing the legend:
DANGER HAZARDOUS/EMERGENCY CONDITION 4,4'-Methylenebis(2-chloroaniline) ENTRY
PROHIBITED EXCEPT UNDER EMERGENCY PROCEDURES
(3) Prescribed emergency procedures shall be posted or available in appropriate locations.
(4) Containers of MBOCA and of unreacted solutions or mixtures containing more than one percent (1%) of MBOCA shall have a label not inconsistent [FNa1] with the following:
CAUTION 4,4'-Methylenebis(2-chloroaniline) AVOID SKIN CONTACT AVOID BREATHING
DUST/VAPOR REGULATED CARCINOGEN
[FNa1] In order to provide legibility, careful and selective shortening of warning statements may be permitted for small containers (1 quart or less) where their size precludes the use of the warning words shown above. In no instance shall the label omit "Regulated Carcinogen."
(5) No statement shall appear on or near any required sign, label, or instruction which contradicts or detracts from the effect of any required warning, information, or instruction.
(6) Lettering on signs required by this subsection shall be conspicuous and legible.
(m) Records.
(1) All records maintained in accordance with this section shall include the name an social security number of each employee where relevant.
(2) Records of required monitoring and measuring, face fit tests, medical records, and authorized personnel rosters shall be made and shall be available upon request for examination and copying to authorized representatives of the Chief. Such records shall also be provided upon request to authorized representatives of the Chief in accordance with Section 3204.
(3) The daily roster of employees entering regulated areas or a summary of the rosters shall be retained for a period of a year. The roster and/or summaries shall be provided upon request to authorized representatives of the Chief.
(4) Monitoring and measuring records shall be maintained for not less than 30 years and shall contain the following information:
(A) Date, location, and concentration of each determination;
(B) Instruments and methods used;
(C) Any additional information necessary to determine individual employee exposure.
(5) Face fit tests shall be maintained for not less than one year and shall include persons tested, method used and results.
(6) The employer shall maintain the originals or true copies of the physician's written opinions regarding each affected employee for the duration of the employment plus 20 years or for 30 years, whichever is longer.
(7) In the event that the employer ceases to do business and there is no successor to receive and retain the records for the prescribed period, these records shall be transmitted by Registered Mail to the Director of National Institute for Occupational Safety and Health, U.S. Department of Health and Human Services.
The employer shall also comply with any additional requirements involving the transfer of records set forth in Section 3204.
(8) Employees, former employees, or their designated representatives shall be provided records of required monitoring and measuring in accordance with Section 3204.
(9) Upon written request of any employee or former employee, a copy of the medical record of that employee shall be furnished to the employee or to any physician or other individual or organization designated by the employee or former employee in accordance with Section 3204.
(n) Reports. See section 5203.
Appendix A
Physical and Chemical Data
(1) Synonyms:
4,4'-methylenebis(2-chloroaniline)
p,p'-methylenebis(o-chloroaniline)
methylene-4,4'-bis(o-chloroaniline)
4,4'-methylenebis(2-chlorobenzenamine)
p,p'-methylenebis(o-chlorobenzenamine)
3,3'-dichloro-4,4'-diaminodiphenylmethane
p,p'-methylenebis(alpha-chloroaniline)
di(4-amino-3-chlorophenyl)methane
di(4-amino-3-clorofenil)metano (Italian)
3,3'dicloro-4,4'diaminodifenilmetano (Italian)
4,4'-metilene-bis-o-cloranilina (Italian)
3,3'-dichlor-4,4'-diaminodiphenylmethan (German)
MBOCA
DACPM
MOCA (R), DuPont
Cyanaset (R), American Cyanamid
Curalon M (R), Uniroyal
Curene 442 (R), Anderson Chemical
Bis-Amine A (R), Wakayama Seiko/Polyester Corp.
CL-MDA
Activator M (R), MVR
Cuamine M, Ihara Chemical
MBK, Kulkman
(2) Identification and General Properties:
Structural formula:
2
2
Molecular weight: 267
Specific gravity of solid: 1.44 at 75<> (24<>C)
Melting range: 212-228<>F (100-109<>C)
Color: light creamy yellow to light gray tan
Odor: slight
Appendix B
Supplemental Medical Information
(1) When required tests under Section 5215(k)(2) reveal abnormalities, the tests should be repeated as soon as practicable within 30 days. If the tests remain abnormal, consideration should be given to withdrawing the employee from contact with 4,4'-methylenebis(2-chloroaniline) while a more comprehensive examination is made.
(2) Additional tests that may be useful;
(A) Pulmonary system
1. Sputum cytology
2. Bronchoscopy with bronchial washings for cytology and tissue biopsy.
3. Computerized axial tomography with or without use of a contrast medium.
(B) Liver
1. Liver scan
2. Percutaneous liver biopsy
3. Hepatic angiography
(C) Urinary system
1. Urine cytology, 24-hour specimen
2. Blood urea nitrogen (BUN)
3. Serum creatinine
4. Creatinine clearance
5. Radioactive renogram
6. Intravenous pyelogram (IVP)
7. Cystoscopy with retrograde pyelogram and/or urinary bladder biopsy, as indicated.
8. Percutaneous renal biopsy.
(D) Breasts
1. Mammography
2. Breasts biopsy
(3) Known toxicity of 4,4'-methylenebis(2-chloroaniline)
(A) Pulmonary carcinoma [FNa1]
(B) Malignant tumors of the liver [FNa1]
(C) Carcinoma of the breast [FNa1]
(D) Carcinoma of the urinary bladder [FNa1]
(E) Kidney irritation
(F) Methemoglobinemia [FNa1]
[FNa1] Observed in experimental animals only
(4) Routes of absorption
(A) Skin (primary)
(B) Inhalation (secondary)
(C) Ingestion (minor)
Appendix C
Analytical Methods
(Laboratory methods used by CAL/OSHA will be furnished on request.)
Note: Authority cited: Sections 142.3, 9020, 9030 and 9040, Labor Code. Reference: Sections 142.3, 9004(d), 9009, 9020, 9030, 9031 and 9040, Labor Code.
s 5216. Lead.
Note: Authority cited: Section 142.3, Labor Code. Reference: Section 142.3, Labor Code.
Appendix A
Substance Data Sheet for Occupational Exposure to Lead
I. Substance Identification
A. Substance: Pure lead (Pb) is a heavy metal at room temperature and pressure and is a basic chemical element. It can combine with various other substances to form numerous lead compounds.
B. Compounds Covered by the Standard: The word "lead" when used in this standard means elemental lead, all inorganic lead compounds and a class of organic lead compounds called lead soaps. This standard does not apply to other organic lead compounds.
C. Uses: Exposure to lead occurs in at least 120 different occupations, including primary and secondary lead smelting, lead storage battery manufacturing, lead pigment manufacturing and use, solder manufacturing and use, shipbuilding and ship repairing, auto manufacturing, and printing.
D. Permissible Exposure: The Permissible Exposure Limit (PEL) set by the standard is 50 micrograms of lead per cubic meter of air (50 m g/M 3), averaged over an 8-hour workday.
E. Action Level: The standard establishes an action level of 30 micrograms per cubic meter of air (30 m g/M 3), time-weighted average, based on an 8-hour workday. The action level initiates several requirements of the standard, such as exposure monitoring, medical surveillance, and training and education.
II. Health Hazard Data
A. Ways in which lead enters your body. When absorbed into your body in certain doses, lead is a toxic substance. The object of the lead standard is to prevent absorption of harmful quantities of lead. The standard is intended to protect you not only from the immediate toxic effects of lead but also from the serious toxic effects that may not become apparent until years of exposure have passed.
Lead can be absorbed into your body by inhalation (breathing) and ingestion (eating). Lead (except for certain organic lead compounds not covered by the standard, such as tetraethyl lead) is not absorbed through your skin. When lead is scattered in the air as a dust, fume or mist it can be inhaled and absorbed through your lungs and upper respiratory tract. Inhalation of airborne lead is generally the most important source of occupational lead absorption. You can also absorb lead through your digestive system if lead gets into your mouth and is swallowed. If you handle food, cigarettes, chewing tobacco, or make-up which have lead on them or handle them with hands contaminated with lead, this will contribute to ingestion.
A significant portion of the lead that you inhale or ingest gets into your blood stream. Once in your blood system, lead is circulated throughout your body and stored in various organs and body tissues. Some of this lead is quickly filtered out of your body and excreted, but some remains in the blood and other tissues. As exposure to lead continues, the amount stored in your body will increase if you are absorbing more lead than your body is excreting. Even though you may not be aware of any immediate symptoms of disease, this lead stored in your tissues can be slowly causing irreversible damage, first to individual cells, then to your organs and whole body systems.
B. Effects of overexposure to lead -(1) Short-term (acute) overexposure. Lead is a potent, systemic poison that serves no known useful function once absorbed by your body. Taken in large enough doses, lead can kill you in a matter of days. A condition affecting the brain called acute encephalopathy may arise which develops quickly to seizures, coma, and death from cardiorespiratory arrest. A short-term dose of lead can lead to acute encephalopathy. Short-term occupational exposures of this magnitude are highly unusual, but not impossible. Similar forms of encephalopathy may, however, arise from extended, chronic exposure to lower doses of lead. There is no sharp dividing line between rapidly developing acute effects of lead and chronic effects which take longer to acquire. Lead adversely affects numerous body systems and causes forms of health impairment and disease which arise after periods of exposure as short as days or as long as several years.
(2) Long-term (chronic) overexposure. Chronic overexposure to lead may result in severe damage to your blood-forming, nervous, urinary and reproductive systems. Some common symptoms of chronic overexposure include loss of appetite, metallic taste in the mouth, anxiety, constipation, nausea, pallor, excessive tiredness, weakness, insomnia, headache, nervous irritability, muscle and joint pain or soreness, fine tremors, numbness, dizziness, hyperactivity and colic. In lead colic there may be severe abdominal pain.
Damage to the central nervous system in general and the brain (encephalopathy) in particular is one of the most severe forms of lead poisoning. The most severe, often fatal, form of encephalopathy may be preceded by vomiting, a feeling of dullness progressing to drowsiness and stupor, poor memory, restlessness, irritability, tremor, and convulsions. It may arise suddenly with the onset of seizures, followed by coma, and death. There is a tendency for muscular weakness to develop at the same time. This weakness may progress to paralysis often observed as a characteristic "wrist drop" or "foot drop" and is a manifestation of a disease to the nervous system called peripheral neuropathy.
Chronic overexposure to lead also results in kidney disease with few, if any, symptoms appearing until extensive and most likely permanent kidney damage has occurred. Routine laboratory tests reveal the presence of this kidney disease only after about two-thirds of kidney function is lost. When overt symptoms of urinary dysfunction arise, it is often too late to correct or prevent worsening conditions, and progression to kidney dialysis or death is possible.
Chronic overexposure to lead impairs the reproductive systems of both men and women. Overexposure to lead may result in decreased sex drive, impotence and sterility in men. Lead can alter the structure of sperm cells raising the risk of birth defects. There is evidence of miscarriage and stillbirth in women whose husbands were exposed to lead or who were exposed to lead themselves. Lead exposure also may result in decreased fertility and abnormal menstrual cycles in women. The course of pregnancy may be adversely affected by exposure to lead since lead crosses the placental barrier and poses risks to developing fetuses. Children born of parents either one of whom were exposed to excess lead levels are more likely to have birth defects, mental retardation, or behavioral disorders or to die during the first year of childhood.
Overexposure to lead also disrupts the blood-forming system resulting in decreased hemoglobin (the substance in the blood that carries oxygen to the cells) and ultimately anemia. Anemia is characterized by weakness, pallor and fatigue as a result of decreased oxygen-carrying capacity in the blood.
(3) Health protection goals of the standard. Prevention of adverse health effects for most workers from exposure to lead throughout a working lifetime requires that worker blood lead levels (PbB) be maintained at or below forty micrograms per one hundred grams of whole blood (40 m g/100g). The blood lead levels of workers (both male and female workers) who intend to have children should be maintained below 30 m g/100g to minimize adverse reproductive health effects to the parents and the developing fetus.
The measurement of your blood lead level is the most useful indicator of the amount of lead being absorbed by your body. Blood lead levels (PbB) are most often reported in units of milligrams (mg) or micrograms ( m g) of lead (1 mg = 1000 m g) per 100 grams (100g), 100 milliliters (100 ml) or deciliter (dl) of blood. These three units are essentially the same. Sometime PbB's are expressed in the form of mg% or m g%. This is a shorthand notation for 100g, 100ml, or dl.
PbB measurements show the amount of lead circulating in your blood stream but do not give any information about the amount of lead stored in your various tissues. PbB measurements merely show current absorption of lead, not the effect that lead is having on your body or the effects that past lead exposure may have already caused. Past research into lead-related diseases, however, has focused heavily on associations between PbBs and various diseases. As a result, the relative level of your PbB is an important indicator of the probability of your acquiring a lead-related health impairment or disease.
Once your blood lead level climbs above 40 m g/100g, your risk of disease increases. There is a wide variability of individual response to lead, thus it is difficult to say that a particular PbB in a given person will cause a particular effect. Studies have associated fatal encephalopathy with PbBs as low as 150 m g/100g. Other studies have shown other forms of disease in some workers with PbBs well below 80 m g/100g. Your PbB is a crucial indicator of the risks to your health, but one other factor is also extremely important. This factor is the length of time you have had elevated PbBs. The longer you have an elevated PbB, the greater the risk that large quantities of lead are being gradually stored in your organs and tissues (body burden). The greater your overall body burden, the greater the chances of substantial permanent damage.
The best way to prevent all forms of lead-related impairments and diseases (both short term and long term) is to maintain your PbB below 40 m g/100g. The provisions of the standard are designed with this end in mind. Your employer has prime responsibility to assure that the provisions of the standard are complied with both by the company and by individual workers. You as a worker, however, also have a responsibility to assist your employer in complying with the standard. You can play a key role in protecting your own health by learning about the lead hazards and their control, learning what the standard requires, following the standard where it governs your own actions, and seeing that your employer complies with provisions governing his actions.
(4) Reporting signs and symptoms of health problems. You should immediately notify your employer if you develop signs or symptoms associated with lead poisoning or if you desire medical advice concerning the effects of current or past exposure to lead on your ability to have a healthy child. You should also notify your employer if you have difficulty breathing during a respirator fit test or while wearing a respirator. In each of these cases your employer must make available to you appropriate medical examinations or consultations. These must be provided at no cost to you and at a reasonable time and place.
The standard contains a procedure whereby you can obtain a second opinion by a physician of your choice if the employer selected the initial physician.
Appendix B
Section 5216 Summary
This appendix summarizes key provisions of the standard that you as a worker should become familiar with.
I. Permissible Exposure Limit (PEL)
The standard sets a permissible exposure limit (PEL) of fifty micrograms of lead per cubic meter of air (50 m g/M 3), averaged over an 8-hour workday. This is the highest level of lead in air to which you may be permissibly exposed over an 8-hour workday. Since it is an 8-hour average it permits short exposures above the PEL so long as for each 8-hour workday your average exposure does not exceed the PEL.
This standard recognizes that your daily exposure to lead can extend beyond a typical 8-hour workday as the result of overtime or other alterations in your work schedule. To deal with this, the standard contains a formula which reduces your permissible exposure when you are exposed more than 8 hours. For example, if you are exposed to lead for 10 hours a day, the maximum permitted average exposure would be 40 m g/M 3.
II. Exposure Monitoring
If lead is present in any quantity in the workplace where you work, your employer is required to make an initial determination of whether the action level is exceeded for any employee. This initial determination must include instrument monitoring of the air for the presence of lead and must cover the exposure of a representative number of employees who are reasonably believed to have the highest exposure levels. If your employer has conducted appropriate air sampling for lead in the past year he may use these results. If there have been any employee complaints of symptoms which may be attributable to exposure to lead or if there is any other information or observations which would indicate employee exposure to lead, this must also be considered as part of the initial determination. This determination must have been completed within 30 days of the effective date of the standard. If this initial determination shows that a reasonable possibility exists that any employee may be exposed, without regard to the use of respirators, over the action level (30 m g/M 3), your employer must set up an air monitoring program to determine the exposure level of every employee exposed to lead at your workplace.
In carrying out this air monitoring program, your employer is not required to monitor the exposure of every employee but must monitor a representative number of employees and job types. Enough sampling must be done to enable each employee's exposure level to be reasonably represented by at least one full-shift (at least 7 hours) air sample. In addition, these air samples must be taken under conditions which represent each employee's regular, daily exposure to lead. All initial exposure monitoring must have been completed within 90 days of the effective date of the standard.
If you are exposed to lead and air sampling is performed, your employer is required to quickly notify you in writing of air monitoring results which represent your exposure. If the results indicate your exposure exceeds the PEL (without regard to your use of respirators), then your employer must also notify you of this in writing and also provide you with a description of the corrective action that will be taken to reduce your exposure.
Your exposure must be rechecked by monitoring every six months if your exposure is over the action level but below the PEL. Air monitoring must be repeated every three months if you are exposed over the PEL. Your employer may discontinue monitoring for you if two consecutive measurements, taken at least two weeks apart, are below the action level. However, whenever there is a production, process, control, or personnel change at your workplace which may result in new or additional exposure to lead, or whenever there is any other reason to suspect a change which may result in new or additional exposure to lead, your employer must perform additional monitoring.
III. Compliance
Except for certain industries, the regulation requires employers to reduce and maintain employee exposure to lead at or below the permissible exposure limit by means of engineering, work practice, and administrative controls to the extent that such controls are feasible. Even though such controls may not be sufficient to effect compliance with the PEL, they must be instituted to achieve the lowest feasible exposure level and the employer must provide supplemental protection in the form of respirators.
The regulation's implementation schedule prescribes deadline dates at which employers in the various industries must have controls in operation to achieve compliance with the PEL without resorting to respirator use, to the extent that such controls are feasible. These dates are based on the projected difficulty in instituting engineering controls and vary from industry to industry. In electronics, gray iron foundries, ink manufacture, paints and coatings manufacture, wallpaper manufacture, can manufacture, and printing, the date is March 7, 1983; in secondary lead smelting and battery manufacturing, the deadline is March 7, 1983; in primary lead production, it is March 7, 1982; and for most other industries, it is September 7, 1984.
The regulation also requires that employers in the above-indicated industries establish a written plan within specified dates which will describe and project the means and implementation schedule whereby compliance with the PEL will be achieved by the applicable deadline.
For certain other industries, the feasibility of complying with the PEL by means of engineering controls has not been established, and as a consequence, employers within these industries are required to implement feasible controls to comply with an employee exposure limit of 150 m g/M 3 and to supplement such controls with respiratory protection to achieve compliance with the PEL. These industries or operations include lead pigment manufacture, nonferrous foundries, leaded steel manufacture, lead chemical manufacture, shipbuilding and ship repair, battery breaking (excluding scrap collection and processing which is part of secondary lead production), the secondary lead smelting of copper, and lead casting.
Where employee exposure above the PEL occurs intermittently for no more than 30 days per year, feasible engineering controls must be implemented to achieve compliance with an exposure limit of 150 m g/M 3 but compliance with the PEL may be accomplished by any combination of engineering, work practice, and administrative controls and respiratory protection.
IV. Respiratory Protection
Your employer is requiredto provide and assure your use of respirators when your exposure to lead is not controlled below the PEL by other means. The employer must pay the cost of the respirator. Whenever you request one, your employer is also required to provide you a respirator even if the air exposure level does not exceed the PEL. You might desire a respirator when, for example, you intend to have children in the near future, and want to reduce the level of lead in your body to minimize adverse reproductive effects. While respirators are the least satisfactory means of controlling your exposure, they are capable of providing significant protection when properly chosen, fitted, worn, cleaned, and maintained and are replaced when they stop providing adequate protection. (continued)