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(continued)

An uncommon sign, which cannot be detected from the smear, but can be elicited by a "sucrose water test" of peripheral blood, is transient paroxysmal nocturnal hemoglobinuria (PNH), which may first occur insidiously during a period of established aplastic anemia, and may be followed within one to a few years by the appearance of rapidly fatal acute myelogenous leukemia. Clinical detection of PNH, which occurs in only one or two percent of those destined to have acute myelogenous leukemia, may be difficult; if the "sucrose water test" is positive, the somewhat more definitive Ham test, also known as the acid-serum hemolysis test, may provide confirmation.
e. Individuals documented to have developed acute myelogenous leukemia years after initial exposure to benzene may have progressed through a preliminary phase of hematologic abnormality. In some instances pancytopenia (i.e., a lowering in the counts of all circulating blood cells of bone marrow origin, but not to the extent implied by the term "aplastic anemia") preceded leukemia for many years. Depression of a single blood cell type or platelets may represent a harbinger of aplasia or leukemia. The finding of two or more cytopenias, or pancytopenia in a benzene-exposed individual, must be regarded as highly suspicious of more advanced although still reversible, toxicity. "Pancytopenia" coupled with the appearance of immature cells (myelocytes, myeloblasts, erythroblasts, etc.), with abnormal cells (pseudo Pelger-Huetanomaly, atypical nuclear heterochromatin, etc.), or unexplained elevations of white blood cells must be regarded as evidence of benzene overexposure unless proved otherwise. Many severely aplastic patients manifested the ominous finding of 5-10 percent myeloblasts in the marrow, occasional myeloblasts and myelocytes in the blood and 20-30% monocytes. It is evident that isolated cytopenias, pancytopenias, and even aplastic anemias induced by benzene may be reversible and complete recovery has been reported on cessation of exposure. However, since any of these abnormalities is serious, the employee must immediately be removed from any possible exposure to benzene vapor. Certain tests may substantiate the employee's prospects for progression or regression. One such test would be an examination of the bone marrow, but the decision to perform a bone marrow aspiration or needle biopsy is made by the hematologist.
The findings of basophilic stippling in circulating red blood cells (usually found in 1 to 5% of red cells following marrow injury), and detection in the bone marrow of what are termed "ringed sideroblasts" must be taken seriously, as they have been noted in recent years to be premonitory signs of subsequent leukemia.
Recently peroxidase-staining of circulating or marrow neutrophil granulocytes, employing benzidine dihydrochloride, have revealed the disappearance of, or diminution in, peroxidase in a sizable proportion of the granulocytes, and this has been reported as an early sign of leukemia. However, relatively few patients have been studied to date. Granulocyte granules are normally strongly peroxidase positive. A steady decline in leukocyte alkaline phosphatase has also been reported as suggestive of early acute leukemia. Exposure to benzene may cause an early rise in serum iron, often but not always associated with a fall in the reticulocyte count. Thus, serial measurements of serum iron levels may provide a means of determining whether or not there is a trend representing sustained suppression of erythropoiesis.
Measurement of serum iron, determination of peroxidase and of alkaline phosphatase activity in peripheral granulocytes can be performed in most pathology laboratories. Peroxidase and alkaline phosphatase staining are usually undertaken when the index of suspicion for leukemia is high.


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.








Appendix D
Sampling and Analytical Methods for Benzene Monitoring and Measurement
Procedures

Measurements taken for the purpose of determining employee exposure to benzene are best taken so that the representative average 8-hour exposure may be determined from a single 8-hour sample or two (2) 4-hour samples. Short-time interval samples (or grab samples) may also be used to determine average exposure level if a minimum of five measurements are taken in a random manner over the 8-hour work shift. Random sampling means that any portion of the workshift has the same chance of being sampled as any other. The arithmetic average of all such random samples taken on one work shift is an estimate of an employee's average level of exposure for that work shift. Air samples should be taken in the employee's breathing zone (air that would most nearly represent that inhaled by the employee). Sampling and analysis must be performed with procedures meeting the requirements of the standard.
There are a number of methods available for monitoring employee exposures to benzene. The sampling and analysis may be performed by collection of the benzene vapor on charcoal absorption tubes, with subsequent chemical analysis by gas chromatography. Sampling and analysis may also be performed by portable direct reading instruments, real-time continuous monitoring systems, passive dosimeters or other suitable methods. The employer has the obligation of selecting a monitoring method which meets the accuracy and precision requirements of the standard under his unique field conditions. The standard requires that the method of monitoring must have an accuracy, to a 95 percent confidence level, of not less than plus or minus 25 percent for concentrations of benzene greater than or equal to 0.5 ppm.
The OSHA Laboratory modified NIOSH Method S311 and evaluated it at a benzene concentration of 1 ppm. A procedure for determining the benzene concentration in bulk material samples was also evaluated. This work, reported in OSHA Laboratory Method No. 12, includes the following two analytical procedures:
1. OSHA Method 12 for Air Samples
Analyte: Benzene
Matrix: Air
Procedure: Adsorption on charcoal, desorption with carbon disulfide, analysis by GC.
Detection limit: 0.04 ppm
Recommend air volume and sampling rate: 10 L at 0.2 L/min.
1. Principle of the Method.
1.1. A known volume of air is drawn through a charcoal tube to trap the organic vapors present.
1.2. The charcoal in the tube is transferred to a small, stoppered vial, and the analyte is desorbed with carbon disulfide.
1.3. An aliquot of the desorbed sample is injected into a gas chromatograph.
1.4. The area of the resulting peak is determined and compared with areas obtained from standards.
2. Advantages and disadvantages of the method.
2.1. Sampling device is small, portable, and involves no liquids. Interferences are minimal, and most of those which do occur can be eliminated by altering chromatographic conditions. The samples are analyzed by means of a quick, instrumental method.
2.2. The amount of sample which can be taken is limited by the number of milligrams that the tube will hold before overloading. When the sample value obtained for the backup section of the charcoal tube exceeds 25 percent of that found on the front section, the possibility of sample loss exists.
3. Apparatus.
3.1. A calibrated personal sampling pump whose flow can be determined within +5 percent at the recommended flow rate.
3.2. Charcoal tubes: Glass with both ends flame sealed, 7cm long with a 6-mm O.D. and a 4-mm I.D., containing 2 sections of 20/40 mesh activated charcoal separated by a 2-mm portion of urethane foam. The activated charcoal is prepared from coconut shells and is fired at 600 degrees C prior to packing. The adsorbing section contains 100 mg of charcoal, the back-up section 50 mg. A 3-mm portion of urethane foam is placed between the outlet and of the tube and the back-up section. A plug of silanized glass wool is placed in front of the adsorbing section. The pressure drop across the tube must be less than one inch of mercury at flow rate of 1 liter per minute.
3.3. Gas chromatograph equipped with a flame ionization detector.
3.4. Column (10-ft x 1/8-in stainless steel) packed with 80/100 Supelcoport coated with 20 percent SP 2100, 0.1 percent CW 1500.
3.5. An electronic integrator or some other suitable method for measuring peak area.
3.6. Two-milliliter sample vials with Teflon-lined caps.
3.7. Microliter syringes: 10-microliter (10-uL) syringe, and other convenient sizes for making standards; 1-uL syringe for sample injections.
3.8. Pipets: 1.0 mL delivery pipets.
3.9. Volumetric flasks: convenient sizes for making standard solutions.
4. Reagents.
4.1. Chromatographic quality carbon disulfide (CS sub2). Most commercially available carbon disulfide contains a trace of benzene which must be removed. It can be removed with the following procedure:
Heat under reflux for 2 to 3 hours, 500 mL of carbon disulfide, 10 mL concentrated sulfuric acid, and 5 drops of concentrated nitric acid. The benzene is converted to nitrobenzene. The carbon disulfide layer is removed, dried with anhydrous sodium sulfate, and distilled. The recovered carbondisulfide should be benzene free. (It has recently been determined that benzene can also be removed by passing the carbon disulfide through 13x molecular sieve.)
4.2. Benzene, reagent grade.
4.3. p-Cymene, reagent grade (internal standard).
4.4. Desorbing reagent. The desorbing reagent is prepared by adding 0.05 mL of p-cymene per milliliter of carbon disulfide. (The internal standard offers a convenient means of correcting analytical response for slight inconsistencies in the size of sample injections. If the external standard technique is preferred, the internal standard can be eliminated).
4.5. Purified GC grade helium, hydrogen and air.
5. Procedure.
5.1. Cleaning of equipment. All glassware used for the laboratory analysis should be properly cleaned and free of organics which could interfere in the analysis.
5.2. Calibration of personal pumps. Each pump must be calibrated with a representative charcoal tube in the line.
5.3. Collection and shipping of samples.
5.3.1. Immediately before sampling, break the ends of the tube to provide an opening at least one-half the internal diameter of the tube (2mm).
5.3.2. The smaller section of the charcoal is used as the backup and should be placed nearest the sampling pump.
5.3.3. The charcoal tube should be placed in a vertical position during sampling to minimize channeling through the charcoal.
5.3.4. Air being sampled should not be passed through any hose or tubing before entering the charcoal tube.
5.3.5. A sample size of 10 liters is recommended. Sample at a flow rate of approximately 0.2 liters per minute. The flow rate should be known with an accuracy of at least +5 percent.
5.3.6. The charcoal tubes should be capped with the supplied plastic caps immediately after sampling.
5.3.7. Submit at least one blank tube (a charcoal tube subjected to the same handling procedures, without having any air drawn through it) with each set of samples.
5.3.8. Take necessary shipping and packing precautions to minimize breakage of samples.
5.4. Analysis of samples.
5.4.1. Preparation of samples. In preparation for analysis, each charcoal tube is scored with a file in front of the first section of charcoal and broken open. The glass wool is removed and discarded. The charcoal in the first (larger) section is transferred to a 2-mL vial. The separating section of foam is removed and discarded; the second section is transferred to another capped vial, these two sections are analyzed separately.
5.4.2. Desorption of samples. Prior to analysis, 1.0 mL of desorbing solution is pipetted into each sample container. The desorbing solution consists of 0.05 uL internal standard per mL of carbon disulfide. The sample vials are capped as soon as the solvent is added. Desorption should be done for 30 minutes with occasional shaking.
5.4.3. GC conditions. Typical operating conditions for the gas chromatograph are:
a. 30 mL/min (60 psig) helium carrier gas flow.
b. 30 mL/min (40 psig) hydrogen gas flow to detector.
c. 240 mL/min (40 psig) air flow to detector.
d. 150 degrees C injector temperature.
e. 250 degrees C detector temperature.
f. 100 degrees C column temperature.
5.4.4. Injection size, 1 uL.
5.4.5. Measurement of area. The peak areas are measured by an electronic integrator or some other suitable form of area measurement.
5.4.6. An internal standard procedure is used. The integrator is calibrated to report results in ppm for a 10 liter air sample after correction for desorption efficiency.
5.5. Determination of desorption efficiency.
5.5.1. Importance of determination. The desorption efficiency of a particular compound can vary from one laboratory to another and from one lot of chemical to another. Thus, it is necessary to determine, at least once, the percentage of the specific compound that is removed in the desorption process, provided the same batch of charcoal is used.
5.5.2. Procedure for determining desorption efficiency. The reference portion of the charcoal tube is removed. To he remaining portion, amounts representing 0.5X, 1X, and 2X (X represents target concentration) and based on a 10 L air sample are injected into several tubes at each level. Dilutions of benzene with carbon disulfide are made to allow injection of measurable quantities. These tubes are then allowed to equilibrate at least overnight. Following equilibration they are analyzed following the same procedure as the samples. Desorption efficiency is determined by dividing the amount of benzene found by amount spiked on the tube.
6. Calibration and standards. A series of standards varying in concentration over the range of interest is prepared and analyzed under the same GC conditions that will be used on the samples. A calibration curve is prepared by plotting concentration (ug/mL) versus peak area.
7. Calculations. Benzene air concentration can be calculated from the following equation:
mg/m [FN3] = (A)(B)/(C)(D)
Where: A = ug/mL benzene, obtained from the calibration curve,
B = desorption volume (1 mL),
C = liters of air sampled, and

D = desorption efficiency.
The concentration in mg/m [FN3] can be converted to ppm (at 25 degrees C and 760 mm) with the following equation:
ppm = (mg/m [FN3])(24.46)/(78.11)
Where: 24.46 = molar volume of an ideal gas at 25 degrees C and 760 mm, and 78.11 = molecular weight of benzene.
8. Backup Data.
8.1. Detection limit -Air Samples.
The detection limit for the analytical procedure is 1.28 ng with a coefficient of variation of 0.023 at this level. This would be equivalent to a concentration of 0.04 ppm for a 10 L air sample. This amount provided a chromatographic peak that could be identifiable in the presence of possible interferences. The detection limit data were obtained by making 1 uL injections of a 1.283 ug/mL standard.


____________________________
Area
Injection Count
____________________________
1........ 655.4
2........ 617.5
3........ 662.0 X = 640.2
4........ 641.1 SD = 14.9
5........ 636.4 CV = 0.023
6........ 629.2
____________________________


8.2. Pooled coefficient of variation -Air Samples. The pooled coefficient of variation for the analytical procedure was determined by 1 uL replicate injections of analytical standards. The standards were 16.04, 32.08, and 64.16 ug/mL, which are equivalent to 0.5, 1.0, and 2.0 ppm for a 10 L air sample respectively.


_________________________________________
Area Counts
Injection _________________________
0.5 ppm 1.0 ppm 2.0 ppm
_________________________________________
1........... 3996.5 8130.2 16481
2........... 4059.4 8235.6 16493
3........... 4052.0 8307.9 16535
4........... 4027.2 8263.2 16609
5........... 4046.8 8291.1 16552
6........... 4137.9 8288.8 16618
X = 4053.3 8254.0 16548.3
SD = 47.2 62.5 57.1
CV = 0.0116 0.0076 0.0034
CV = 0.008.... ....... ....... .......
_________________________________________


8.3. Storage Data -Air Sample.
Samples were generated at 1.03 ppm benzene at 80% relative humidity, 20 degrees C, and 643mm. All samples were taken for 50 minutes at 0.2 L/min. Six samples were analyzed immediately and the rest of the samples were divided into two groups by fifteen samples each. One group was stored at refrigerated temperature of - 25 degrees C, and the other group was stored at ambient temperature (approximately 23 degrees C). These samples were analyzed over a period of fifteen days. The results are tabulated below.
PERCENT RECOVERY


_______________________________________________________
Day
Analyzed Refrigerated --Ambient
_______________________________________________________
0....... 97.4 98.7 98.9 97.4 98.7 98.9
0....... 97.1 100.6 100.9 97.1 100.6 100.9
2....... 95.8 96.4 95.4 95.4 96.6 96.9
5....... 93.9 93.7 92.4 92.4 94.3 94.1
9....... 93.6 95.5 94.6 95.2 95.6 96.6
13...... 94.3 95.3 93.7 91.0 95.0 94.6

15...... 96.8 95.8 94.2 92.9 96.3 95.9
_______________________________________________________


8.4. Desorption data.
Samples were prepared by injecting liquid benzene onto the A section of charcoal tubes. Samples were prepared that would be equivalent to 0.5, 1.0, and 2.0 ppm for a 10 L air sample.
PERCENT RECOVERY


________________________________
0.5 1.0 2.0
Sample ppm ppm ppm
________________________________
1..... 99.4 98.8 99.5
2..... 99.5 98.7 99.7
3..... 99.2 98.6 99.8
4..... 99.4 99.1 100.0

5..... 99.2 99.0 99.7
6..... 99.8 99.1 99.9
X =..... 99.4 98.9 99.8
SD =.... 0.22 0.21 0.18
CV =.... 0.0022 0.0021 0.0018
X = 99.4
________________________________


8.5. Carbon disulfide.
Carbon disulfide from a number of sources was analyzed for benzene contamination. The results are given in the following table. The benzene contaminant can be removed with the procedures given in section 4.1.
II. OSHA Laboratory Method No. 12 for Bulk Samples
Analyte: Benzene.

_______________________________________________________________

ppm equivalent
Sample ug Benzene/ml (for 10 L air sample)
_______________________________________________________________
Aldrich Lot 83017....... 4.20 0.13
Baker Lot 720364........ 1.01 0.03
Baker Lot 822351........ 1.01 0.03
Mallinkrodt Lot WEMP.... 1.74 0.05
Mallinkrodt Lot WDSJ.... 5.65 0.18
Mallindrodt Lot WHGA.... 2.90 0.09
Treated SC 2 ......... ..............
_______________________________________________________________


Matrix: Bulk Samples.
Procedure: Bulk samples are analyzed directly by high performance liquid chromatography (HPLC).
Detection limits: 0.01% by volume.
1. Principle of the method.
1.1. An aliquot of the bulk sample to be analyzed is injected into a liquid chromatograph.
1.2. The peak area for benzene is determined and compared to areas obtained from standards.
2. Advantages and disadvantages of the method.
2.1. The analytical procedure is quick, sensitive, and reproducible.
2.2. Reanalysis of samples is possible.
2.3. Interferences can be circumvented by proper selection of HPLC parameters.
2.4. Samples must be free of any particulates that may clog the capillary tubing in the liquid chromatograph. This may require distilling the sample or clarifying with a clarification kit.
3. Apparatus.
3.1. Liquid chromatograph equipped with a UV detector.
3.2. HPLC column that will separate benzene from other components in the bulk sample being analyzed. The column used for validation studies was a Waters uBondapack C18, 30 cm x 3.9 mm.
3.3. A clarification kit to remove any particulates in the bulk if necessary.
3.4. A micro-distillation apparatus to distill any samples if necessary.
3.5. An electronic integrator or some other suitable method of measuring peak areas.
3.6. Microliter syringes-10 uL syringe and other convenient sizes for making standards. 10 uL syringe for sample injections.
3.7. Volumetric flasks, 5 mL and other convenient sizes for preparing standards and making dilutions.
4. Reagents.
4.1. Benzene, reagent grade.
4.2. HPLC grade water , methyl, alcohol, and isopropyl alcohol.
5. Collection and shipment of samples.
5.1. Samples should be transported in glass containers with Teflon-lined caps.
5.2. Samples should not be put in the same container used for air samples.
6. Analysis of samples.
6.1. Sample preparation. If necessary, the samples are distilled or clarified. Samples are analyzed undiluted. If the benzene concentration is out of the working range, suitable dilutions are made with isopropyl alcohol.
6.2. HPLC conditions.
The typical operating conditions for the high performance liquid chromatograph are:

a. Mobile phase -Methyl alcohol/water, 50/50
b. Analytical wavelength -254 mm
c. Injection size -10 uL
6.3. Measurement of peak area and calibration. Peak areas are measured by an integrator or other suitable means. The integrator is calibrated to report results in % benzene by volume.
7. Calculations.
Since the integrator is programmed to report results in % benzene by volume in an undiluted sample, the following equation is used:
% Benzene by Volume = A x
Where: A = % by volume on report, and
B = Dilution factor

(B = 1 for undiluted sample).
8. Backup Data.
8.1. Detection limit -Bulk samples.
The detection limit for the analytical procedure for bulk samples is 0.88 ug, with a coefficient of variation of 0.019 at this level. This amount provided a chromatographic peak that could be identifiable in the presence of possible interferences. The detection limit data were obtained by making 10 uL injections of a 0.10% by volume standard.

_________________________
1.... 45386
2.... 44214
3.... 43822 X = 44040.1
4.... 44062 SD = 852.5
6.... 42724 CV = 0.019
_________________________



8.2. Pooled coefficient of variation -Bulk Samples. The pooled coefficient of variation for the analytical procedure was determined by 50 uL replicate injections of analytical standards. The standards were 0.01, 0.02, 0.04, 0.10, 1.0, and 2.0% benzene by volume.
AREA COUNT (PERCENT)


_____________________________________________________________________
Injection 0.01 0.02 0.04 0.10 1.0 2.0
_____________________________________________________________________
1 45386 84737 166097 448497 4395380 9339150
2 44241 84300 170832 441299 4590800 9484900
3 43822 83835 164160 443719 4593200 9557580
4 44062 84381 164445 444842 4642350 9677060
5 44006 83012 168398 442564 4646430 9766240
6 42724 81957 173002 443975 4646260 ........
X = 44040.1 83703.6 167872 444149 4585767 9564986
SD = 852.5 1042.2 3589.8 2459.1 96839.3 166233
CV = 0.0194 0.0125 0.0213 0.0055 0.0211 0.0174

CV = 0.017
_____________________________________________________________________
_____________________________________________________________________




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.






Appendix E
Qualitative and Quantitative Fit Testing Protocols

[See Section 5144, Appendix A]



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 5219. Ethylene Dibromide (EDB).
(a) Scope and Application.
(1) This section establishes requirements for the control of employee exposure to ethylene dibromide (EDB) including exposures which may result after EDB use as a fumigant. Because of the higher risk of harm due to exposure above the permissible exposure limit, noncompliance with subsections (c), (e) through (k), and (n) constitutes a real and apparent hazard.
(2) This section applies to the manufacture, reaction, packaging, repackaging, storage, transportation, distribution, sale, handling and use of ethylene dibromide.
(3) This section does not apply to the storage, transportation, distribution or sale of EDB in intact containers sealed in such a manner as to prevent the release of EDB vapor or liquid except for the following provisions:
(A) Notification of use and emergencies (subsection (d));
(B) Emergency Procedures (subsection (i));
(C) Training (subsection (j)); and
(D) Posting and notification of shipment (subsection (k)).
(4) This section, with the exception of subsection (c), Permissible Exposure Limit, does not apply to:

(A) The distribution, storage, bulk handling, or use of leaded fuel;
Note: This section applies to the entering of leaded fuel storage tanks.
(B) The handling and storage of EDB-treated materials at or between wholesale and retail establishments provided the requirements of subsection (n), Receipt of EDB-Treated Materials, have been met;
(C) Liquid mixtures that contain less than 0.01% EDB by weight or volume.
(5) This section does not apply to the use of EDB by pest control applicators who are regulated by the California Department of Food and Agriculture. Employees who may be exposed to EDB as a result of the activities of such applicators are covered by this section.
(6) The provisions of this section are subject to the requirements of the Occupational Carcinogens Control Act of 1976 (Health and Safety Code, Division 20, Chapter 2).
(b) Definitions.
Action level. An 8-hour time-weighted average concentration of 15 parts of EDB per billion parts of air by volume (ppb) but not exceeding 130 ppb over any 15- minute period.
Chief. Chief of the Division of Occupational Safety and Health, P.O Box 420603, San Francisco, CA 94142.
First receiver. A retail warehouse, wholesale establishment, or container freight station where any portion of a shipment of EDB-treated material is first unloaded in California.
Shipping container. The smallest unit into which EDB-treated materials are packaged for distribution in commerce in California, for example, a box, crate, or pallet.
Supplier. The shipper or shipper's agent who arranges for shipment of treated materials between the point of treatment and the first receiver under the requirements of (n), Receipt of EDB-Treated Materials.
(c) Permissible Exposure Limit (PEL).

(1) Inhalation. The employer shall assure that no employee is exposed to a concentration of airborne EDB in excess of 130 parts of EDB per billion parts of air by volume (ppb) as an 8-hour, time-weighted average (TWA), and in excess of a ceiling concentration of airborne EDB of 130 ppb, as measured over a 15- minute period.
(2) Dermal and Eye Exposure. The employer shall assure that no employee is exposed to eye or skin contact with liquid EDB or liquid mixtures containing greater than 0.1% EDB by weight.
(d) Reporting of Use and Emergencies. See section 5203.
(e) Exposure Monitoring.
(1) General.
(A) Determinations of exposure levels shall be made from air samples that are representative of each employee's 8-hour time-weighted average and peak exposure to airborne EDB.

(B) For the purpose of this subsection, employee exposure is that exposure which would occur if the employee were not using a respirator.
(2) Initial. Each employer who has a place of employment in which EDB is present shall monitor each such workplace and work operation to accurately determine the 8-hour time-weighted average and peak concentrations of airborne EDB to which employees may be exposed. Such monitoring shall be conducted as soon as possible but not later than 30 days following the effective date of this section or within 30 days following the initial introduction of EDB into the workplace.
(3) Frequency.
(A) If monitoring required by this section reveals employee exposures to be below the action level, no additional monitoring of such employees is necessary other than as required by paragraph (e)(4).
(B) If the monitoring required by this section reveals employee exposures to be below the permissible exposure limit, but at or above the action level, the employer shall repeat exposure measurements representative of each such employee's exposure at least quarterly. The employer shall continue quarterly monitoring until at least two consecutive measurements taken at least seven (7) days apart are below the action level.
(C) If the monitoring required by this section reveals employee exposures to be in excess of the permissible exposure limit, the employer shall repeat exposure measurements representative of each such employee at least monthly. The employer shall continue monthly monitoring until at least two consecutive measurements, taken at least seven (7) days apart, are below the permissible exposure limit. Thereafter the employer shall monitor as required by paragraphs (e)(3) and (e)(4).
(4) Additional. Whenever there has been a production, process, or engineering control change or leak or spill which may result in any new or additional exposure to EDB, or whenever the employer has any reason to suspect new or additional exposures to EDB, the employer shall monitor the employees potentially affected by such change for the purpose of redetermining their exposure. Monitoring shall be conducted as soon as possible but not later than 15 days after the change. Subsequent monitoring shall be in accordance with paragraph (e)(3).
(5) Employee Notification.

(A) Within five (5) working days after the receipt of monitoring results, the employer shall notify each employee in writing, through conspicuous posting or through letter, of the monitoring results which represent the employee's exposure. Posting shall be for at least 30 days.
(B) Whenever the results indicate that employee exposure exceeds the permissible exposure limit, the employer shall include in the written notice a statement that the permissible exposure limit was exceeded and a description of the corrective action being taken to reduce exposure to or below the permissible exposure limit.
(6) Accuracy of Measurement. The employer shall use NIOSH Method No. P&CAM 260 or a method of equivalent accuracy.
(f) Methods of Compliance. Where employee exposure exceeds the limits specified in subsection (c), exposure shall be controlled by the following methods:
(1) Feasible engineering and work practice controls shall immediately be used to reduce exposures.

(2) Where engineering controls are not feasible to control employee exposure within the limits specified in subsection (c), or during the time such controls are being implemented, worker exposure shall be controlled by administrative and work practice controls, and by appropriate personal protective equipment as described in (g) and (h).
(g) Protective Clothing and Equipment.
(1) Provision and Use. Where there is a possibility of eye or skin contact with liquid EDB or liquid mixtures containing greater than 0.1% EDB by weight, the employer shall provide at no cost to the employee, and require that the employee wears, resistant protective clothing and equipment to protect the area of the body which may come into such contact with EDB. Eye and face protection and protective clothing and equipment shall comply with the requirements of Sections 3380, 3382 and 3384 of the General Industry Safety Orders.
(2) Removal and Storage.
(A) The employer shall require that employees promptly remove any protective equipment an clothing which becomes contaminated with EDB-containing liquids. This clothing and equipment shall not be reworn until it has been decontaminated.
(B) EDB-contaminated protective devices and work clothing shall be placed and stored in containers which prevent dispersion of the EDB into the workplace.
(C) Containers of EDB-contaminated protective devices or work clothing shall bear labels with the legend specified under paragraph (k) (2) (B).
(3) Cleaning and Replacement.
(A) The employer shall clean, launder, repair, or replace protective clothing and equipment required by this section to maintain their effectiveness. The employer shall provide uncontaminated protective clothing and equipment to each affected employee as required.
(B) The employer shall inform any person who launders or cleans EDB-contaminated protective clothing or equipment of the potentially harmful effects of exposure to EDB.
(h) Respiratory Protection. Where respiratory protection is required in subsection (f), or during emergencies, respiratory protection shall be provided and used in accordance with General Industry Safety Order 5144 and the following table:

CONCENTRATIONS OF
AIRBORNE EDB OR
CONDITION OF USE RESPIRATOR TYPE [FN1]
(A) Not greater than 0.130 Respirators not required.
ppm
(130 ppb)
(B) Not greater than 1.3 ppm. 1. Any supplied-air respirator; or
(1300 ppb) 2. Any self-contained breathing
apparatus.
(C) Not greater than 6.5 ppm. 1. Any supplied-air respirator
(6500 ppb) with full facepiece, helmet, or
hood; or
2. Any self-contained breathing
apparatus with full facepiece.
(D) Not greater than 130 ppm. A Type C supplied-air respirator
(130,000 ppb) operated in pressure-demand or

the positive pressure or continuous flow mode.
(E) Not greater than 260 ppm. A Type C supplied-air respirator
(260,000 ppb) with full facepiece operated inpressure-de-
mand or other positive pressure mode, or
with full face-piece, helmet, or hood oper-
ated in continuous flow mode.
(F) Greater than 260 ppm or 1.A combination respirator which includes
entry and escape from unknown a Type C supplied-air respirator with
concentrations. full facepiece operated in pressure-demand
or other positive pressure or continuous
flow mode and an auxiliary self-contained
breathing apparatus operated in pressure-
demand or positive pressure mode; or
2. A self-contained breathing apparatus
with full facepiece operated in pressure-
demand mode.
(G) Firefighting A self-contained breathing apparatus with
full facepiece operated in pressure demand
mode.
[FN1] Respirators specified for high concentrations can be used for lower
concentrations of EDB.



(i) Emergency Procedures.
(1) Skin or Eye Contact. When skin or eye contact with liquid EDB or liquid mixtures containing greater than 0.1% EDB by weight occurs, the employer shall assure that affected employees immediately flush contaminated eyes with water for 15 minutes and remove all contaminated clothing and shoes and flush contaminated skin with water. Appropriate medical treatment shall be provided.
Note: For proper selection, installation, and maintenance of emergency wash facilities, consult American National Standards Institute (ANSI) Z358.1-1981.
(2) Written Procedures. Each facility that stores, handles, or otherwise uses liquid EDB or liquid mixtures containing greater than 0.1% EDB by weight shall develop and implement as necessary, a written operation plan such that:
(A) Employees engaged in correcting emergency situations are protected in accordance with this section;
(B) Employees not engaged in correcting emergency situations are evacuated from areas of potential overexposure;
(C) Employees who have eye or kin contact with EDB are decontaminated and given treatment in accordance with paragraph (1) above, and;
(D) Employees who may have inhaled airborne EDB at concentrations greater than the permissible exposure limit are directed to and provided appropriate medical treatment and offered annual medical examinations.
(j) Training.
(1) Each employee who may be exposed at or above the action level regardless of respirator use or work practice, and all employees subject to skin or eye contact with liquid EDB or liquid mixtures containing greater than 0.1% EDB by weight shall be provided a training and education program relating to the hazards of EDB and precautions for its safe use. The employer shall provide initial training prior to working with EDB and at least annually thereafter. The training shall be appropriate to the jobs to which the worker is assigned and presented in a language the employee understands.
(2) The training program shall include and cover:

(A) A Material Safety Data Sheet on EDB or the EDB-containing mixture;
Note: An MSDS for the chemical or pesticide may be obtained from the manufacturer or seller.
(B) Safe work practices on EDB;
(C) The purpose for, proper use, and limitations of respiratory protective devices, if such devices are required;
(D) The purpose for, proper use, and limitations of personal protective clothing and equipment, if such clothing and equipment are required;
(E) The purpose for and a description of the medical surveillance program, if one is required;
(F) Emergency procedures as required by subsection (i);
(G) The interaction of disulfiram (Antabuse) and similar compounds with EDB; and

(H) Section 5219, including employee rights granted by paragraphs (a)(1) and (e)(5).
(I) In addition, for uses of EDB as a pesticide, a copy and discussion of the Hazard Evaluation System and Information Service (HESIS) Hazard Alert on EDB.
Note: The Hazard Alert is available in both English and Spanish from the Hazard Evaluation System and Information Service (HESIS), Departments of Health Services and Industrial Relations, 2151 Berkeley Way, Room 504, Berkeley, CA 94704.
(k) Signs and Notification of Shipment.
(1) General.
(A) The employer may use labels or signs required by other statutes, regulations or ordinances in addition to, or in combination with, signs required by this subsection.
(B) The employer shall assure that no statement appears on or near any sign required by this subsection which contradicts or detracts from the required sign.
(2) Posting.
(A) The employer shall post a precautionary sign in areas where employee exposure may exceed the action level or where liquid EDB or mixtures of greater than 0.1% EDB by weight are transferred or stored.
(B) Intermodal containers containing EDB-treated materials received at marine terminals shall be conspicuously posted at the door end with a notice equivalent to (k)(2)(C) or the Notification of Shipment required by (k)(3).
(C) The employer shall assure that the precautionary signs required by this subsection are readily visible, legible, and understood by the employee. The signs shall bear the following legend in both Spanish and English:
DANGER ETHYLENE DIBROMIDE CANCER HAZARD MAY CAUSE STERILITY IN MALES

For instructions concerning safe work practices, contact your employer.
PELIGRO ETHYLENE DIBROMIDE RIESGO DE CANCER PUEDE CAUSAR ESTERILIDAD A LOS
HOMBRES

Pida a su patron instrucciones para seguridad en el trabajo.
(3) Notification of Shipment. All employers shipping or handling material treated with EDB shall provide the recipient of the material with a written notice informing the recipient that the material was treated with EDB and the date of treatment. The notice shall be provided prior to any handling of the treated material by the recipient.
(l) Recordkeeping. The employer shall establish and maintain an accurate record of all monitoring and medical surveillance required by this section, allow employee access to all such records, and otherwise conform to the requirements set forth in General Industry Safety Order 3204.
(m) Medical Surveillance. A medical surveillance program shall be provided for employees assigned to areas where exposure monitoring required by (e) indicates employees will be exposed at or above the action level. The comprehensive medical examination shall include but not be limited to:

(1) Preassignment and annual examinations.
(2) The employee's personal, reproductive, and family history insofar as these are related to pertinent genetic, occupational, and environmental factors.
(3) A consideration by the physician of whether factors exist which would predispose the employee to increased risk, such as reduced immunological competence, treatment with steroids or cytotoxic agents, pregnancy, and cigarette smoking.
(4) The examining physician shall be provided with:
(A) The HESIS Hazard Alert or MSDS.
(B) A copy of Section 5219, and
(C) Information on the interaction of disulfiram (Antabuse R) and similar compounds with EDB.
(5) Employee medical records shall be retained in accordance with Section 3204.
(n) Receipt of EDB-Treated Materials.
(1) First receivers or suppliers on their behalf shall submit a written application to the Chief for approval which shall include, but not be limited to, the following:
(A) A written plan for packaging and shipping EDB-treated material which will result in exposures of 15 ppb or less over a maximum 30-minute period to employees off-loading such material.
(B) Measurements of airborne levels of EDB taken in the operator's breathing zone demonstrating that exposure to employees will be as specified in (A) for all shipments. Sampling data shall include:
1. Test results for shipments treated with EDB on three different days within one month of the start of treatment each season, if applicable; and
2. One test on any representative shipment per month thereafter.
(C) A plan to make copies of the Appendix available to employees off-loading treated materials.

(2) The supplier shall provide the first receiver with a written notice that the material was treated with EDB and the date of treatment. The notice shall be provided prior to any handling of the treated material by the recipient.
(3) Where the first receiver consolidates EDB-treated materials into intermodal containers, he shall provide the recipient of the intermodal container with a written notice that the material was treated with EDB and the date of treatment. The notice shall be provided prior to any handling of the intermodal container by the recipient.
(4) Shipping containers shall be clearly labeled in 10 point type or larger as follows:
This produce has been fumigated with Ethylene Dibromide (EDB) for the control of fruit fly infestation. Procedures approved by Cal/OSHA have been undertaken by the supplier to assure safe exposure levels at this workplace. For further information contact your employer, Cal/OSHA Consultation Service at 1-800-652- 1476, or your local Cal/OSHA office.
(5) Where the first receiver consolidates EDB-treated materials into intermodal containers, the first receiver shall clearly label the container at the door end with a notice equivalent to that in (n)(3)(A) or the Notification of Shipment required by (k)(3).
(6) In addition to procedures outlined in the shipping plan, (n)(1), trucks hauling materials between treatment and the first receiver shall have:
(A) Trailer vents opened, forward and rear, during the last two hours in transit; and
(B) Trailer doors opened upon arrival.
(7) Failure by suppliers to comply with subsection (n) subjects first receivers, upon notice by the Division, to the full requirements of this section.
Exception: The handling of sealed intermodal containers.The handling of sealed intermodal containers.
Exception: For skin contact with liquid mixtures containing EDB, an appropriate cleaning agent may precede a flush with water.For skin contact with liquid mixtures containing EDB, an appropriate cleaning agent may precede a flush with water.






Appendix
Information for Persons Handling Fresh Produce and Other Materials Treated with Ethylene Dibromide (EDB)
The cartons you will be handling contain fruit that has been fumigated with Ethylene Dibromide (EDB). Fumigation with EDB is done only when it is required by law to prevent the spread of fruit flies that lay eggs on citrus fruit, mangos, and papayas. High concentrations of EDB cause cancer and reproductive problems in animals. Even though these effects have not been seen in humans, special precautions, required by law, have been undertaken to make sure you are exposed to only very low levels of this chemical.
The shipper of this fumigated fruit has applied to the California Division of Occupational Safety and Health (Cal/OSHA) with his plan to pack and ship fruit assuring that when it is unloaded, only trace amounts of EDB will remain in the trailer or shipping container. Cal/OSHA regulations require that truck trailer vents be opened the last two hours on the road and the trailer doors be opened upon arrival.
Fruit shipments handled according to Cal/OSHA's requirements are safe to unload and will have a notice on each carton to confirm this. If you want more information you should consult your employer or call Cal/OSHA (Toll Free) at 1- 800-652-1476.


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 5220. Ethylene Oxide.
(a) Scope and Application.
(1) This section applies to all occupational exposures to ethylene oxide (EtO) except as provided in subsection (a)(2).

(2) This section does not apply to the processing, use, or handling of products made from or containing EtO where objective data demonstrate that the product is not capable of releasing airborne EtO in concentrations at or above the action level under conditions of processing, use, or handling that would reasonably be expected to cause the greatest possible release.
(3) Where a product is exempted pursuant to subsection (a)(2), the employer shall maintain a record of the objective data supporting that exemption and the basis for the employer's reliance on the data, as provided in subsection (k)(1).
(4) Sections 5221 and 5222 also apply where EtO is used in walk-in chambers for fumigation or sterilization purposes.
(5) Every employer using EtO shall report such use(s) to the Chief in accordance with subsection (m) except to the extent that the use of EtO is exempt under the provisions of subsection (a)(2).
(b) Definitions: For the purpose of this section, the following definitions shall apply:
"Action Level." Employee exposure to airborne EtO at an 8-hour time-weighted average concentration of 0.5 part EtO per million parts of air (0.5 ppm).
"Authorized Person." Any person specifically authorized by the employer whose duties require the person to enter a regulated area, or any person entering such an area as a designated representative of employees for the purpose of exercising the right to observe monitoring and measuring procedures under subsection (3).
"Chief." The chief administrative officer of the Division of Occupational Safety and Health, P.O. Box 420603, San Francisco, CA 94142.
"Director." The Director of the National Institute for Occupational Safety and Health, U.S. Department of Health and Human Services, or designee.
"Emergency." Any occurrence such as, but not limited to, equipment failure, rupture of containers, or failure of control equipment that is likely to or does result in an unexpected significant release of EtO.
"Employee Exposure." Exposure to airborne EtO without regard to the employee's use of respiratory protective equipment.
"Ethylene Oxide" or "EtO." The three-membered ring compound with the empirical chemical formula, C2H4O, and Chemical Abstracts Service Register No. 75-21-8.
(c) Permissible Exposure Limit (PEL).
(1) Permissible Exposure Limit (PEL). The employer shall ensure that no employee is exposed to an 8-hour time-weighted average concentration of airborne EtO in excess of one (1) part EtO per million parts of air (1 ppm).
(2) Short Term Exposure Limit (STEL). The employer shall ensure that no employee is exposed to a concentration of airborne EtO in excess of 5 parts of EtO per million parts of air (5 ppm) as averaged over a sampling period of fifteen (15) minutes.
(d) Exposure Monitoring.
(1) General.
(A) Determinations of employee exposure shall be made from breathing zone air samples that are representative of the 8-hour time-weighted average exposure of each employee.
(B) Determinations of representative employee exposure shall be based on oneor more samples representing full-shift exposure for each shift for each job classification in each work area. (continued)