General Occupational Health Standards

Table of Contents



Air Contaminants (Specific)
Chapter 296-62 WAC, Part I (Continued)

WAC 296-62-07544 Appendix B--Sampling strategy and analytical methods for formaldehyde.

(1) To protect the health of employees, exposure measurements must be unbiased and representative of employee exposure. The proper measurement of employee exposure requires more than a token commitment on the part of the employer. WISHA's mandatory requirements establish a baseline; under the best of circumstances all questions regarding employee exposure will be answered. Many employers, however, will wish to conduct more extensive monitoring before undertaking expensive commitments, such as engineering controls to assure that the modifications are truly necessary. The following sampling strategy, which was developed at NIOSH by Nelson A. Leidel, Kenneth A. Busch, and Jeremiah R. Lynch and described in NIOSH publication No. 77-173 (Occupational Exposure Sampling Strategy Manual) will assist the employer in developing a strategy for determining the exposure of his or her employees.

(2) There is no one correct way to determine employee exposure. Obviously, measuring the exposure of every employee exposed to formaldehyde will provide the most information on any given day. Where few employees are exposed, this may be a practical solution. For most employers, however, use of the following strategy will give just as much information at less cost.

(3) Exposure data collected on a single day will not automatically guarantee the employer that his or her workplace is always in compliance with the formaldehyde standard. This does not imply, however, that it is impossible for an employer to be sure that his or her worksite is in compliance with the standard.

Indeed, a properly designed sampling strategy showing that all employees are exposed below the PELs, at least with a ninety-five percent certainty, is compelling evidence that the exposure limits are being achieved provided that measurements are conducted using valid sampling strategy and approved analytical methods.

(4) There are two PELs, the TWA concentration and the STEL.

(a) Most employers will find that one of these two limits is more critical in the control of their operations, and WISHA expects that the employer will concentrate monitoring efforts on the critical component.

(b) If the more difficult exposure is controlled, this information, along with calculations to support the assumptions, should be adequate to show that the other exposure limit is also being achieved.

(5) Sampling strategy.

(a) Determination of the need for exposure measurements.

(b) The employer must determine whether employees may be exposed to concentrations in excess of the action level. This determination becomes the first step in an employee exposure monitoring program that minimizes employer sampling burdens while providing adequate employee protection.

(c) If employees may be exposed above the action level, the employer must measure exposure. Otherwise, an objective determination that employee exposure is low provides adequate evidence that exposure potential has been examined.

(d) The employer should examine all available relevant information, e.g., insurance company and trade association data and information from suppliers or exposure data collected from similar operations.

(e) The employer may also use previously-conducted sampling including area monitoring. The employer must make a determination relevant to each operation although this need not be on a separate piece of paper.

(f) If the employer can demonstrate conclusively that no employee is exposed above the action level or the STEL through the use of objective data, the employer need proceed no further on employee exposure monitoring until such time that conditions have changed and the determination is no longer valid.

(g) If the employer cannot determine that employee exposure is less than the action level and the STEL, employee exposure monitoring will have to be conducted.

(6) Workplace material survey.

(a) The primary purpose of a survey of raw material is to determine if formaldehyde is being used in the work environment and if so, the conditions under which formaldehyde is being used.

(b) The first step is to tabulate all situations where formaldehyde is used in a manner such that it may be released into the workplace atmosphere or contaminate the skin. This information should be available through analysis of company records and information on the MSDSs available through provisions of this standard and the hazard communication standard.

(c) If there is an indication from materials handling records and accompanying MSDSs that formaldehyde is being used in the following types of processes or work operations, there may be a potential for releasing formaldehyde into the workplace atmosphere:

(i) Any operation that involves grinding, sanding, sawing, cutting, crushing, screening, sieving, or any other manipulation of material that generates formaldehyde-bearing dust.

(ii) Any processes where there have been employee complaints or symptoms indicative of exposure to formaldehyde.

(iii) Any liquid or spray process involving formaldehyde.

(iv) Any process that uses formaldehyde in preserved tissue.

(v) Any process that involves the heating of a formaldehyde-bearing resin.

Processes and work operations that use formaldehyde in these manners will probably require further investigation at the worksite to determine the extent of employee monitoring that should be conducted.

(7) Workplace observations.

(a) To this point, the only intention has been to provide an indication as to the existence of potentially exposed employees. With this information, a visit to the workplace is needed to observe work operations, to identify potential health hazards, and to determine whether any employees may be exposed to hazardous concentrations of formaldehyde.

(b) In many circumstances, sources of formaldehyde can be identified through the sense of smell. However, this method of detection should be used with caution because of olfactory fatigue.

(c) Employee location in relation to source of formaldehyde is important in determining if an employee may be significantly exposed to formaldehyde. In most instances, the closer a worker is to the source, the higher the probability that a significant exposure will occur.

(d) Other characteristics should be considered. Certain high temperature operations give rise to higher evaporation rates. Locations of open doors and windows provide natural ventilation that tend to dilute formaldehyde emissions. General room ventilation also provides a measure of control.

(8) Calculation of potential exposure concentrations.

(a) By knowing the ventilation rate in a workplace and the quantity of formaldehyde generated, the employer may be able to determine by calculation if the PELs might be exceeded.

(b) To account for poor mixing of formaldehyde into the entire room, locations of fans and proximity of employees to the work operation, the employer must include a safety factor.

(c) If an employee is relatively close to a source, particularly if he or she is located downwind, a safety factor of one hundred may be necessary.

(d) For other situations, a factor of ten may be acceptable. If the employer can demonstrate through such calculations that employee exposure does not exceed the action level or the STEL, the employer may use this information as objective data to demonstrate compliance with the standard.

(9) Sampling strategy.

(a) Once the employer determines that there is a possibility of substantial employee exposure to formaldehyde, the employer is obligated to measure employee exposure.

(b) The next step is selection of a maximum risk employee. When there are different processes where employees may be exposed to formaldehyde, a maximum risk employee should be selected for each work operation.

(c) Selection of the maximum risk employee requires professional judgment. The best procedure for selecting the maximum risk employee is to observe employees and select the person closest to the source of formaldehyde. Employee mobility may affect this selection; e.g., if the closest employee is mobile in his tasks, he may not be the maximum risk employee. Air movement patterns and differences in work habits will also affect selection of the maximum risk employee.

(d) When many employees perform essentially the same task, a maximum risk employee cannot be selected. In this circumstance, it is necessary to resort to random sampling of the group of workers. The objective is to select a subgroup of adequate size so that there is a high probability that the random sample will contain at least one worker with high exposure if one exists. The number of persons in the group influences the number that need to be sampled to ensure that at least one individual from the highest ten percent exposure group is contained in the sample. For example, to have ninety percent confidence in the results, if the group size is ten, nine should be sampled; for fifty, only eighteen need to be sampled.

(e) If measurement shows exposure to formaldehyde at or above the action level or the STEL, the employer needs to identify all other employees who may be exposed at or above the action level or STEL and measure or otherwise accurately characterize the exposure of these employees.

(f) Whether representative monitoring or random sampling are conducted, the purpose remains the same to determine if the exposure of any employee is above the action level. If the exposure of the most exposed employee is less than the action level and the STEL, regardless of how the employee is identified, then it is reasonable to assume that measurements of exposure of the other employees in that operation would be below the action level and the STEL.

(10) Exposure measurements.

(a) There is no “best” measurement strategy for all situations. Some elements to consider in developing a strategy are:

(i) Availability and cost of sampling equipment;

(ii) Availability and cost of analytic facilities;

(iii) Availability and cost of personnel to take samples;

(iv) Location of employees and work operations;

(v) Intraday and interday variations in the process;

(vi) Precision and accuracy of sampling and analytic methods; and

(vii) Number of samples needed.

(b) Samples taken for determining compliance with the STEL differ from those that measure the TWA concentration in important ways. STEL samples are best taken in a nonrandom fashion using all available knowledge relating to the area, the individual, and the process to obtain samples during periods of maximum expected concentrations. At least three measurements on a shift are generally needed to spot gross errors or mistakes; however, only the highest value represents the STEL.

(c) If an operation remains constant throughout the workshift, a much greater number of samples would need to be taken over the thirty-two discrete nonoverlapping periods in an 8-hour workshift to verify compliance with a STEL. If employee exposure is truly uniform throughout the workshift, however, an employer in compliance with the 1 ppm TWA would be in compliance with the 2 ppm STEL, and this determination can probably be made using objective data.

(11) Need to repeat the monitoring strategy.

(a) Interday and intraday fluctuations in employee exposure are mostly influenced by the physical processes that generate formaldehyde and the work habits of the employee. Hence, in-plant process variations influence the employer's determination of whether or not additional controls need to be imposed. Measurements that employee exposure is low on a day that is not representative of worst conditions may not provide sufficient information to determine whether or not additional engineering controls should be installed to achieve the PELs.

(b) The person responsible for conducting sampling must be aware of systematic changes which will negate the validity of the sampling results. Systematic changes in formaldehyde exposure concentration for an employee can occur due to:

(i) The employee changing patterns of movement in the workplace;

(ii) Closing of plant doors and windows;

(iii) Changes in ventilation from season to season;

(iv) Decreases in ventilation efficiency or abrupt failure of engineering control equipment; and

(v) Changes in the production process or work habits of the employee.

(c) Any of these changes, if they may result in additional exposure that reaches the next level of action (i.e., 0.5 or 1.0 ppm as an 8-hour average or 2 ppm over fifteen minutes) require the employer to perform additional monitoring to reassess employee exposure.

(d) A number of methods are suitable for measuring employee exposure to formaldehyde or for characterizing emissions within the worksite. The preamble to this standard describes some methods that have been widely used or subjected to validation testing. A detailed analytical procedure derived from the WISHA Method A.C.R.O. for acrolein and formaldehyde is presented below for informational purposes.

(e) Inclusion of WISHA's method in this appendix in no way implies that it is the only acceptable way to measure employee exposure to formaldehyde. Other methods that are free from significant interferences and that can determine formaldehyde at the permissible exposure limits within .25 percent of the “true” value at the ninety-five percent confidence level are also acceptable. Where applicable, the method should also be capable of measuring formaldehyde at the action level to 35 percent of the “true” value with a ninety-five percent confidence level. WISHA encourages employers to choose methods that will be best for their individual needs. The employer must exercise caution, however, in choosing an appropriate method since some techniques suffer from interferences that are likely to be present in workplaces of certain industry sectors where formaldehyde is used.

(12) WISHA's analytical laboratory method.

A.C.R.O. (also use methods F.O.R.M. and F.O.R.M. 2 when applicable).

(a) Matrix: Air.

(b) Target concentration: 1 ppm (1.2 mg/m3).

(c) Procedures: Air samples are collected by drawing known volumes of air through sampling tubes containing XAD-2 adsorbent which have been coated with 2-(hydroxymethyl) piperidine. The samples are desorbed with toluene and then analyzed by gas chromatography using a nitrogen selective detector.

(d) Recommended sampling rate and air volumes: 0.1 L/min and 24 L.

(e) Reliable quantitation limit: 16 ppb (20 g/m3).

(f) Standard error of estimate at the target concentration: 7.3%.

(g) Status of the method: A sampling and analytical method that has been subjected to the established evaluation procedures of the organic methods evaluation branch.

(h) Date: March, 1985.

(13) General discussion.

(a) Background: The current WISHA method for collecting acrolein vapor recommends the use of activated 13X molecular sieves. The samples must be stored in an ice bath during and after sampling and also they must be analyzed within forty-eight hours of collection. The current WISHA method for collecting formaldehyde vapor recommends the use of bubblers containing ten percent methanol in water as the trapping solution.

(b) This work was undertaken to resolve the sample stability problems associated with acrolein and also to eliminate the need to use bubblers to sample formaldehyde. A goal of this work was to develop and/or to evaluate a common sampling and analytical procedure for acrolein and formaldehyde.

(c) NIOSH has developed independent methodologies for acrolein and formaldehyde which recommend the use of reagent-coated adsorbent tubes to collect the aldehydes as stable derivatives. The formaldehyde sampling tubes contain Chromosorb 102 adsorbent coated with N-benzylethanolamine (BEA) which reacts with formaldehyde vapor to form a stable oxazolidine compound. The acrolein sampling tubes contain XAD-2 adsorbent coated with 2-(hydroxymethyl) piperidine (2-HMP) which reacts with acrolein vapor to form a different, stable oxazolidine derivative. Acrolein does not appear to react with BEA to give a suitable reaction product. Therefore, the formaldehyde procedure cannot provide a common method for both aldehydes. However, formaldehyde does react with 2-HMP to form a very suitable reaction product. It is the quantitative reaction of acrolein and formaldehyde with 2-HMP that provides the basis for this evaluation.

(d) This sampling and analytical procedure is very similar to the method recommended by NIOSH for acrolein. Some changes in the NIOSH methodology were necessary to permit the simultaneous determination of both aldehydes and also to accommodate WISHA laboratory equipment and analytical techniques.

(14) Limit-defining parameters: The analyte air concentrations reported in this method are based on the recommended air volume for each analyte collected separately and a desorption volume of 1 mL. The amounts are presented as acrolein and/or formaldehyde, even though the derivatives are the actual species analyzed.

(15) Detection limits of the analytical procedure: The detection limit of the analytical procedure was 386 pg per injection for formaldehyde. This was the amount of analyte which gave a peak whose height was about five times the height of the peak given by the residual formaldehyde derivative in a typical blank front section of the recommended sampling tube.

(16) Detection limits of the overall procedure: The detection limits of the overall procedure were 482 ng per sample (16 ppb or 20 g/m3 for formaldehyde). This was the amount of analyte spiked on the sampling device which allowed recoveries approximately equal to the detection limit of the analytical procedure.

(17) Reliable quantitation limits:

(a) The reliable quantitation limit was 482 ng per sample (16 ppb or 20 g/m3) for formaldehyde. These were the smallest amounts of analyte which could be quantitated within the limits of a recovery of at least seventy-five percent and a precision (1.96 SD) of 25% or better.

(b) The reliable quantitation limit and detection limits reported in the method are based upon optimization of the instrument for the smallest possible amount of analyte. When the target concentration of an analyte is exceptionally higher than these limits, they may not be attainable at the routine operating parameters.

(18) Sensitivity: The sensitivity of the analytical procedure over concentration ranges representing 0.4 to 2 times the target concentration, based on the recommended air volumes, was seven thousand five hundred eighty-nine area units per mg/mL for formaldehyde. This value was determined from the slope of the calibration curve. The sensitivity may vary with the particular instrument used in the analysis.

(19) Recovery: The recovery of formaldehyde from samples used in an eighteen-day storage test remained above ninety-two percent when the samples were stored at ambient temperature. These values were determined from regression lines which were calculated from the storage data. The recovery of the analyte from the collection device must be at least seventy-five percent following storage.

(20) Precision (analytical method only): The pooled coefficient of variation obtained from replicate determinations of analytical standards over the range of 0.4 to 2 times the target concentration was 0.0052 for formaldehyde ((d)(C)(iii) of this subsection).

(21) Precision (overall procedure): The precision at the ninety-five percent confidence level for the ambient temperature storage tests was 14.3% for formaldehyde. These values each include an additional 5% for sampling error. The overall procedure must provide results at the target concentrations that are 25% at the ninety-five percent confidence level.

(22) Reproducibility: Samples collected from controlled test atmospheres and a draft copy of this procedure were given to a chemist unassociated with this evaluation. The formaldehyde samples were analyzed following fifteen days storage. The average recovery was 96.3% and the standard deviation was 1.7%.

(23) Advantages:

(a) The sampling and analytical procedures permit the simultaneous determination of acrolein and formaldehyde.

(b) Samples are stable following storage at ambient temperature for at least eighteen days.

(24) Disadvantages: None.

(25) Sampling procedure.

(a) Apparatus:

(i) Samples are collected by use of a personal sampling pump that can be calibrated to within 5% of the recommended 0.1 L/min sampling rate with the sampling tube in line.

(ii) Samples are collected with laboratory prepared sampling tubes. The sampling tube is constructed of silane treated glass and is about 8-cm long. The ID is 4 mm and the OD is 6 mm. One end of the tube is tapered so that a glass wool end plug will hold the contents of the tube in place during sampling. The other end of the sampling tube is open to its full 4-mm ID to facilitate packing of the tube. Both ends of the tube are fire-polished for safety.

The tube is packed with a 75-mg backup section, located nearest the tapered end and a 150-mg sampling section of pretreated XAD-2 adsorbent which has been coated with 2-HMP. The two sections of coated adsorbent are separated and retained with small plugs of silanized glass wool. Following packing, the sampling tubes are sealed with two 7/32 inch OD plastic and caps. Instructions for the pretreatment and the coating of XAD-2 adsorbent are presented in (d) of this subsection.

(b) Sampling tubes, similar to those recommended in this method, are marketed by Supelco, Inc. These tubes were not available when this work was initiated; therefore, they were not evaluated.

(26) Reagents: None required.

(27) Technique:

(a) Properly label the sampling tube before sampling and then remove the plastic end caps.

(b) Attach the sampling tube to the pump using a section of flexible plastic tubing such that the large, front section of the sampling tube is exposed directly to the atmosphere. Do not place any tubing ahead of the sampling tube. The sampling tube should be attached in the worker's breathing zone in a vertical manner such that it does not impede work performance.

(c) After sampling for the appropriate time, remove the sampling tube from the pump and then seal the tube with plastic end caps.

(d) Include at least one blank for each sampling set. The blank should be handled in the same manner as the samples with the exception that air is not drawn through it.

(e) List any potential interferences on the sample data sheet.

 

(28) Breakthrough:

(a) Breakthrough was defined as the relative amount of analyte found on a backup sample in relation to the total amount of analyte collected on the sampling train.

(b) For formaldehyde collected from test atmospheres containing six times the PEL, the average five percent breakthrough air volume was 41 L. The sampling rate was 0.1 L/min and the average mass of formaldehyde collected was 250 mg.

(29) Desorption efficiency: No desorption efficiency corrections are necessary to compute air sample results because analytical standards are prepared using coated adsorbent. Desorption efficiencies were determined, however, to investigate the recoveries of the analytes from the sampling device. The average recovery over the range of 0.4 to 2 times the target concentration, based on the recommended air volumes, was 96.2% for formaldehyde. Desorption efficiencies were essentially constant over the ranges studied.

(30) Recommended air volume and sampling rate:

(a) The recommended air volume for formaldehyde is 24 L.

(b) The recommended sampling rate is 0.1 L/min.

(31) Interferences:

(a) Any collected substance that is capable of reacting with 2-HMP and thereby depleting the derivatizing agent is a potential interference. Chemicals which contain a carbonyl group, such as acetone, may be capable of reacting with 2-HMP.

(b) There are no other known interferences to the sampling method.

(32) Safety precautions:

(a) Attach the sampling equipment to the worker in such a manner that it will not interfere with work performance or safety.

(b) Follow all safety practices that apply to the work area being sampled.

(33) Analytical procedure.

(a) Apparatus:

(i) A gas chromatograph (GC), equipped with a nitrogen selective detector. A Hewlett-Packard model 5840A GC fitted with a nitrogen phosphorus flame ionization detector (NPD) was used for this evaluation. Injections were performed using a Hewlett-Packard model 7671A automatic sampler.

(ii) A GC column capable of resolving the analytes from any interference. A 6 ft x 1/4 in OD (2mm ID) glass GC column containing 10% UCON 50-HB-5100 + 2% KOH on 80/100 mesh Chromosorb W-AW was used for the evaluation. Injections were performed on-column.

(iii) Vials, glass 2-mL with Teflonlined caps.

(iv) Volumetric flasks, pipets, and syringes for preparing standards, making dilutions, and performing injections.

(b) Reagents:

(i) Toluene and dimethylformamide. Burdick and Jackson solvents were used in this evaluation.

(ii) Helium, hydrogen, and air, GC grade.

(iii) Formaldehyde, thirty-seven percent by weight, in water. Aldrich Chemical, ACS Reagent Grade formaldehyde was used in this evaluation.

(iv) Amberlite XAD-2 adsorbent coated with 2-(hydroxymethyl) piperidine (2-HMP), 10% by weight ((d) of this subsection).

(v) Desorbing solution with internal standard. This solution was prepared by adding 20 uL of dimethylformamide to 100 mL of toluene.

(c) Standard preparation:

(i) Formaldehyde: Prepare stock standards by diluting known volumes of thirty-seven percent formaldehyde solution with methanol. A procedure to determine the formaldehyde content of these standards is presented in (d) of this subsection. A standard containing 7.7 mg/mL formaldehyde was prepared by diluting 1 mL of the thirty-seven percent reagent to 50 mL with methanol.

(ii) It is recommended that analytical standards be prepared about sixteen hours before the air samples are to be analyzed in order to ensure the complete reaction of the analytes with 2-HMP. However, rate studies have shown the reaction to be greater than ninety-five percent complete after four hours. Therefore, one or two standards can be analyzed after this reduced time if sample results are outside the concentration range of the prepared standards.

(iii) Place 150-mg portions of coated XAD-2 adsorbent, from the same lot number as used to collect the air samples, into each of several glass 2-mL vials. Seal each vial with a Teflonlined cap.

(iv) Prepare fresh analytical standards each day by injecting appropriate amounts of the diluted analyte directly onto 150-mg portions of coated adsorbent. It is permissible to inject both acrolein and formaldehyde on the same adsorbent portion. Allow the standards to stand at room temperature. A standard, approximately the target levels, was prepared by injecting 11 uL of the acrolein and 12 uL of the formaldehyde stock standards onto a single coated XAD-2 adsorbent portion.

(v) Prepare a sufficient number of standards to generate the calibration curves. Analytical standard concentrations should bracket sample concentrations. Thus, if samples are not in the concentration range of the prepared standards, additional standards must be prepared to determine detector response.

(vi) Desorb the standards in the same manner as the samples following the sixteen-hour reaction time.

(d) Sample preparation:

(i) Transfer the 150-mg section of the sampling tube to a 2-mL vial. Place the 75-mg section in a separate vial. If the glass wool plugs contain a significant number of dsorbent beads, place them with the appropriate sampling tube section. Discard the glass wool plugs if they do not contain a significant number of adsorbent beads.

(ii) Add 1 mL of desorbing solution to each vial.

(iii) Seal the vials with Teflonlined caps and then allow them to desorb for one hour. Shake the vials by hand with vigorous force several times during the desorption time.

(iv) Save the used sampling tubes to be cleaned and recycled.

(e) Analysis:

(f) GC conditions.

(34) Column temperature:

(a) Bi-level temperature program.

(i) First level: 100C to 140C at 4C/min following completion of the first level.

(ii) Second level: 140C to 180C at 20C/min following completion of the first level.

(b) Isothermal period: Hold column at 180C until the recorder pen returns to baseline (usually about twenty-five minutes after injection).

(c) Injector temperature: 180C.

(d) Helium flow rate: 30 mL/min (detector response will be reduced if nitrogen is substituted for helium carrier gas).

(e) Injection volume: 51 0.8 uL.

(f) GC column: Six-ft x 1/4-in OD (2 mm ID) glass GC column containing 10% UCON 50-HB-5100NZG651+512% KOH on 80/100 Chromosorb W-AW.

(g) NPD conditions:

(i) Hydrogen flow rate: 3 mL/min.

(ii) Air flow rate: 50 mL/min.

(h) Detector temperature: 275 5151C.

(i) Use a suitable method, such as electronic integration, to measure detector response.

(ii) Use an internal standard method to prepare the calibration curve with several standard solutions of different concentrations. Prepare the calibration curve daily. Program the integrator to report results in mg/mL.

(iii) Bracket sample concentrations with standards.

(iv) Interferences (analytical).

(A) Any compound with the same general retention time as the analytes and which also gives a detector response is a potential interference. Possible interferences should be reported to the laboratory with submitted samples by the industrial hygienist.

(B) GC parameters (temperature, column, etc.), may be changed to circumvent interferences.

(C) A useful means of structure designation is GC/MS. It is recommended this procedure be used to confirm samples whenever possible.

(D) The coated adsorbent usually contains a very small amount of residual formaldehyde derivative.

(i) Calculations:

(i) Results are obtained by use of calibration curves. Calibration curves are prepared by plotting detector response against concentration for each standard. The best line through the data points is determined by curve fitting.

(ii) The concentration, in mg/mL, for a particular sample is determined by comparing its detector response to the calibration curve. If either of the analytes is found on the backup section, it is added to the amount found on the front section. Blank corrections should be performed before adding the results together.

(iii) The acrolein and/or formaldehyde air concentration can be expressed using the following equation:

Mg/m3 = (A)(B)/C.

where A = g/mL from 3.7.2, B = desorption volume, and C = L of air sampled.

No desorption efficiency corrections are required.

(iv) The following equation can be used to convert results in mg/m51351 to ppm.

ppm = (mg/m3)(24.45)/MW

where mg/m3 = result from 3.7.3, 24.45 = molar volume of an ideal gas at 760 mm Hg and 25 5151C, MW = molecular weight (Formaldehyde = 30.0).

(j) Backup data. Backup data on detection limits, reliable quantitation limits, sensitivity and precision of the analytical method, breakthrough, desorption efficiency, storage, reproducibility, and generation of test atmospheres are available in OSHA Method 52, developed by the Organics Methods Evaluation Branch, OSHA Analytical Laboratory, Salt Lake City, Utah.

(k) Procedure to coat XAD-2 adsorbent with 2-HMP:

(i) Apparatus: Soxhlet extraction apparatus, rotary evaporation apparatus, vacuum dessicator, 1-L vacuum flask, 1-L round-bottomed evaporative flask, 1-L Erlenmeyer flask, 250-mL Buchner funnel with a coarse fritted disc, etc.

(ii) Reagents:

(A) Methanol, isooctane, and toluene.

(B) (Hydroxymethyl) piperidine.

(C) Amberlite XAD-2 nonionic polymeric adsorbent, twenty to sixty mesh, Aldrich Chemical XAD-2 was used in this evaluation.

(l) Procedure: Weigh 125 g of crude XAD-2 adsorbent into a 1-L Erlenmeyer flask. Add about 200 mL of water to the flask and then swirl the mixture to wash the adsorbent. Discard any adsorbent that floats to the top of the water and then filter the mixture using a fritted Buchner funnel. Air dry the adsorbent for two minutes. Transfer the adsorbent back to the Erlenmeyer flask and then add about 200 mL of methanol to the flask. Swirl and then filter the mixture as before. Transfer the washed adsorbent back to the Erlenmeyer flask and then add about 200 mL of methanol to the flask. Swirl and then filter the mixture as before. Transfer the washed adsorbent to a 1-L round-bottomed evaporative flask, add 13 g of 2-HMP and then 200 mL of methanol, swirl the mixture and then allow it to stand for one hour. Remove the methanol at about 40oC and reduced pressure using a rotary evaporation apparatus. Transfer the coated adsorbent to a suitable container and store it in a vacuum desiccator at room temperature overnight. Transfer the coated adsorbent to a Soxhlet extractor and then extract the material with toluene for about twenty-four hours. Discard the contaminated toluene, add methanol in its place and then continue the Soxhlet extraction for an additional four hours. Transfer the adsorbent to a weighted 1-L round-bottom evaporative flask and remove the methanol using the rotary evaporation apparatus. Determine the weight of the adsorbent and then add an amount of 2-HMP, which is ten percent by weight of the adsorbent. Add 200 mL of methanol and then swirl the mixture. Allow the mixture to stand for one hour. Remove the methanol by rotary evaporation. Transfer the coated adsorbent to a suitable container and store it in a vacuum dessicator until all traces of solvents are gone. Typically, this will take two to three days. The coated adsorbent should be protected from contamination. XAD-2 adsorbent treated in this manner will probably not contain residual acrolein derivative. However, this adsorbent will often contain residual formaldehyde derivative levels of about 0.1 mg per 150 mg of adsorbent. If the blank values for a batch of coated adsorbent are too high, then the batch should be returned to the Soxhlet extractor, extracted with toluene again and then recoated. This process can be repeated until the desired blank levels are attained.

The coated adsorbent is now ready to be packed into sampling tubes. The sampling tubes should be stored in a sealed container to prevent contamination. Sampling tubes should be stored in the dark at room temperature. The sampling tubes should be segregated by coated adsorbent lot number. A sufficient amount of each lot number of coated adsorbent should be retained to prepare analytical standards for use with air samples from that lot number.

(m) A procedure to determine formaldehyde by acid titration:

(i) Standardize the 0.1 N HC1 solution using sodium carbonate and methyl orange indicator.

(ii) Place 50 mL of 0.1 M sodium sulfite and three drops of thymophthalein indicator into a 250-mL Erlenmeyer flask. Titrate the contents of the flask to a colorless endpoint with 0.1 N HC1 (usually one or two drops is sufficient). Transfer 10 mL of the formaldehyde/methanol solution ((b)(iii)(A) of this subsection) into the same flask and titrate the mixture with 0.1 N HC1, again, to a colorless endpoint. The formaldehyde concentration of the standard may be calculated by the following equation:

acid titer x acid normality x 30.0

Formaldehyde, mg/mL =

mL of Sample

(iii) This method is based on the quantitative liberation of sodium hydroxide when formaldehyde reacts with sodium sulfite to form the formaldehyde-bisulfite addition product. The volume of sample may be varied depending on the formaldehyde content but the solution to be titrated must contain excess sodium sulfite. Formaldehyde solutions containing substantial amounts of acid or base must be neutralized before analysis.

[Statutory Authority: Chapter 49.17 RCW. 91-11-070 (Order 91-01), 296-62-07544, filed 5/20/91, effective 6/20/91; 90-03-029 (Order 89-20), 296-62-07544, filed 1/11/90, effective 2/26/90; 89-11-035 (Order 89-03), 296-62-07544, filed 5/15/89, effective 6/30/89; 88-21-002 (Order 88-23), 296-62-07544, filed 10/6/88, effective 11/7/88.]

 

WAC 296-62-07546 Appendix C medical surveillance--Formaldehyde.

(1) Health hazards. The occupational health hazards of formaldehyde are primarily due to its toxic effects after inhalation, after direct contact with the skin or eyes by formaldehyde in liquid or vapor form, and after ingestion.

(2) Toxicology.

(a) Acute effects of exposure.

(i) Inhalation (breathing): Formaldehyde is highly irritating to the upper airways. The concentration of formaldehyde that is immediately dangerous to life and health is 100 ppm. Concentrations above 50 ppm can cause severe pulmonary reactions within minutes. These include pulmonary edema, pneumonia, and bronchial irritation which can result in death. Concentrations above 5 ppm readily cause lower airway irritation characterized by cough, chest tightness, and wheezing. There is some controversy regarding whether formaldehyde gas is a pulmonary sensitizer which can cause occupational asthma in a previously normal individual. Formaldehyde can produce symptoms of bronchial asthma in humans. The mechanism may be either sensitization of the individual by exposure to formaldehyde or direct irritation by formaldehyde in persons with preexisting asthma. Upper airway irritation is the most common respiratory effect reported by workers and can occur over a wide range of concentrations, most frequently above 1 ppm. However, airway irritation has occurred in some workers with exposures to formaldehyde as low as 0.1 ppm. Symptoms of upper airway irritation include dry or sore throat, itching and burning sensations of the nose, and nasal congestion. Tolerance to this level of exposure may develop within one to two hours. This tolerance can permit workers remaining in an environment of gradually increasing formaldehyde concentrations to be unaware of their increasingly hazardous exposure.

(ii) Eye contact: Concentrations of formaldehyde between 0.05 ppm and 0.5 ppm produce a sensation of irritation in the eyes with burning, itching, redness, and tearing. Increased rate of blinking and eye closure generally protects the eye from damage at these low levels, but these protective mechanisms may interfere with some workers' work abilities. Tolerance can occur in workers continuously exposed to concentrations of formaldehyde in this range. Accidental splash injuries of human eyes to aqueous solutions of formaldehyde (formalin) have resulted in a wide range of ocular injuries including corneal opacities and blindness. The severity of the reactions have been directly dependent on the concentration of formaldehyde in solution and the amount of time lapsed before emergency and medical intervention.

(iii) Skin contact: Exposure to formaldehyde solutions can cause irritation of the skin and allergic contact dermatitis. These skin diseases and disorders can occur at levels well below those encountered by many formaldehyde workers. Symptoms include erythema, edema, and vesiculation or hives. Exposure to liquid formalin or formaldehyde vapor can provoke skin reactions in sensitized individuals even when airborne concentrations of formaldehyde are well below 1 ppm.

(iv) Ingestion: Ingestion of as little as 30 ml of a thirty-seven percent solution of formaldehyde (formalin) can result in death. Gastrointestinal toxicity after ingestion is most severe in the stomach and results in symptoms which can include nausea, vomiting, and severe abdominal pain. Diverse damage to other organ systems including the liver, kidney, spleen, pancreas, brain, and central nervous systems can occur from the acute response to ingestion of formaldehyde.

(b) Chronic effects of exposure. Long-term exposure to formaldehyde has been shown to be associated with an increased risk of cancer of the nose and accessory sinuses, nasopharyngeal and oropharyngeal cancer, and lung cancer in humans. Animal experiments provide conclusive evidence of a causal relationship between nasal cancer in rats and formaldehyde exposure. Concordant evidence of carcinogenicity includes DNA binding, genotoxicity in short-term tests, and cytotoxic changes in the cells of the target organ suggesting both preneoplastic changes and a dose-rate effect. Formaldehyde is a complete carcinogen and appears to exert an effect on at least two stages of the carcinogenic process.

(3) Surveillance considerations.

(a) History.

(i) Medical and occupational history: Along with its acute irritative effects, formaldehyde can cause allergic sensitization and cancer. One of the goals of the work history should be to elicit information on any prior or additional exposure to formaldehyde in either the occupational or the nonoccupational setting.

(ii) Respiratory history: As noted above, formaldehyde has recognized properties as an airway irritant and has been reported by some authors as a cause of occupational asthma. In addition, formaldehyde has been associated with cancer of the entire respiratory system of humans. For these reasons, it is appropriate to include a comprehensive review of the respiratory system in the medical history. Components of this history might include questions regarding dyspnea on exertion, shortness of breath, chronic airway complaints, hyperreactive airway disease, rhinitis, bronchitis, bronchiolitis, asthma, emphysema, respiratory allergic reaction, or other preexisting pulmonary disease.

In addition, generalized airway hypersensitivity can result from exposures to a single sensitizing agent. The examiner should, therefore, elicit any prior history of exposure to pulmonary irritants, and any short-term or long-term effects of that exposure.

Smoking is known to decrease mucociliary clearance of materials deposited during respiration in the nose and upper airways. This may increase a worker's exposure to inhaled materials such as formaldehyde vapor. In addition, smoking is a potential confounding factor in the investigation of any chronic respiratory disease, including cancer. For these reasons, a complete smoking history should be obtained.

(iii) Skin disorders: Because of the dermal irritant and sensitizing effects of formaldehyde, a history of skin disorders should be obtained. Such a history might include the existence of skin irritation, previously documented skin sensitivity, and other dermatologic disorders. Previous exposure to formaldehyde and other dermal sensitizers should be recorded.

(iv) History of atopic or allergic diseases: Since formaldehyde can cause allergic sensitization of the skin and airways, it might be useful to identify individuals with prior allergen sensitization. A history of atopic disease and allergies to formaldehyde or any other substances should also be obtained. It is not definitely known at this time whether atopic diseases and allergies to formaldehyde or any other substances should also be obtained. Also it is not definitely known at this time whether atopic individuals have a greater propensity to develop formaldehyde sensitivity than the general population, but identification of these individuals may be useful for ongoing surveillance.

(v) Use of disease questionnaires: Comparison of the results from previous years with present results provides the best method for detecting a general deterioration in health when toxic signs and symptoms are measured subjectively. In this way recall bias does not affect the results of the analysis. Consequently, WISHA has determined that the findings of the medical and work histories should be kept in a standardized form for comparison of the year-to-year results.

(b) Physical examination.

(i) Mucosa of eyes and airways: Because of the irritant effects of formaldehyde, the examining physician should be alert to evidence of this irritation. A speculum examination of the nasal mucosa may be helpful in assessing possible irritation and cytotoxic changes, as may be indirect inspection of the posterior pharynx by mirror.

(ii) Pulmonary system: A conventional respiratory examination, including inspection of the thorax and auscultation and percussion of the lung fields should be performed as part of the periodic medical examination. Although routine pulmonary function testing is only required by the standard once every year for persons who are exposed over the TWA concentration limit, these tests have an obvious value in investigating possible respiratory dysfunction and should be used wherever deemed appropriate by the physician. In cases of alleged formaldehyde-induced airway disease, other possible causes of pulmonary dysfunction (including exposures to other substances) should be ruled out. A chest radiograph may be useful in these circumstances. In cases of suspected airway hypersensitivity or allergy, it may be appropriate to use bronchial challenge testing with formaldehyde or methacholine to determine the nature of the disorder. Such testing should be performed by or under the supervision of a physician experienced in the procedures involved.

(iii) Skin: The physician should be alert to evidence of dermal irritation of sensitization, including reddening and inflammation, urticaria, blistering, scaling, formation of skin fissures, or other symptoms. Since the integrity of the skin barrier is compromised by other dermal diseases, the presence of such disease should be noted. Skin sensitivity testing carries with it some risk of inducing sensitivity, and therefore, skin testing for formaldehyde sensitivity should not be used as a routine screening test. Sensitivity testing may be indicated in the investigation of a suspected existing sensitivity. Guidelines for such testing have been prepared by the North American Contact Dermatitis Group.

(4) Additional examinations or tests. The physician may deem it necessary to perform other medical examinations or tests as indicated. The standard provides a mechanism whereby these additional investigations are covered under the standard for occupational exposure to formaldehyde.

(5) Emergencies. The examination of workers exposed in an emergency should be directed at the organ systems most likely to be affected. Much of the content of the examination will be similar to the periodic examination unless the patient has received a severe acute exposure requiring immediate attention to prevent serious consequences. If a severe overexposure requiring medical intervention or hospitalization has occurred, the physician must be alert to the possibility of delayed symptoms. Followup nonroutine examinations may be necessary to assure the patient's well-being.

(6) Employer obligations. The employer is required to provide the physician with the following information: A copy of this standard and appendices A, C, D, and E; a description of the affected employee's duties as they relate to his or her exposure concentration; an estimate of the employee's exposure including duration (e.g., fifteen hr./wk., three eight-hour shifts, full-time); a description of any personal protective equipment, including respirators, used by the employee; and the results of any previous medical determinations for the affected employee related to formaldehyde exposure to the extent that this information is within the employer's control.

(7) Physician's obligations. The standard requires the employer to obtain a written statement from the physician. This statement must contain the physician's opinion as to whether the employee has any medical condition which would place him or her at increased risk of impaired health from exposure to formaldehyde or use of respirators, as appropriate. The physician must also state his opinion regarding any restrictions that should be placed on the employee's exposure to formaldehyde or upon the use of protective clothing or equipment such as respirators. If the employee wears a respirator as a result of his or her exposure to formaldehyde, the physician's opinion must also contain a statement regarding the suitability of the employee to wear the type of respirator assigned. Finally, the physician must inform the employer that the employee has been told the results of the medical examination and of any medical conditions which require further explanation or treatment. This written opinion is not to contain any information on specific findings or diagnoses unrelated to occupational exposure to formaldehyde.

The purpose in requiring the examining physician to supply the employer with a written opinion is to provide the employer with a medical basis to assist the employer in placing employees initially, in assuring that their health is not being impaired by formaldehyde, and to assess the employee's ability to use any required protective equipment.

[Statutory Authority: Chapter 49.17 RCW. 88-21-002 (Order 88-23), 296-62-07546, filed 10/6/88, effective 11/7/88.]

 

WAC 296-62-07548 Appendix D--Nonmandatory medical disease questionnaire.

(1) Identification.

(a) Plant name:

(b) Date:

(c) Employee name:

(d) Social Security number:

(e) Job title:

(f) Birthdate:

(g) Age:

(h) Sex:

(i) Height:

(j) Weight:

(2) Medical history.

(a) Have you ever been in the hospital as a patient?

Yes    No

If yes, what kind of problem were you having?

(b) Have you ever had any kind of operation?

Yes    No

If yes, what kind?

(c) Do you take any kind of medicine regularly?

Yes    No

If yes, what kind?

(d) Are you allergic to any drugs, foods, or chemicals?

Yes    No

If yes, what kind of allergy is it?

What causes the allergy?

(e) Have you ever been told that you have asthma, hayfever, or sinusitis?

Yes    No

(f) Have you ever been told that you have emphysema, bronchitis, or any other respiratory problems?

Yes    No

(g) Have you ever been told you had hepatitis?

Yes    No

(h) Have you ever been told that you have cirrhosis?

Yes    No

(i) Have you ever been told that you had cancer?

Yes    No

(j) Have you ever had arthritis or joint pain?

Yes    No

(k) Have you ever been told that you had high blood pressure?

Yes    No

(l) Have you ever had a heart attack or heart trouble?

Yes    No

(3) Medical history update.

(a) Have you been in the hospital as a patient any time within the past year?

Yes    No

If so, for what condition?

(b) Have you been under the care of a physician during the past year?

Yes    No

If so, for what condition?

(c) Is there any change in your breathing since last year?

Yes    No

(i) Better?

(ii) Worse?

(iii) No change?

If change, do you know why?

(d) Is your general health different this year from last year?

Yes    No

If different, in what way?

(e) Have you in the past year or are you now taking any medication on a regular basis?

Yes    No

(i) Name Rx

(ii) Condition being treated

(4) Occupational history.

(a) How long have you worked for your present employer?

(b) What jobs have you held with this employer? Include job title and length of time in each job.

(c) In each of these jobs, how many hours a day were you exposed to chemicals?

(d) What chemicals have you worked with most of the time?

(e) Have you ever noticed any type of skin rash you feel was related to your work?

Yes   No

(f) Have you ever noticed that any kind of chemical makes you cough?

Yes   No

(i) Wheeze:

Yes    No

(ii) Become short of breath or cause your chest to become tight?

Yes    No

(g) Are you exposed to any dust or chemicals at home?

Yes    No

If yes, explain:

(h) In other jobs, have you ever had exposure to:

(i) Wood dust?

Yes    No

(ii) Nickel or chromium?

Yes    No

(iii) Silica (foundry, sand blasting)?

Yes    No

(iv) Arsenic or asbestos?

Yes    No

(v) Organic solvents?

Yes    No

(vi) Urethane foams?

Yes    No

(5) Occupational history update.

(a) Are you working on the same job this year as you were last year?

Yes    No

If not, how has your job changed?

(b) What chemicals are you exposed to on your job?

(c) How many hours a day are you exposed to chemicals?

(d) Have you noticed any skin rash within the past year you feel was related to your work?

Yes    No

If so, explain circumstances:

(e) Have you noticed that any chemical makes you cough, be short of breath, or wheeze?

Yes   No

If so, can you identify it?

(6) Miscellaneous.

(a) Do you smoke?

Yes   No

If so, how much and for how long?

(i) Pipe(ii) 

Cigars

(iii) Cigarettes

(b) Do you drink alcohol in any form?

Yes    No

If so, how much, how long, and how often?

(c) Do you wear glasses or contact lenses?

Yes    No

(d) Do you get any physical exercise other than that required to do your job?

Yes    No

If so, explain:

(e) Do you have any hobbies or “side jobs” that require you to use chemicals, such as furniture stripping, sand blasting, insulation or manufacture of urethane foam, furniture, etc.?

Yes    No

If so, please describe, giving type of business or hobby, chemicals used and length of exposures.

(7) Symptoms questionnaire.

(a) Do you ever have any shortness of breath?

Yes    No

(i) If yes, do you have to rest after climbing several flights of stairs?

Yes   No

(ii) If yes, if you walk on the level with people your own age, do you walk slower than they do?

Yes    No

(iii) If yes, if you walk slower than a normal pace, do you have to limit the distance that you walk?

Yes   No

(iv) If yes, do you have to stop and rest while bathing or dressing?

Yes    No

(b) Do you cough as much as three months out of the year?

Yes    No

(i) If yes, have you had this cough for more than two years?

Yes    No

(ii) If yes, do you ever cough anything up from the chest?

Yes    No

(c) Do you ever have a feeling of smothering, unable to take a deep breath, or tightness in your chest?

Yes    No

(i) If yes, do you notice that this occurs on any particular day of the week?

Yes    No

(ii) If yes, what day of the week?

(iii) If yes, do you notice that this occurs at any particular place?

Yes    No

(iv) If yes, do you notice that this is worse after you have returned to work after being off for several days?

Yes    No

(d) Have you ever noticed any wheezing in your chest?

Yes    No

(i) If yes, is this only with colds or other infections?

Yes   No

(ii) Is this caused by exposure to any kind of dust or other material?

Yes    No

(iii) If yes, what kind?

(e) Have you noticed any burning, tearing, or redness of your eyes when you are at work?

Yes    No

If so, explain circumstances:

(f) Have you noticed any sore or burning throat or itchy or burning nose when you are at work?

Yes    No

If so, explain circumstances:

(g) Have you noticed any stuffiness or dryness of your nose?

Yes    No

(h) Do you ever have swelling of the eyelids or face?

Yes    No

(i) Have you ever been jaundiced?

Yes    No

If yes, was this accompanied by any pain?

Yes    No

(j) Have you ever had a tendency to bruise easily or bleed excessively?

Yes    No

(k) Do you have frequent headaches that are not relieved by aspirin or tylenol?

Yes    No

(i) If yes, do they occur at any particular time of the day or week?

Yes    No

(ii) If yes, when do they occur?

(l) Do you have frequent episodes of nervousness or irritability?

Yes    No

(m) Do you tend to have trouble concentrating or remembering?

Yes    No

(n) Do you ever feel dizzy, light-headed, excessively drowsy, or like you have been drugged?

Yes    No

(o) Does your vision ever become blurred?

Yes    No

(p) Do you have numbness or tingling of the hands or feet or other parts of your body?

Yes   No

(q) Have you ever had chronic weakness or fatigue?

Yes    No

(r) Have you every had any swelling of your feet or ankles to the point where you could not wear your shoes?

Yes    No

(s) Are you bothered by heartburn or indigestion?

Yes    No

(t) Do you ever have itching, dryness, or peeling and scaling of the hands?

Yes    No

(u) Do you ever have a burning sensation in the hands, or reddening of the skin?

Yes    No

(v) Do you ever have cracking or bleeding of the skin on your hands?

Yes    No

(w) Are you under a physician's care?

Yes    No

If yes, for what are you being treated?

(x) Do you have any physical complaints today?

Yes   No

If yes, explain:

(y) Do you have other health conditions not covered by these questions?

Yes    No

If yes, explain:

[Statutory Authority: Chapter 49.17 RCW. 88-21-002 (Order 88-23), 296-62-07548, filed 10/6/88, effective 11/7/88.]

WAC 296-62-076 Methylenedianiline.

[Statutory Authority: Chapter 49.17 RCW. 93-04-111 (Order 92-15), 296-62-076, filed 2/3/93, effective 3/15/93.]

WAC 296-62-07601 Scope and application.

(1) WAC 296-62-076 applies to all occupational exposures to MDA, Chemical Abstracts Service Registry No. 101-77-9, except as provided in subsections (2) through (7) of this section.

(2) Except as provided in subsection (8) of this section and WAC 296-62-07609(5), this section does not apply to the processing, use, and handling of products containing MDA where initial monitoring indicates that the product is not capable of releasing MDA in excess of the action level under the expected conditions of processing, use, and handling which will cause the greatest possible release; and where no “dermal exposure to MDA” can occur.

(3) Except as provided in subsection (8) of this section, WAC 296-62-076 does not apply to the processing, use, and handling of products containing MDA where objective data are reasonably relied upon which demonstrate the product is not capable of releasing MDA under the expected conditions of processing, use, and handling which will cause the greatest possible release; and where no “dermal exposure to MDA” can occur.

(4) WAC 296-62-076 does not apply to the storage, transportation, distribution, or sale of MDA in intact containers sealed in such a manner as to contain the MDA dusts, vapors, or liquids, except for the provisions of WAC 296-62-054, 296-62-07607 and 296-800-170.

(5) WAC 296-62-076 does not apply to the construction industry as defined in WAC 296-155-012(6). (Exposure to MDA in the construction industry is covered by WAC 296-155-173.)

(6) Except as provided in subsection (8) of this section, WAC 296-62-076 does not apply to materials in any form which contain less than 0.1% MDA by weight or volume.

(7) Except as provided in subsection (8) of this section, WAC 296-62-076 does not apply to “finished articles containing MDA.”

(8) Where products containing MDA are exempted under subsections (2) through (7) of this section, the employer shall maintain records of the initial monitoring results or objective data supporting that exemption and the basis for the employer's reliance on the data, as provided in the recordkeeping provision of WAC 296-62-07631.

[Statutory Authority: RCW 49.17.010, .040, .050. 01-11-038, (Order 99-36), 296-62-07601, filed 05/09/01, effective 09/01/01. Statutory Authority: Chapter 49.17 RCW. 93-04-111 (Order 92-15), 296-62-07601, filed 2/3/93, effective 3/15/93.]

 

WAC 296-62-07603 Definitions. 

For the purpose of WAC 296-62-076, the following definitions shall apply:

(1) “Action level” means a concentration of airborne MDA of 5 ppb as an 8-hour time-weighted average.

(2) “Authorized person” means 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 WAC 296-62-07633 of WAC 296-62-076, or any other person authorized by WISHA or regulations issued by WISHA.

(3) “Container” means any barrel, bottle, can, cylinder, drum, reaction vessel, storage tank, commercial packaging, or the like, but does not include piping systems.

(4) “Dermal exposure to MDA” occurs where employees are engaged in the handling, application, or use of mixtures or materials containing MDA, with any of the following nonairborne forms of MDA:

(a) Liquid, powdered, granular, or flaked mixtures containing MDA in concentrations greater than 0.1% by weight or volume; and

(b) Materials other than “finished articles” containing MDA in concentrations greater than 0.1% by weight or volume.

(5) “Director” means the director of the department of labor and industries, or his/her designated representative.

(6) “Emergency” means any occurrence such as, but not limited to, equipment failure, rupture of containers, or failure of control equipment which results in an unexpected and potentially hazardous release of MDA.

(7) “Employee exposure” means exposure to MDA which would occur if the employee were not using respirators or protective work clothing and equipment.

(8) “Finished article containing MDA” is defined as a manufactured item:

(a) Which is formed to a specific shape or design during manufacture;

(b) Which has end use function(s) dependent in whole or part upon its shape or design during end use; and

(c) Where applicable, is an item which is fully cured by virtue of having been subjected to the conditions (temperature, time) necessary to complete the desired chemical reaction.

(9) “4,4' methylenedianiline” or “MDA” means the chemical 4,4'- diaminodiphenylmethane, Chemical Abstract Service Registry number 101-77-9, in the form of a vapor, liquid, or solid. The definition also includes the salts of MDA.

(10) “Regulated areas” means areas where airborne concentrations of MDA exceed or can reasonably be expected to exceed, the permissible exposure limits, or where dermal exposure to MDA can occur.

(11) “STEL” means short-term exposure limit as determined by any 15 minute sample period.

[Statutory Authority: Chapter 49.17 RCW. 93-04-111 (Order 92-15), 296-62-07603, filed 2/3/93, effective 3/15/93.]

WAC 296-62-07605 Permissible exposure limits (PEL). 

The employer shall assure that no employee is exposed to an airborne concentration of MDA in excess of ten parts per billion (10 ppb) as an 8-hour time-weighted average or a STEL of 100 ppb.

[Statutory Authority: Chapter 49.17 RCW. 93-04-111 (Order 92-15), 296-62-07605, filed 2/3/93, effective 3/15/93.]

WAC 296-62-07607 Emergency situations.

(1) Written plan.

(a) A written plan for emergency situations shall be developed for each workplace where there is a possibility of an emergency. Appropriate portions of the plan shall be implemented in the event of an emergency.

(b) The plan shall specifically provide that employees engaged in correcting emergency conditions shall be equipped with the appropriate personal protective equipment and clothing as required in WAC 296-62-07615 and 296-62-07617 until the emergency is abated.

(c) The plan shall specifically include provisions for alerting and evacuating affected employees as well as the elements prescribed in chapter 296-24 WAC, Part G-1, “Employee emergency plans and fire prevention plans.”

(2) Alerting employees. Where there is the possibility of employee exposure to MDA due to an emergency, means shall be developed to alert promptly those employees who have the potential to be directly exposed. Affected employees not engaged in correcting emergency conditions shall be evacuated immediately in the event that an emergency occurs. Means shall also be developed and implemented for alerting other employees who may be exposed as a result of the emergency.

[Statutory Authority: Chapter 49.17 RCW. 93-04-111 (Order 92-15), 296-62-07607, filed 2/3/93, effective 3/15/93.]

 

WAC 296-62-07609 Exposure monitoring.

(1) General.

(a) Determinations of employee exposure shall be made from breathing zone air samples that are representative of each employee's exposure to airborne MDA over an 8-hour period. Determination of employee exposure to the STEL shall be made from breathing zone air samples collected over a 15 minute sampling period.

(b) Representative employee exposure shall be determined on the basis of one or more samples representing full shift exposure for each shift for each job classification in each work area where exposure to MDA may occur.

(c) Where the employer can document that exposure levels are equivalent for similar operations in different work shifts, the employer shall only be required to determine representative employee exposure for that operation during one shift.

(2) Initial monitoring. Each employer who has a workplace or work operation covered by this standard shall perform initial monitoring to determine accurately the airborne concentrations of MDA to which employees may be exposed.

(3) Periodic monitoring and monitoring frequency.

(a) If the monitoring required by subsection (2) of this section reveals employee exposure at or above the action level, but at or below the PELs, the employer shall repeat such representative monitoring for each such employee at least every six months.

(b) If the monitoring required by subsection (2) of this section reveals employee exposure above the PELs, the employer shall repeat such monitoring for each such employee at least every three months.

(c) The employer may alter the monitoring schedule from every three months to every six months for any employee for whom two consecutive measurements taken at least 7 days apart indicate that the employee exposure has decreased to below the TWA but above the action level.

(4) Termination of monitoring.

(a) If the initial monitoring required by subsection (2) of this section reveals employee exposure to be below the action level, the employer may discontinue the monitoring for that employee, except as otherwise required by subsection (5) of this section.

(b) If the periodic monitoring required by subsection (3) of this section reveals that employee exposures, as indicated by at least two consecutive measurements taken at least 7 days apart, are below the action level the employer may discontinue the monitoring for that employee, except as otherwise required by subsection (5) of this section.

(5) Additional monitoring. The employer shall institute the exposure monitoring required under subsections (2) and (3) of this section when there has been a change in production process, chemicals present, control equipment, personnel, or work practices which may result in new or additional exposures to MDA, or when the employer has any reason to suspect a change which may result in new or additional exposures.

(6) Accuracy of monitoring. Monitoring shall be accurate, to a confidence level of 95 percent, to within plus or minus 25 percent for airborne concentrations of MDA.

(7) Employee notification of monitoring results.

(a) The employer shall, within 15 working days after the receipt of the results of any monitoring performed under this standard, notify each employee of these results, in writing, either individually or by posting of results in an appropriate location that is accessible to affected employees.

(b) The written notification required by subdivision (a) of this subsection shall contain the corrective action being taken by the employer to reduce the employee exposure to or below the PELs, wherever the PELs are exceeded.

(8) Visual monitoring. The employer shall make routine inspections of employee hands, face, and forearms potentially exposed to MDA. Other potential dermal exposures reported by the employee must be referred to the appropriate medical personnel for observation. If the employer determines that the employee has been exposed to MDA the employer shall:

(a) Determine the source of exposure;

(b) Implement protective measures to correct the hazard; and

(c) Maintain records of the corrective actions in accordance with WAC 296-62-07631.

[Statutory Authority: Chapter 49.17 RCW. 93-04-111 (Order 92-15), 296-62-07609, filed 2/3/93, effective 3/15/93.]

WAC 296-62-07611 Regulated areas.

(1) Establishment.

(a) Airborne exposures. The employer shall establish regulated areas where airborne concentrations of MDA exceed or can reasonably be expected to exceed, the permissible exposure limits.

(b) Dermal exposures. Where employees are subject to dermal exposure to MDA the employer shall establish those work areas as regulated areas.

(2) Demarcation. Regulated areas shall be demarcated from the rest of the workplace in a manner that minimizes the number of persons potentially exposed.

(3) Access. Access to regulated areas shall be limited to authorized persons.

(4) Personal protective equipment and clothing. Each person entering a regulated area shall be supplied with, and required to use, the appropriate personal protective clothing and equipment in accordance with WAC 296-62-07615 and 296-62-07617.

(5) Prohibited activities. The employer shall ensure that employees do not eat, drink, smoke, chew tobacco or gum, or apply cosmetics in regulated areas.

[Statutory Authority: Chapter 49.17 RCW. 93-04-111 (Order 92-15), 296-62-07611, filed 2/3/93, effective 3/15/93.]

WAC 296-62-07613 Methods of compliance.

(1) Engineering controls and work practices.

(a) The employer shall institute engineering controls and work practices to reduce and maintain employee exposure to MDA at or below the PELs except to the extent that the employer can establish that these controls are not feasible or where the provisions of subdivision (b) of this subsection or WAC 296-62-07615(1) apply.

(b) Wherever the feasible engineering controls and work practices which can be instituted are not sufficient to reduce employee exposure to or below the PELs, the employer shall use them to reduce employee exposure to the lowest levels achievable by these controls and shall supplement them by the use of respiratory protective devices which comply with the requirements of WAC 296-62-07615.

(2) Compliance program.

(a) The employer shall establish and implement a written program to reduce employee exposure to or below the PELs by means of engineering and work practice controls, as required by subsection (1) of this section, and by use of respiratory protection where permitted under WAC 296-62-076. The program shall include a schedule for periodic maintenance (e.g., leak detection) and shall include the written plan for emergency situations as specified in WAC 296-62-07607.

(b) Upon request this written program shall be furnished for examination and copying to the director, affected employees, and designated employee representatives. The employer shall review and, as necessary, update such plans at least once every 12 months to make certain they reflect the current status of the program.

(3) Employee rotation. Employee rotation shall not be permitted as a means of reducing exposure.

[Statutory Authority: Chapter 49.17 RCW. 93-04-111 (Order 92-15), 296-62-07613, filed 2/3/93, effective 3/15/93.]

 

WAC 296-62-07615 Respiratory protection.

(1) General. For employees who use respirators required by this section, the employer must provide each employee an appropriate respirator that complies with the requirements of this subsection. Respirators must be used during:

(a) Periods necessary to install or implement feasible engineering and work-practice controls;

(b) Work operations for which the employer establishes that engineering and work-practice controls are not feasible;

(c) Work operations for which feasible engineering and work-practice controls are not yet sufficient to reduce exposure to or below the PEL;

(d) Emergencies.

(2) Respirator program. The employer must develop, implement and maintain a respiratory protection program as required by chapter 296-842 WAC, Respirators, which covers each employee requuired by this chapter to use a respirator.

(3) Respirator selection.

(a) The employer must select and provide to employees appropriate respirators as specified in this section and WAC 296-842-13005 in the respirator rule.

(b) Any employee who cannot use a negative-pressure respirator must be given the option of using a positive-pressure respirator, or a supplied-air respirator operated in the continuous-flow or pressure-demand mode.

(c) Provide HEPA filters or N-, R-, or P-100 filters for powered air-purifying respirators (PAPRs) and negative-pressure air-purifying respirators.

(d) Provide to employees, for escape, one of the following respirator options:

(i) Any self-contained breathing apparatus with a full-facepiece or hood, operated in the positive-pressure or continuous-flow mode.

OR

(ii) A full-facepiece air-purifying respirator.

(e) Provide a combination HEPA filter (or N-, R-, P-100 filter) and organic vapor canister or cartridge with air-purifying respirators when MDA is in liquid form or used as part of a process requiring heat.

[Statutory Authority: RCW 49.17.010, .040, .050, and .060. 09-15-145 (Order 09-04) § 296-62-07521, filed 07/21/09, effective 09/01/09. Statutory Authority: RCW 49.17.010, .040, .050, and .060. 07-05-072 (Order 06-39) § 296-62-07615, filed 02/20/07, effective 04/01/07. Statutory Authority: RCW 49.17.010, .040, .050, and .060. 05-03-093 (Order 04-41), § 296-62-07615, filed 01/18/05, effective 03/01/05. Statutory Authority: RCW 49.17.010, .040, .050. 99-10 (Order 98-10) 296-62-07615, filed 05/04/99, effective 09/01/99.] Statutory Authority: Chapter 49.17 RCW. 93-04-111 (Order 92-15), 296-62-07615, filed 2/3/93, effective 3/15/93.]

WAC 296-62-07617 Protective work clothing and equipment.

(1) Provision and use. Where employees are subject to dermal exposure to MDA, where liquids containing MDA can be splashed into the eyes, or where airborne concentrations of MDA are in excess of the PEL, the employer shall provide, at no cost to the employee, and ensure that the employee uses, appropriate protective work clothing and equipment which prevent contact with MDA such as, but not limited to:

(a) Aprons, coveralls, or other full-body work clothing;

(b) Gloves, head coverings, and foot coverings; and

(c) Face shields, chemical goggles; or

(d) Other appropriate protective equipment which comply with WAC 296-800-160.

(2) Removal and storage.

(a) The employer shall ensure that, at the end of their work shift, employees remove MDA-contaminated protective work clothing and equipment that is not routinely removed throughout the day in change rooms provided in accordance with the provisions established for change rooms.

(b) The employer shall ensure that, during their work shift, employees remove all other MDA-contaminated protective work clothing or equipment before leaving a regulated area.

(c) The employer shall ensure that no employee takes MDA-contaminated work clothing or equipment out of the change room, except those employees authorized to do so for the purpose of laundering, maintenance, or disposal.

(d) MDA-contaminated work clothing or equipment shall be placed and stored in closed containers which prevent dispersion of the MDA outside the container.

(e) Containers of MDA-contaminated protective work clothing or equipment which are to be taken out of change rooms or the workplace for cleaning, maintenance, or disposal shall bear labels warning of the hazards of MDA.

(3) Cleaning and replacement.

(a) The employer shall provide the employee with clean protective clothing and equipment. The employer shall ensure that protective work clothing or equipment required by this paragraph is cleaned, laundered, repaired, or replaced at intervals appropriate to maintain its effectiveness.

(b) The employer shall prohibit the removal of MDA from protective work clothing or equipment by blowing, shaking, or any methods which allow MDA to reenter the workplace.

(c) The employer shall ensure that laundering of MDA-contaminated clothing shall be done so as to prevent the release of MDA in the workplace.

(d) Any employer who gives MDA-contaminated clothing to another person for laundering shall inform such person of the requirement to prevent the release of MDA.

(e) The employer shall inform any person who launders or cleans protective clothing or equipment contaminated with MDA of the potentially harmful effects of exposure.

(f) MDA-contaminated clothing shall be transported in properly labeled, sealed, impermeable bags or containers.

[Statutory Authority: RCW 49.17.010, .040, .050. 01-11-038, (Order 99-36), 296-62-07617, filed 05/09/01, effective 09/01/01. Statutory Authority: Chapter 49.17 RCW. 94-20-057 (Order 94-16), 296-62-07617, filed 9/30/94, effective 11/20/94; 93-04-111 (Order 92-15), 296-62-07617, filed 2/3/93, effective 3/15/93.]

 

WAC 296-62-07619 Hygiene facilities and practices.

(1) Change rooms.

(a) The employer shall provide clean change rooms for employees, who must wear protective clothing, or who must use protective equipment because of their exposure to MDA.

(b) Change rooms must be equipped with separate storage for protective clothing and equipment and for street clothes which prevents MDA contamination of street clothes.

(2) Showers.

(a) The employer shall ensure that employees, who work in areas where there is the potential for exposure resulting from airborne MDA (e.g., particulates or vapors) above the action level, shower at the end of the work shift.

(i) Shower facilities required by this section shall comply with WAC 296-24-12010.

(ii) The employer shall ensure that employees who are required to shower pursuant to the provisions contained herein do not leave the workplace wearing any protective clothing or equipment worn during the work shift.

(b) Where dermal exposure to MDA occurs, the employer shall ensure that materials spilled or deposited on the skin are removed as soon as possible by methods which do not facilitate the dermal absorption of MDA.

(3) Lunch facilities.

(a) Availability and construction.

(i) Whenever food or beverages are consumed at the worksite and employees are exposed to MDA at or above the PEL or are subject to dermal exposure to MDA the employer shall provide readily accessible lunch areas.

(ii) Lunch areas located within the workplace and in areas where there is the potential for airborne exposure to MDA at or above the PEL shall have a positive pressure, temperature controlled, filtered air supply.

(iii) Lunch areas may not be located in areas within the workplace where the potential for dermal exposure to MDA exists.

(b) The employer shall ensure that employees who have been subjected to dermal exposure to MDA or who have been exposed to MDA above the PEL wash their hands and faces with soap and water prior to eating, drinking, smoking, or applying cosmetics.

(c) The employer shall ensure that employees exposed to MDA do not enter lunch facilities with MDA-contaminated protective work clothing or equipment.

[Statutory Authority: Chapter 49.17 RCW. 93-04-111 (Order 92-15), 296-62-07619, filed 2/3/93, effective 3/15/93.]

WAC 296-62-07621 Communication of hazards to employees.

(1) Signs and labels.

(a) The employer shall post and maintain legible signs demarcating regulated areas and entrances or accessways to regulated areas that bear the following legend:

DANGER MDA MAY CAUSE CANCER LIVER TOXIN

AUTHORIZED PERSONNEL ONLY RESPIRATORS AND PROTECTIVE CLOTHING

MAY BE REQUIRED TO BE WORN IN THIS AREA

(b) The employer shall ensure that labels or other appropriate forms of warning are provided for containers of MDA within the workplace. The labels shall comply with the requirements of chapter 296-839 WAC, Content and distribution of material safety data sheets (MSDSs) and label information and WAC 296-800-170 of the safety and health core rules, and the labels shall include the following legend:

(i) For pure MDA

DANGER CONTAINS MDA MAY CAUSE CANCER LIVER TOXIN

(ii) For mixtures containing MDA

DANGER CONTAINS MDA CONTAINS MATERIALS

WHICH MAY CAUSE CANCER LIVER TOXIN

(2) Material safety data sheets (MSDS).

(a) Employers shall obtain or develop, and shall provide access to their employees, to a material safety data sheet (MSDS) for MDA. In meeting this obligation, employers shall make appropriate use of the information found in Appendices A and B.

(b) Employers who are manufacturers or importers shall:

(i) Comply with subdivision (1)(b) of this section as appropriate; and

(ii) Comply with the requirement in WISHA hazard communication standard, chapter 296-839 WAC, that they deliver to downstream employers an MSDS for MDA.

(3) Information and training.

(a) The employer shall provide employees with information and training on MDA, in accordance with WAC 296-800-170, at the time of initial assignment and at least annually thereafter.

(b) In addition to the information required under WAC 296-800-170, the employer shall:

(i) Provide an explanation of the contents of WAC 296-62-076, including Appendices A and B, and indicate to employees where a copy of the standard is available;

(ii) Describe the medical surveillance program required under WAC 296-62-07625, and explain the information contained in Appendix C; and

(iii) Describe the medical removal provision required under WAC 296-62-07625.

(4) Access to training materials.

(a) The employer shall make readily available to all affected employees, without cost, all written materials relating to the employee training program, including a copy of this regulation.

(b) The employer shall provide to the director, upon request, all information and training materials relating to the employee information and training program.

[Statutory Authority: RCW 49.17.010, .040, .050, and .060. . 07-03-163, (Order 06-30), 296-62-07621, filed01/24/07, effective 04/01/07. Statutory Authority: RCW 49.17.010, .040, .050. 01-11-038, (Order 99-36), 296-62-07621, filed 05/09/01, effective 09/01/01. Statutory Authority: Chapter 49.17 RCW. 93-04-111 (Order 92-15), 296-62-07621, filed 2/3/93, effective 3/15/93.]

WAC 296-62-07623 Housekeeping.

(1) All surfaces shall be maintained as free as practicable of visible accumulations of MDA.

(2) The employer shall institute a program for detecting MDA leaks, spills, and discharges, including regular visual inspections of operations involving liquid or solid MDA.

(3) All leaks shall be repaired and liquid or dust spills cleaned up promptly.

(4) Surfaces contaminated with MDA may not be cleared by the use of compressed air.

(5) Shoveling, dry sweeping, and other methods of dry clean-up of MDA may be used where HEPA-filtered vacuuming and/or wet cleaning are not feasible or practical.

(6) Waste, scrap, debris, bags, containers, equipment, and clothing contaminated with MDA shall be collected and disposed of in a manner to prevent the reentry of MDA into the workplace.

[Statutory Authority: Chapter 49.17 RCW. 93-04-111 (Order 92-15), 296-62-07623, filed 2/3/93, effective 3/15/93.]

 

WAC 296-62-07625 Medical surveillance.

(1) General.

(a) The employer shall make available a medical surveillance program for employees exposed to MDA:

(i) Employees exposed at or above the action level for 30 or more days per year;

(ii) Employees who are subject to dermal exposure to MDA for 15 or more days per year;

(iii) Employees who have been exposed in an emergency situation;

(iv) Employees whom the employer, based on results from compliance with WAC 296-62-07609(8), has reason to believe are being dermally exposed; and

(v) Employees who show signs or symptoms of MDA exposure.

(b) The employer shall ensure that all medical examinations and procedures are performed by, or under the supervision of, a licensed physician, at a reasonable time and place, and provided without cost to the employee.

(2) Initial examinations.

(a) Within 150 days of the effective date of this standard, or before the time of initial assignment, the employer shall provide each employee covered by subdivision (1)(a) of this section with a medical examination including the following elements:

(i) A detailed history which includes:

(A) Past work exposure to MDA or any other toxic substances;

(B) A history of drugs, alcohol, tobacco, and medication routinely taken (duration and quantity); and

(C) A history of dermatitis, chemical skin sensitization, or previous hepatic disease.

(ii) A physical examination which includes all routine physical examination parameters, skin examination, and signs of liver disease.

(iii) Laboratory tests including:

(A) Liver function tests; and

(B) Urinalysis.

(iv) Additional tests as necessary in the opinion of the physician.

(b) No initial medical examination is required if adequate records show that the employee has been examined in accordance with the requirements of WAC 296-62-076 within the previous six months prior to the effective date of this standard or prior to the date of initial assignment.

(3) Periodic examinations.

(a) The employer shall provide each employee covered by WAC 296-62-076 with a medical examination at least annually following the initial examination. These periodic examinations shall include at least the following elements:

(i) A brief history regarding any new exposure to potential liver toxins, changes in drug, tobacco, and alcohol intake, and the appearance of physical signs relating to the liver and the skin;

(ii) The appropriate tests and examinations including liver function tests and skin examinations; and

(iii) Appropriate additional tests or examinations as deemed necessary by the physician.

(b) If in the physicians' opinion the results of liver function tests indicate an abnormality, the employee shall be removed from further MDA exposure in accordance with WAC 296-62-07627 and 296-62-07629. Repeat liver function tests shall be conducted on advice of the physician.

(4) Emergency examinations. If the employer determines that the employee has been exposed to a potentially hazardous amount of MDA in an emergency situation as addressed in WAC 296-62-07607, the employer shall provide medical examinations in accordance with subsection (3) of this section. If the results of liver function testing indicate an abnormality, the employee shall be removed in accordance with WAC 296-62-07627 and 296-62-07629. Repeat liver function tests shall be conducted on the advice of the physician. If the results of the tests are normal, tests must be repeated two to three weeks from the initial testing. If the results of the second set of tests are normal and on the advice of the physician, no additional testing is required.

(5) Additional examinations. Where the employee develops signs and symptoms associated with exposure to MDA, the employer shall provide the employee with an additional medical examination including a liver function test. Repeat liver function tests shall be conducted on the advice of the physician. If the results of the tests are normal, tests must be repeated two to three weeks from the initial testing. If the results of the second set of tests are normal and, on the advice of the physician, no additional testing is required.

(6) Multiple physician review mechanism.

(a) If the employer selects the initial physician who conducts any medical examination or consultation provided to an employee under WAC 296-62-076, and the employee has signs or symptoms of occupational exposure to MDA (which could include an abnormal liver function test), and the employee disagrees with the opinion of the examining physician, and this opinion could affect the employee's job status, the employee may designate an appropriate, mutually acceptable second physician:

(i) To review any findings, determinations, or recommendations of the initial physician; and

(ii) To conduct such examinations, consultations, and laboratory tests as the second physician deems necessary to facilitate this review.

(b) The employer shall promptly notify an employee of the right to seek a second medical opinion after each occasion that an initial physician conducts a medical examination or consultation pursuant to WAC 296-62-076. The employer may condition its participation in, and payment for, the multiple physician review mechanism upon the employee doing the following within fifteen days after receipt of the foregoing notification, or receipt of the initial physician's written opinion, whichever is later:

(i) The employee informing the employer that he or she intends to seek a second medical opinion; and

(ii) The employee initiating steps to make an appointment with a second physician.

(c) If the findings, determinations, or recommendations of the second physician differ from those of the initial physician, then the employer and the employee shall assure that efforts are made for the two physicians to resolve any disagreement.

(d) If the two physicians have been unable to resolve quickly their disagreement, then the employer and the employee through their respective physicians shall designate a third physician:

(i) To review any findings, determinations, or recommendations of the prior physicians; and

(ii) To conduct such examinations, consultations, laboratory tests, and discussions with the prior physicians as the third physician deems necessary to resolve the disagreement of the prior physicians.

(e) The employer shall act consistent with the findings, determinations, and recommendations of the third physician, unless the employer and the employee reach an agreement which is otherwise consistent with the recommendations of at least one of the three physicians.

(7) Information provided to the examining and consulting physicians.

(a) The employer shall provide the following information to the examining physician:

(i) A copy of this regulation and its appendices;

(ii) A description of the affected employee's duties as they relate to the employee's potential exposure to MDA;

(iii) The employee's current actual or representative MDA exposure level;

(iv) A description of any personal protective equipment used or to be used; and

(v) Information from previous employment-related medical examinations of the affected employee.

(b) The employer shall provide the foregoing information to a second physician under this section upon request either by the second physician or by the employee.

(8) Physician's written opinion.

(a) For each examination under WAC 296-62-076, the employer shall obtain, and provide the employee with a copy of, the examining physician's written opinion within 15 days of its receipt. The written opinion shall include the following:

(i) The occupationally-pertinent results of the medical examination and tests;

(ii) The physician's opinion concerning whether the employee has any detected medical conditions which would place the employee at increased risk of material impairment of health from exposure to MDA;

(iii) The physician's recommended limitations upon the employee's exposure to MDA or upon the employee's use of protective clothing or equipment and respirators; and

(iv) A statement that the employee has been informed by the physician of the results of the medical examination and any medical conditions resulting from MDA exposure which require further explanation or treatment.

(b) The written opinion obtained by the employer shall not reveal specific findings or diagnoses unrelated to occupational exposures.

[Statutory Authority: Chapter 49.17 RCW. 93-04-111 (Order 92-15), 296-62-07625, filed 2/3/93, effective 3/15/93.]

WAC 296-62-07627 Medical removal--Temporary medical removal of an employee. Temporary medical removal of an employee.

(1) Temporary removal resulting from occupational exposure. The employee shall be removed from work environments in which exposure to MDA is at or above the action level or where dermal exposure to MDA may occur, following an initial examination (WAC 296-62-07625(2)), periodic examinations (WAC 296-62-07625(3)), an emergency situation (WAC 296-62-07625(4)), or an additional examination (WAC 296-62-07625(5)) in the following circumstances:

(a) When the employee exhibits signs and/or symptoms indicative of acute exposure to MDA; or

(b) When the examining physician determines that an employee's abnormal liver function tests are not associated with MDA exposure but that the abnormalities may be exacerbated as a result of occupational exposure to MDA.

(c) Temporary removal due to a final medical determination.

(i) The employer shall remove an employee from work environments in which exposure to MDA is at or above the action level or where dermal exposure to MDA may occur, on each occasion that there is a final medical determination or opinion that the employee has a detected medical condition which places the employee at increased risk of material impairment to health from exposure to MDA.

(ii) For the purposes of WAC 296-62-076, the phrase “final medical determination” shall mean the outcome of the physician review mechanism used pursuant to the medical surveillance provisions of this section.

(iii) Where a final medical determination results in any recommended special protective measures for an employee, or limitations on an employee's exposure to MDA, the employer shall implement and act consistent with the recommendation.

(2) Return of the employee to former job status.

(a) The employer shall return an employee to his or her former job status:

(i) When the employee no longer shows signs or symptoms of exposure to MDA or upon the advice of the physician.

(ii) When a subsequent final medical determination results in a medical finding, determination, or opinion that the employee no longer has a detected medical condition which places the employee at increased risk of material impairment to health from exposure to MDA.

(b) For the purposes of this section, the requirement that an employer return an employee to his or her former job status is not intended to expand upon or restrict any rights an employee has or would have had, absent temporary medical removal, to a specific job classification or position under the terms of a collective bargaining agreement.

(3) Removal of other employee special protective measure or limitations. The employer shall remove any limitations placed on an employee, or end any special protective measures provided to an employee, pursuant to a final medical determination, when a subsequent final medical determination indicates that the limitations or special protective measures are no longer necessary.

(4) Employer options pending a final medical determination. Where the physician review mechanism used pursuant to the medical surveillance provisions of WAC 296-62-076, has not yet resulted in a final medical determination with respect to an employee, the employer shall act as follows:

(a) Removal. The employer may remove the employee from exposure to MDA, provide special protective measures to the employee, or place limitations upon the employee, consistent with the medical findings, determinations, or recommendations of any of the physicians who have reviewed the employee's health status.

(b) Return. The employer may return the employee to his or her former job status, and end any special protective measures provided to the employee, consistent with the medical findings, determinations, or recommendations of any of the physicians who have reviewed the employee's health status, with two exceptions.

(i) If the initial removal, special protection, or limitation of the employee resulted from a final medical determination which differed from the findings, determinations, or recommendations of the initial physician; or

(ii) If the employee has been on removal status for the preceding six months as a result of exposure to MDA, then the employer shall await a final medical determination.

[Statutory Authority: Chapter 49.17 RCW. 93-04-111 (Order 92-15), 296-62-07627, filed 2/3/93, effective 3/15/93.]

WAC 296-62-07629 Medical removal protection benefits.

(1) Provisions of medical removal protection benefits. The employer shall provide to an employee up to six months of medical removal protection benefits on each occasion that an employee is removed from exposure to MDA or otherwise limited pursuant to this section.

(2) Definition of medical removal protection benefits. For the purposes of this section, the requirement that an employer provide medical removal protection benefits means that the employer shall maintain the earnings, seniority, and other employment rights and benefits of an employee as though the employee had not been removed from normal exposure to MDA or otherwise limited.

(3) Follow-up medical surveillance during the period of employee removal or limitations. During the period of time that an employee is removed from normal exposure to MDA or otherwise limited, the employer may condition the provision of medical removal protection benefits upon the employee's participation in follow-up medical surveillance made available pursuant to WAC 296-62-076.

(4) Workers' compensation claims. If a removed employee files a claim for workers' compensation payments for an MDA-related disability, then the employer shall continue to provide medical removal protection benefits pending disposition of the claim. To the extent that an award is made to the employee for earnings lost during the period of removal, the employer's medical removal protection obligation shall be reduced by such amount. The employer shall receive no credit for workers' compensation payments received by the employee for treatment-related expenses.

(5) Other credits. The employer's obligation to provide medical removal protection benefits to a removed employee shall be reduced to the extent that the employee receives compensation for earnings lost during the period of removal either from a publicly or employer-funded compensation program, or receives income from non-MDA-related employment with any employer made possible by virtue of the employee's removal.

(6) Employees who do not recover within the 6 months of removal. The employer shall take the following measures with respect to any employee removed from exposure to MDA:

(a) The employer shall make available to the employee a medical examination pursuant to this section to obtain a final medical determination with respect to the employee;

(b) The employer shall assure that the final medical determination obtained indicates whether or not the employee may be returned to his or her former job status, and, if not, what steps should be taken to protect the employee's health;

(c) Where the final medical determination has not yet been obtained, or, once obtained indicates that the employee may not yet be returned to his or her former job status, the employer shall continue to provide medical removal protection benefits to the employee until either the employee is returned to former job status, or a final medical determination is made that the employee is incapable of ever safely returning to his or her former job status; and

(d) Where the employer acts pursuant to a final medical determination which permits the return of the employee to his or her former job status, despite what would otherwise be an abnormal liver function test, later questions concerning removing the employee again shall be decided by a final medical determination. The employer need not automatically remove such an employee pursuant to the MDA removal criteria provided by WAC 296-62-076.

(7) Voluntary removal or restriction of an employee. Where an employer, although not required by WAC 296-62-076 to do so, removes an employee from exposure to MDA or otherwise places limitations on an employee due to the effects of MDA exposure on the employee's medical condition, the employer shall provide medical removal protection benefits to the employee equal to that required by this section.

[Statutory Authority: Chapter 49.17 RCW. 93-04-111 (Order 92-15), 296-62-07629, filed 2/3/93, effective 3/15/93.]

 

WAC 296-62-07631 Recordkeeping.

(1) Monitoring data for exempted employers.

(a) Where as a result of the initial monitoring the processing, use, or handling of products made from or containing MDA are exempted from other requirements of this section under WAC 296-62-07601(2), the employer shall establish and maintain an accurate record of monitoring relied on in support of the exemption.

(b) This record shall include at least the following information:

(i) The product qualifying for exemption;

(ii) The source of the monitoring data (e.g., was monitoring performed by the employer or a private contractor);

(iii) The testing protocol, results of testing, and/or analysis of the material for the release of MDA;

(iv) A description of the operation exempted and how the data support the exemption (e.g., are the monitoring data representative of the conditions at the affected facility); and

(v) Other data relevant to the operations, materials, processing, or employee exposures covered by the exemption.

(c) The employer shall maintain this record for the duration of the employer's reliance upon such objective data.

(2) Objective data for exempted employers.

(a) Where the processing, use, or handling of products made from or containing MDA are exempted from other requirements of WAC 296-62-076 under WAC 296-62-07601, the employer shall establish and maintain an accurate record of objective data relied upon in support of the exemption.

(b) This record shall include at least the following information:

(i) The product qualifying for exemption;

(ii) The source of the objective data;

(iii) The testing protocol, results of testing, and/or analysis of the material for the release of MDA;

(iv) A description of the operation exempted and how the data support the exemption; and

(v) Other data relevant to the operations, materials, processing, or employee exposures covered by the exemption.

(c) The employer shall maintain this record for the duration of the employer's reliance upon such objective data.

(3) Exposure measurements.

(a) The employer shall establish and maintain an accurate record of all measurements required by WAC 296-62-07609, in accordance with Part B of this chapter.

(b) This record shall include:

(i) The dates, number, duration, and results of each of the samples taken, including a description of the procedure used to determine representative employee exposures;

(ii) Identification of the sampling and analytical methods used;

(iii) A description of the type of respiratory protective devices worn, if any; and

(iv) The name, Social Security number, job classification, and exposure levels of the employee monitored and all other employees whose exposure the measurement is intended to represent.

(c) The employer shall maintain this record for at least 30 years, in accordance with Part B of this chapter.

(4) Medical surveillance.

(a) The employer shall establish and maintain an accurate record for each employee subject to medical surveillance required by WAC 296-62-07625, 296-62-07627, and 296-62-07629, in accordance with Part B of this chapter.

(b) This record shall include:

(i) The name, Social Security number, and description of the duties of the employee;

(ii) The employer's copy of the physician's written opinion on the initial, periodic, and any special examinations, including results of medical examination and all tests, opinions, and recommendations;

(iii) Results of any airborne exposure monitoring done for that employee and the representative exposure levels supplied to the physician; and

(iv) Any employee medical complaints related to exposure to MDA.

(c) The employer shall keep, or assure that the examining physician keeps, the following medical records:

(i) A copy of this standard and its appendices, except that the employer may keep one copy of the standard and its appendices for all employees provided the employer references the standard and its appendices in the medical surveillance record of each employee;

(ii) A copy of the information provided to the physician as required by any sections in the regulatory text;

(iii) A description of the laboratory procedures and a copy of any standards or guidelines used to interpret the test results or references to the information;

(iv) A copy of the employee's medical and work history related to exposure to MDA.

(d) The employer shall maintain this record for at least the duration of employment plus 30 years, in accordance with Part B of this chapter.

(5) Medical removals.

(a) The employer shall establish and maintain an accurate record for each employee removed from current exposure to MDA pursuant to WAC 296-62-07625, 296-62-07627, and 296-62-07629.

(b) Each record shall include:

(i) The name and Social Security number of the employee;

(ii) The date of each occasion that the employee was removed from current exposure to MDA as well as the corresponding date on which the employee was returned to his or her former job status;

(iii) A brief explanation of how each removal was or is being accomplished; and

(iv) A statement with respect to each removal indicating the reason for the removal.

(c) The employer shall maintain each medical removal record for at least the duration of an employee's employment plus 30 years.

(6) Availability.

(a) The employer shall assure that records required to be maintained by WAC 296-62-076 shall be made available, upon request, to the director for examination and copying.

(b) Employee exposure monitoring records required by WAC 296-62-076 shall be provided upon request for examination and copying to employees, employee representatives, and the director in accordance with the applicable sections of WAC 296-800-170.

(c) Employee medical records required by this section shall be provided upon request for examination and copying, to the subject employee, to anyone having the specific written consent of the subject employee, and to the director in accordance with Part B of this chapter.

(7) Transfer of records.

(a) The employer shall comply with the requirements involving transfer of records set forth in chapter 296-802 WAC.

(b) If the employer ceases to do business and there is no successor employer to receive and retain the records for the prescribed period, the employer shall notify the director, at least 90 days prior to disposal, and transmit the records to the director if so requested by the director within that period.

[Statutory Authority: RCW 49.17.010, .040, .050. 01-11-038, (Order 99-36), 296-62-07631, filed 05/09/01, effective 09/01/01. Statutory Authority: Chapter 49.17 RCW. 93-04-111 (Order 92-15), 296-62-07631, filed 2/3/93, effective 3/15/93.]

WAC 296-62-07633 Observation of monitoring.

(1) Employee observation. The employer shall provide affected employees, or their designated representatives, an opportunity to observe the measuring or monitoring of employee exposure to MDA conducted pursuant to WAC 296-62-07609.

(2) Observation procedures. When observation of the measuring or monitoring of employee exposure to MDA requires entry into areas where the use of protective clothing and equipment or respirators is required, the employer shall provide the observer with personal protective clothing and equipment or respirators required to be worn by employees working in the area, assure the use of such clothing and equipment or respirators, and require the observer to comply with all other applicable safety and health procedures.

[Statutory Authority: Chapter 49.17 RCW. 93-04-111 (Order 92-15), 296-62-07633, filed 2/3/93, effective 3/15/93.]

WAC 296-62-07637 Appendices. 

The information contained in Appendices A, B, C, and D of WAC 296-62-076 is not intended by itself, to create any additional obligations not otherwise imposed by this standard nor detract from any existing obligation. The protocols for respiratory fit testing in Appendix E of WAC 296-62-076 are mandatory.

[Statutory Authority: Chapter 49.17 RCW. 93-04-111 (Order 92-15), 296-62-07637, filed 2/3/93, effective 3/15/93.]

WAC 296-62-07654 Appendix A to WAC 296-62-076--Substance data sheet, for 4,4'-methylenedianiline.

(1) Substance identification.

(a) Substance: Methylenedianiline (MDA).

(b) Permissible exposure:

(i) Airborne: Ten parts per billion parts of air (10 ppb), time-weighted average (TWA) for an 8-hour workday and an action level of five parts per billion parts of air (5 ppb).

(ii) Dermal: Eye contact and skin contact with MDA are not permitted.

(c) Appearance and odor: White to tan solid; amine odor.

(2) Health hazard data.

(a) Ways in which MDA affects your health. MDA can affect your health if you inhale it, or if it comes in contact with your skin or eyes. MDA is also harmful if you happen to swallow it. Do not get MDA in eyes, on skin, or on clothing.

(b) Effects of overexposure.

(i) Short-term (acute) overexposure: Overexposure to MDA may produce fever, chills, loss of appetite, vomiting, jaundice. Contact may irritate skin, eyes, and mucous membranes. Sensitization may occur.

(ii) Long-term (chronic) exposure. Repeated or prolonged exposure to MDA, even at relatively low concentrations, may cause cancer. In addition, damage to the liver, kidneys, blood, and spleen may occur with long-term exposure.

(iii) Reporting signs and symptoms: You should inform your employer if you develop any signs or symptoms which you suspect are caused by exposure to MDA including yellow staining of the skin.

(3) Protective clothing and equipment.

(a) Respirators. Respirators are required for those operations in which engineering controls or work practice controls are not adequate or feasible to reduce exposure to the permissible limit. If respirators are worn, they must have the joint Mine Safety and Health Administration and National Institute for Occupational Safety and Health (NIOSH) seal of approval, and cartridges or canisters must be replaced as necessary to maintain the effectiveness of the respirator. If you experience difficulty breathing while wearing a respirator, you may request a positive pressure respirator from your employer. You must be thoroughly trained to use the assigned respirator, and the training will be provided by your employer. MDA does not have a detectable odor except at levels well above the permissible exposure limits. Do not depend on odor to warn you when a respirator canister is exhausted. If you can smell MDA while wearing a respirator, proceed immediately to fresh air. If you experience difficulty breathing while wearing a respirator, tell your employer.

(b) Protective clothing. You may be required to wear coveralls, aprons, gloves, face shields, or other appropriate protective clothing to prevent skin contact with MDA. Where protective clothing is required, your employer is required to provide clean garments to you, as necessary, to assure that the clothing protects you adequately. Replace or repair impervious clothing that has developed leaks. MDA should never be allowed to remain on the skin. Clothing and shoes which are not mpervious to MDA should not be allowed to become contaminated with MDA, and if they do, the clothing and shoes should be promptly removed and decontaminated. The clothing should be laundered to remove MDA or discarded. Once MDA penetrates shoes or other leather articles, they should not be worn again.

(c) Eye protection. You must wear splashproof safety goggles in areas where liquid MDA may contact your eyes. Contact lenses should not be worn in areas where eye contact with MDA can occur. In addition, you must wear a face shield if your face could be splashed with MDA liquid.

(4) Emergency and first aid procedures.

(a) Eye and face exposure. If MDA is splashed into the eyes, wash the eyes for at least 15 minutes. See a doctor as soon as possible.

(b) Skin exposure. If MDA is spilled on your clothing or skin, remove the contaminated clothing and wash the exposed skin with large amounts of soap and water immediately. Wash contaminated clothing before you wear it again.

(c) Breathing. If you or any other person breathes in large amounts of MDA, get the exposed person to fresh air at once. Apply artificial respiration if breathing has stopped. Call for medical assistance or a doctor as soon as possible. Never enter any vessel or confined space where the MDA concentration might be high without proper safety equipment and at least one other person present who will stay outside. A life line should be used.

(d) Swallowing. If MDA has been swallowed and the patient is conscious, do not induce vomiting. Call for medical assistance or a doctor immediately.

(5) Medical requirements. If you are exposed to MDA at a concentration at or above the action level for more than 30 days per year, or exposed to liquid mixtures more than 15 days per year, your employer is required to provide a medical examination, including a medical history and laboratory tests, within 60 days of the effective date of this standard and annually thereafter. These tests shall be provided without cost to you. In addition, if you are accidentally exposed to MDA (either by ingestion, inhalation, or skin/eye contact) under conditions known or suspected to constitute toxic exposure to MDA, your employer is required to make special examinations and tests available to you.

(6) Observation of monitoring. Your employer is required to perform measurements that are representative of your exposure to MDA and you or your designated representative are entitled to observe the monitoring procedure. You are entitled to observe the steps taken in the measurement procedure and to record the results obtained. When the monitoring procedure is taking place in an area where respirators or personal protective clothing and equipment are required to be worn, you and your representative must also be provided with, and must wear, the protective clothing and equipment.

(7) Access to records. You or your representative are entitled to see the records of measurements of your exposure to MDA upon written request to your employer. Your medical examination records can be furnished to your physician or designated representative upon request by you to your employer.

(8) Precautions for safe use, handling, and storage.

(a) Material is combustible. Avoid strong acids and their anhydrides. Avoid strong oxidants. Consult supervisor for disposal requirements.

(b) Emergency clean-up. Wear self-contained breathing apparatus and fully clothe the body in the appropriate personal protective clothing and equipment.

[Statutory Authority: Chapter 49.17 RCW. 93-04-111 (Order 92-15), 296-62-07654, filed 2/3/93, effective 3/15/93.]

WAC 296-62-07656 Appendix B to WAC 296-62-076--Substance technical guidelines, MDA.

(1) Identification.

(a) Substance identification. Synonyms: CAS No. 101-77-9. 4,4'-methylenedianiline; 4,4'-methylenebisaniline; methylenedianiline; dianilinomethane.

(b) Formula: C13H14N2.

(2) Physical data.

(a) Appearance and odor: White to tan solid; amine odor.

(b) Molecular weight: 198.26.

(c) Boiling point: 398-399 degrees C. at 760 mm Hg.

(d) Melting point: 88-93 degrees C. (190-100 degrees F.).

(e) Vapor pressure: 9 mmHg at 232 degrees C.

(f) Evaporation rate (n-butyl acetate = 1): Negligible.

(g) Vapor density (Air = 1): Not applicable.

(h) Volatile fraction by weight: Negligible.

(i) Specific gravity (Water = 1): Slight.

(j) Heat of combustion: -8.40 kcal/g.

(k) Solubility in water: Slightly soluble in cold water, very soluble in alcohol, benzene, ether, and many organic solvents.

(3) Fire, explosion, and reactivity hazard data.

(a) Flash point: 190 degrees C. (374 degrees F.) Setaflash closed cup.

(b) Flash point: 226 degrees C. (439 degrees F.) Cleveland open cup.

(c) Extinguishing media: Water spray; dry chemical; carbon dioxide.

(d) Special fire fighting procedures: Wear self-contained breathing apparatus and protective clothing to prevent contact with skin and eyes.

(e) Unusual fire and explosion hazards: Fire or excessive heat may cause production of hazardous decomposition products.

(f) Hazardous polymerization: Will not occur.

(4) Reactivity data.

(a) Stability: Stable

(b) Incompatibility: Strong oxidizers.

(c) Hazardous decomposition products: At with any other organic material, combustion may produce carbon monoxide. Oxides of nitrogen may also be present.

(5) Spill and leak procedures.

(a) Sweep material onto paper and place in fiber carton.

(b) Package appropriately for safe feed to an incinerator or dissolve in compatible waste solvents prior to incineration.

(c) Dispose of in an approved incinerator equipped with afterburner and scrubber or contract with licensed chemical waste disposal service.

(d) Discharge treatment or disposal may be subject to federal, state, or local laws.

(e) Wear appropriate personal protective equipment.

(6) Special storage and handling precautions.

(a) High exposure to MDA can occur when transferring the substance from one container to another. Such operations should be well ventilated and good work practices must be established to avoid spills.

(b) Pure MDA is a solid with a low vapor pressure. Grinding or heating operations increase the potential for exposure.

(c) Store away from oxidizing materials.

(d) Employers shall advise employees of all areas and operations where exposure to MDA could occur.

(7) Housekeeping and hygiene facilities.

(a) The workplace should be kept clean, orderly, and in a sanitary condition. The employer should institute a leak and spill detection program for operations involving MDA in order to detect sources of fugitive MDA emissions.

(b) Adequate washing facilities with hot and cold water are to be provided and maintained in a sanitary condition. Suitable cleansing agents should also be provided to assure the effective removal of MDA from the skin.

(8) Common operations. Common operations in which exposure to MDA is likely to occur include the following: Manufacture of MDA; manufacture of methylene diisocyanate; curing agent for epoxy resin structures; wire coating operations; and filament winding.

[Statutory Authority: Chapter 49.17 RCW. 93-04-111 (Order 92-15), 296-62-07656, filed 2/3/93, effective 3/15/93.]

WAC 296-62-07658 Appendix C to WAC 296-62-076--Medical surveillance guidelines for MDA.

(1) Route of entry:

Inhalation; skin absorption; ingestion. MDA can be inhaled, absorbed through the skin, or ingested.

(2) Toxicology:

MDA is a suspect carcinogen in humans. There are several reports of liver disease in humans and animals resulting from acute exposure to MDA. A well documented case of an acute cardiomyopathy secondary to exposure to MDA is on record. Numerous human cases of hepatitis secondary to MDA are known. Upon direct contact MDA may also cause damage to the eyes. Dermatitis and skin sensitization have been observed. Almost all forms of acute environmental hepatic injury in humans involve the hepatic parenchyma and produce hepatocellular jaundice. This agent produces intrahepatic cholestasis. The clinical picture consists of cholestatic jaundice, preceded or accompanied by abdominal pain, fever, and chills. Onset in about 60 percent of all observed cases is abrupt with severe abdominal pain. In about 30 percent of observed cases, the illness presented and evolved more slowly and less dramatically, with only slight abdominal pain. In about 10 percent of the cases only jaundice was evident. The cholestatic nature of the jaundice is evident in the prominence of itching, the histologic predominance of bile stasis, and portal inflammatory infiltration, accompanied by only slight parenchymal injury in most cases, and by the moderately elevated transaminase values. Acute, high doses, however, have been known to cause hepatocellular damage resulting in elevated SGPT, SGOT, alkaline phosphatase, and bilirubin.

Absorption through the skin is rapid. MDA is metabolized and excreted over a 48-hour period. Direct contact may be irritating to the skin, causing dermatitis. Also MDA which is deposited on the skin is not thoroughly removed through washing.

MDA may cause bladder cancer in humans. Animal data supporting this assumption is not available nor is conclusive human data. However, human data collected on workers at a helicopter manufacturing facility where MDA is used suggests a higher incidence of bladder cancer among exposed workers.

(3) Signs and symptoms:

Skin may become yellow from contact with MDA.

Repeated or prolonged contact with MDA may result in recurring dermatitis (red-itchy, cracked skin) and eye irritation. Inhalation, ingestion, or absorption through the skin at high concentrations may result in hepatitis, causing symptoms such as fever and chills, nausea and vomiting, dark urine, anorexia, rash, right upper quadrant pain, and jaundice. Corneal burns may occur when MDA is splashed in the eyes.

(4) Treatment of acute toxic effects/emergency situation:

If MDA gets into the eyes, immediately wash eyes with large amounts of water. If MDA is splashed on the skin, immediately wash contaminated skin with mild soap or detergent. Employee should be removed from exposure and given proper medical treatment. Medical tests required under the emergency section of the medical surveillance subsection (13)(d) must be conducted. If the chemical is swallowed do not induce vomiting but remove by gastric lavage.

[Statutory Authority: Chapter 49.17 RCW. 93-04-111 (Order 92-15), 296-62-07658, filed 2/3/93, effective 3/15/93.]

 

WAC 296-62-07660 Appendix D to WAC 296-62-076--Sampling and analytical methods for MDA monitoring and measurement procedures. 

Measurements taken for the purpose of determining employee exposure to MDA are best taken so that the representative average 8-hour exposure may be determined from a single 8-hour sample or two 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 work shift 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).

There are a number of methods available for monitoring employee exposures to MDA. The method WISHA currently uses is included below.

The employer, however, has the obligation of selecting any monitoring method which meets the accuracy and precision requirements of the standard under his/her 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 the select PEL.

WISHA methodology.

Sampling procedure.

Apparatus:

Samples are collected by use of a personal sampling pump that can be calibrated within +5 percent of the recommended flow rate with the sampling filter in line.

Samples are collected on 37 mm Gelman type A/E glass fiber filters treated with sulfuric acid. The filters are prepared by soaking each filter with 0.5 mL of 0.26N H2SO4. (0.26 N H2SO4 can be prepared by diluting 1.5 mL of 36N H2SO4 to 200 mL with deionized water.) The filters are dried in an oven at 100 degrees C. for one hour and then assembled into three-piece 37 mm polystyrene cassettes without backup pads. The front filter is separated from the back filter by a polystyrene spacer. The cassettes are sealed with shrink bands and the ends are plugged with plastic plugs.

After sampling, the filters are carefully removed from the cassettes and individually transferred to small vials containing approximately 2 mL deionized water. The vials must be tightly sealed. The water can be added before or after the filters are transferred. The vials must be sealable and capable of holding at least 7 mL of liquid. Small glass scintillation vials with caps containing Teflon liners are recommended.

Reagents:

Deionized water is needed for addition to the vials.

Sampling technique:

Immediately before sampling, remove the plastic plugs from the filter cassettes.

Attach the cassette to the sampling pump with flexible tubing and place the cassette in the employee's breathing zone.

After sampling, seal the cassettes with plastic plugs until the filters are transferred to the vials containing deionized water.

At some convenient time within 10 hours of sampling, transfer the sample filters to vials.

Seal the small vials lengthwise.

Submit at least one blank filter with each sample set. Blanks should be handled in the same manner as samples, but no air is drawn through them.

Record sample volumes (in L of air) for each sample, along with any potential interferences.

Retention efficiency:

A retention efficiency study was performed by drawing 100 L of air (80 percent relative humidity) at 1 L/min through sample filters that had been spiked with 0.814 microgram MDA. Instead of using backup pads, blank acid-treated filters were used as backups in each cassette. Upon analysis, the top filters were found to have an average of 91.8 percent of the spiked amount. There was no MDA found on the bottom filters, so the amount lost was probably due to the slight instability of the MDA salt.

Extraction efficiency:

The average extraction efficiency for six filters spiked at the target concentration is 99.6 percent.

The stability of extracted and derivatized samples was verified by reanalyzing the above six samples the next day using fresh standards. The average extraction efficiency for the reanalyzed samples is 98.7 percent.

Recommended air volume and sampling rate:

The recommended air volume is 100 L.

The recommended sampling rate is 1 L/min.

Interferences (sampling):

MDI appears to be a positive interference. It was found that when MDI was spiked onto an acid-treated filter, the MDI converted to MDA after air was drawn through it.

Suspected interferences should be reported to the laboratory with submitted samples.

Safety precautions (sampling):

Attach the sampling equipment to the employees so that it will not interfere with work performance or safety.

Follow all safety procedures that apply to the work area being sampled.

Analytical procedure:

Apparatus: The following are required for analysis.

A GC equipped with an electron capture detector. For this evaluation a Hewlett Packard 5880 Gas Chromatograph equipped with a Nickel 63 High Temperature Electron Capture Detector and a Linearizer was used.

A GC column capable of separating the MDA derivative from the solvent and interferences. A 6 ft X 2 mm ID glass column packed with 3 percent OV-101 coated on 100/120 Gas Chrom Q or a 25 meter DB-1 or DB-5 capillary column is recommended for this evaluation.

A electronic integrator or some other suitable means of measuring peak areas or heights.

Small resealable vials with Teflonlined caps capable of holding 4 mL.

A dispenser or pipet for toluene capable of delivering 2.0 mL.

Pipets (or repipets with plastic or Teflon tips) capable of delivering 1 mL for the sodium hydroxide and buffer solutions.

A repipet capable of delivering 25 micro-L HFAA.

Syringes for preparation of standards and injection of standards and samples into a GC.

Volumetric flasks and pipets to dilute the pure MDA in preparation of standards.

Disposable pipets to transfer the toluene layers after the samples are extracted.

Reagents:

0.5 NaOH prepared from reagent grade NaOH.

Toluene, pesticide grade. Burdick and Jackson distilled in glass toluene was used.

Heptafluorobutyric acid anhydride (HFAA). HFAA from Pierce Chemical Company was used.

pH 7.0 phosphate buffer, prepared from 136 g potassium dihydrogen phosphate and 1 L deionized water. The pH is adjusted to 7.0 with saturated sodium hydroxide solution.

4,4'-Methylenedianiline (MDA), reagent grade.

Standard preparation:

Concentrated stock standards are prepared by diluting pure MDA with toluene. Analytical standards are prepared by injecting uL amounts of diluted stock standards into vials that contain 2.0 mL toluene.

25 L HFAA are added to each vial and the vials are capped and shaken for 10 seconds.

After 10 min, 1 mL of buffer is added to each vial.

The vials are recapped and shaken for 10 seconds.

After allowing the layers to separate, aliquots of the toluene (upper) layers are removed with a syringe and analyzed by GC.

Analytical standard concentrations should bracket sample concentrations. Thus, if samples fall out of the range of prepared standards, additional standards must be prepared to ascertain detector response.

Sample preparation:

The sample filters are received in vials containing deionized water.

1 mL of 0.5N NaOH and 2.0 mL toluene are added to each vial.

The vials are recapped and shaken for 10 min.

After allowing the layers to separate, approximately 1 mL aliquots of the toluene (upper) layers are transferred to separate vials with clean disposable pipets.

The toluene layers are treated and analyzed.

Analysis:

GC conditions

Zone temperatures:

Column--220 degrees C.

Injector--235 degrees C.

Detector--335 degrees C.

C Gas flows, N2 Column--30 mL/min

He Column 0.9 mL/min. (capillary) with 30 mL/min. ArCH4 (95/5) makeup gas

Injection volume: 5.0 uL

Column: 6 ft X 1/8 in ID glass, 3% OV-101 on 100/120 Gas Chrom Q or 25 meter x .25 mm DB-1 or DB-5 capillary

Retention time of MDA derivative: 2.5 to 3.5, depending on column and flow

Chromatogram:

Peak areas or heights are measured by an integrator or other suitable means.

A calibration curve is constructed by plotting response (peak areas or heights) of standard injections versus mg of MDA per sample. Sample concentrations must be bracketed by standards.

Interferences (analytical):

Any compound that gives an electron capture detector response and has the same general retention time as the HFAA derivative of MDA is a potential interference. Suspected interferences reported to the laboratory with submitted samples by the industrial hygienist must be considered before samples are derivatized.

GC parameters may be changed to possibly circumvent interferences.

Retention time on a single column is not considered proof of chemical identity. Analyte identity should be confirmed by GC/MS if possible.

Calculations:

The analyte concentration for samples is obtained from the calibration curve in terms of mg MDA per sample. The extraction efficiency is 100 percent. If any MDA is found on the blank, that amount is subtracted from the sample amounts. The air concentrations are calculated using the following formulae: Microgram/m3 = (microgram MDA per sample) (1000)/(L of air sampled) ppb = (microgram/m3) (24.46)/(198.3) = (microgram/m3)(0.1233) where 24.46 is the molar volume at 25 degrees C. and 760 mm Hg.

Safety precautions (analytical):

Avoid skin contact and inhalation of all chemicals.

Restrict the use of all chemicals to a fume hood if possible.

Wear safety glasses and a lab coat at all times while in the lab area.

[Statutory Authority: Chapter 49.17 RCW. 93-04-111 (Order 92-15), 296-62-07660, filed 2/3/93, effective 3/15/93.]

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