CHAPTER 1: CONTAMINANTS - Oregon

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Section II(previously Section I of Oregon OSHA’s Technical Manual)SAMPLING, MEASUREMENTSMETHODS and INSTRUMENTSCHAPTER 1:PERSONAL SAMPLING FOR AIRCONTAMINANTSCHAPTER 2:OCCUPATIONAL SKIN EXPOSURECHAPTER 3:TECHNICAL EQUIPMENT: ON-SITEMEASURMENTSCHAPTER 4:SAMPLE SHIPPING AND HANDLINGSection II / Chapter 2 - Page 1

SECTION II: CHAPTER 2SURFACE CONTAMINANTS, SKIN EXPOSURE,BIOLOGICAL MONITORING AND OTHER ANALYSESChapter Revision Information: This chapter was previously identified as Section 1, Chapter 2 inOregon OSHA’s circa 1996 Technical Manual. The Section numberwas modified from Section I to Section II in December 2014 to provideuniformity with the Federal OSHA Technical Manual (OTM). In December 2014, the original “Sampling for SurfaceContamination” chapter was replaced by Federal OSHA’s February11th,2014 update “Personal Sampling for Air Contaminants”. In December 2014, Federal OSHA’s February 11th,2014 TechnicalManual update “Occupational Skin Exposure” was customized tomake the document’s instructions specific to Oregon OSHA’s samplingequipment, laboratory and state specific regulations. In December 2014, several references to Federal OSHA CPL’s,Directives, and Field Operations Manual (FOM) were revised whenappropriate to reflect Oregon OSHA’s Field Inspection ReferenceManual (FIRM).Section II / Chapter 2 - Page 2

SECTION II: CHAPTER 2SURFACE CONTAMINANTS, SKIN EXPOSURE,BIOLOGICAL MONITORING AND OTHER ANALYSESTABLE OF CONTENTSI.INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5II.BASICS OF SKIN EXPOSURE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6A. Effects on the Skin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6B. Skin Absorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7C. Risk Assessment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8D. Estimating the Extent of Absorption of Chemicals through Skin . . .10E.Glove Permeability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .12WIPE SAMPLING, FIELD PORTABLE X-RAY FLUORESCENCESAMPLING, DERMAL SAMPLING AND BIOLOGICALMONITORING . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .13A. Surface Wipe Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .13B. Field Portable X-Ray Fluorescence . . . . . . . . . . . . . . . . . . . . . . . . . . .14C. Dermal Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .15D. Biological Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .15SAMPLING METHODOLOGY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .16A. Surface Wipe Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .16B. Skin Sampling Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .18C. Biological Monitoring Methodology . . . . . . . . . . . . . . . . . . . . . . . . . .19V.ENFORCEMENT RECOMMENDATIONS . . . . . . . . . . . . . . . . . . . . . .22VI.CUSTOM SERVICES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .24A. Mass Spectrometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .24B. Materials Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .25C. Sampling for Biological Pathogens . . . . . . . . . . . . . . . . . . . . . . . . . . .25D. Explosibility Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .25REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .27III.IV.VII.Section II / Chapter 2 - Page 3

LIST OF APPDENENDICESAPPENDIX: AChemicals Noted for Skin Absorption . . . . . . . . . . .29APPENDIX: B-1Biological Exposure Guidelines (BEI & OES) . . . .40APPENDIX: B-2Biological Exposure Guidelines (General Industry) .46APPENDIX: CProcedures for Collecting Wipe Samples . . . . . . . . .53APPENDIX: DCombustible Dust Bulk Sampling . . . . . . . . . . . . . . .55Section II / Chapter 2 - Page 4

I. IntroductionThe purpose of this chapter is to provide guidance to OSHA Compliance Safety and HealthOfficers (CSHOs) and to the industrial hygiene community on the potential for skin exposure tochemicals in the workplace and the available means of assessing the extent of skin exposure.This chapter provides guidance for the use and interpretation of surface wipe sampling forassessing potential contamination which may lead to biological uptake through inhalation,ingestion, or dermal exposure. This chapter discusses methods for assessing skin contamination,such as dermal dosimeters (e.g., sorbent pads) and dermal wipe sampling, and provides guidancefor monitoring of biological uptake. Finally, this chapter provides guidance for certainspecialized analyses unrelated to dermal exposure, such as soil analysis, materials failureanalysis, explosibility determinations, and identification of unknowns.Skin exposure to chemicals in the workplace is a significant problem in the United States. Boththe number of cases and the rate of skin disorders exceed recordable respiratory conditions. In2010, 34,400 recordable skin diseases or disorders were reported by the Bureau of LaborStatistics (BLS) at a rate of 3.4 illnesses per 10,000 full-time employees, compared to 19,300respiratory conditions with a rate of 1.9 illnesses per 10,000 full-time employees (BLS, 2011).In addition to causing skin diseases, many chemicals that are readily absorbed through the skincan cause other health effects and contribute to the dose absorbed by inhalation of the chemicalfrom the air. Skin absorption can occur without being noticed by the worker. This is particularlytrue for non-volatile chemicals that are hazardous and which remain on work surfaces for longperiods of time. The number of occupational illnesses caused by skin absorption of chemicals isnot known. However, of the estimated 60,000 deaths and 860,000 occupational illnesses per yearin the United States attributed to occupational exposures, even a relatively small percentagecaused by skin absorption would represent a significant health risk (Boeniger, 2003).Biological monitoring refers to testing which is conducted to determine whether uptake of achemical into the body has occurred. Biological monitoring tests assess a sample of a worker’surine, blood, exhaled breath, or other biological media to evaluate the presence of a chemical orits metabolite, or a biochemical change characteristic of exposure to a particular chemical.Biological exposure guidelines such as the American Conference of Governmental IndustrialHygienists (ACGIH) Biological Exposure Indices (BEIs) are numerical values below which it isbelieved nearly all workers will not experience adverse health effects. The BEI valuescorrespond to the biological uptake that would occur in workers exposed to airborneconcentrations at the ACGIH Threshold Limit Value (TLV). When biological monitoringindicates that workers have been exposed to a chemical, but the airborne concentrations arebelow any exposure limits, it suggests that exposures are occurring by another route, such asdermal absorption and/or ingestion.Where other exposure routes are suspected, surface wipe sampling may be useful. Surface wipesampling in areas where food and beverages are consumed and stored (including water bubblers,coolers, and drinking fountains) can be used to assess the potential for ingestion or dermalexposure. Such wipe sampling results can be used to support citations for violations of theSanitation standard, 1910.141, or the applicable housekeeping provisions of the expanded healthstandards, such as Chromium (VI), 1910.1026. To assess the potential for skin absorption,Section II / Chapter 2 - Page 5

surface wipe sampling in work areas may be used to show the potential for contact withcontaminated surfaces. Such results could be used to support violations of the PersonalProtective Equipment (PPE) standard, OAR 437-002-0134, or applicable provisions of theexpanded health standards, such as the Methylenedianiline standard, 1910.1050. For directassessment of skin contamination, skin wipe sampling or dermal dosimetry may be used.In addition, Section VI of this chapter, Custom Services, provides guidance for submittingsamples to the Oregon OSHA Lab for specialized analyses including: Materials failure analysis.Explosibility determinations including:o Combustible dust analysiso Flash pointso Energetic reactivity of chemicalso Autoignition temperaturesBiological sampling for organisms (or chemicals associated with their presence)such as:o Fungio Bacteria (such as Legionella)o Endotoxin (component of the outer membrane of certain gram-negativebacteria)Mass spectrometry analysis for identification of unknown materials in:o Industrial processeso Indoor air sampleso Contaminated water samplesMany of these tests are labor intensive and custom in nature. Always discuss the need forspecialized analysis with the Oregon OSHA Lab prior to collecting or sending samples.Appendix D discusses techniques for combustible dust sampling. Such sampling is conductedwhere the potential for rapid combustion/burning (deflagration) or violent burning with rapidrelease of pressure (explosion) is suspected due to the presence of accumulations of settled dust.Bulk samples of settled dust may be collected and submitted to the Oregon OSHA Lab to send tothe federal OSHA Salt Lake Technical Center (SLTC). Contact the Oregon OSHA Laboratoryprior to collecting samples. Lab analysis is used to determine whether the composition of thedust poses an explosion hazard.II. Basics of Skin ExposureA. Effects on the SkinSkin contact with chemicals can result in irritation, allergic response, chemical burns, andallergic contact dermatitis. Irritant dermatitis may be caused by a variety of substances such asstrong acids and bases (primary irritants). Some examples of chemicals which are potent irritantsinclude: ammonia, hydrogen chloride, and sodium hydroxide. Generally, primary irritantsproduce redness of the skin shortly after exposure with the extent of damage to the tissue relatedto the relative irritant properties of the chemical. In most instances, the symptoms of primarySection II / Chapter 2 - Page 6

irritation are observed shortly after exposure; however, some chemicals produce a delayedirritant effect because the chemicals are absorbed through the skin and then undergodecomposition within aqueous portions of the skin to produce primary irritants. Ethylene oxide,epichlorohydrin, hydroxylamines, and the chemical mustard agents, such as bis (2-chloroethyl)sulfide, are classic examples of chemicals which must first decompose in the aqueous layers ofthe skin to produce irritation.Allergic contact dermatitis, unlike primary irritation, is caused by chemicals which sensitize theskin. This condition is usually caused by repeated exposure to a relatively low concentrationchemical which ultimately results in an irritant response. Frequently, the sensitized area of skin iswell defined, providing an indication of the area of the skin which has been in contact with thesensitizing material.A wide variety of both organic and inorganic chemicals can produce contact dermatitis. Someexamples of these chemicals include: aromatic nitro compounds (e.g., 2,4-dinitrochlorobenzene),diphenols (e.g., hydroquinone, resorcinol), hydrazines and phenylhydrazines, piperazines,acrylates, aldehydes, aliphatic and aromatic amines, epoxy resins, isocyanates, many otherorganic chemicals, and metals (e.g., hexavalent chromium). These substances can also producecontact sensitization. Allergic contact dermatitis is present in virtually every industry, includingagriculture, chemical manufacturing, rubber industry, wood, painting, bakeries, pulp and papermills, healthcare and many others. Also associated with both irritant and allergic contactdermatitis are metalworking fluids (see federal OSHA’s Safety and Health Topics page onMetalworking Fluids).Lastly, there is a class of chemicals which can produce allergic reactions on the skin afterexposure to sunlight or ultraviolet (UV) light. These chemicals are called photosensitizers.Polynuclear aromatic compounds from coke ovens and the petroleum-based tars are examples ofchemicals which can be photoactivated on the skin to cause an irritant response.B. Skin AbsorptionIn addition to the effects that chemicals can directly have on the skin, the skin also acts as apathway for chemicals to be absorbed into the body. The skin primarily consists of two layers—the epidermis and the dermis. The outer layer of the epidermis is composed of a compacted layerof dead epidermal cells called the stratum corneum which is approximately 10 40 micrometersthick. The stratum corneum is the primary barrier for protection against chemical penetration intothe body. Its chemical composition is approximately 40 percent protein, 40 percent water, and 20percent lipid or fat. Because skin cells are constantly being produced by the body, the stratumcorneum is replaced by the body approximately every two weeks.Chemical absorption through the stratum corneum occurs by a passive process in which thechemical diffuses through this dead skin barrier. Estimates of the amount of chemicals absorbedthrough the skin as discussed below assume that the chemicals passively diffuse through thisdead skin barrier and are then carried into the body by the blood flow supplied to the dermis.A number of conditions can affect the rate at which chemicals penetrate the skin. Physicallydamaged skin or skin damaged from chemical irritation or sensitization or sunburn will generallySection II / Chapter 2 - Page 7

absorb chemicals at a much greater rate than intact skin. Organic solvents which defat the skinand damage the stratum corneum may also result in an enhanced rate of chemical absorption. If achemical breakthrough occurs while wearing gloves or other protective clothing, the substancebecomes trapped against the skin, leading to a much higher rate of permeability than withuncovered skin. A worker who wears a glove for an extended period of time experiencesenhanced hydration to the skin simply because of the normal moisture which becomes trappedunderneath the glove. Under these conditions, chemical breakthrough or a pinhole leak in a glovecan result in greater chemical absorption due to increased friction, contact time with thesubstance and increased temperature resulting in a higher overall absorption through the skin. Inanother example, a worker may remove a glove to perform a task which requires increaseddexterity, exposing the skin to additional chemical exposure even after redonning the glove.C. Risk Assessment (Establishing a Significant Risk of Skin Exposure)Risk is determined from the degree of hazard associated with a material, together with the degreeof exposure. Note that dermal exposures may vary widely between workers based on individualhygiene practices. The dermal hazard can be ranked based upon the degree of skin damage orsystemic toxicity associated with the chemical of interest. Those settings with both a high degreeof potential exposure and a high degree of dermal hazard would warrant the closest attention, andjustify collecting sampling data to document the potential exposure, such as wipe sampling, skinsampling, or biological monitoring.In estimating the potential exposure, consider the following: The risk of chemical splash.Significant differences in work practices between individuals.Use of gloves versus hand tools when in direct contact with chemicals.Use of shared tools.Cleaning frequencies for tools and equipment, including doorknobs, telephones,light switches, keyboards and actuators on control panels.The dermal exposure potential can be ranked based upon the: Frequency and duration of skin contact.The amount of skin in contact with the chemical.The concentration of the chemical.The likely retention time of the material on the skin (e.g., highly volatile or drypowdery materials are not likely to remain in contact with the skin, whereasmaterials with a higher molecular weight and sticky materials will remain in contactwith the skin and thus be available for dermal exposure).The potential for dermal absorption, as described below.The absorption of chemicals through the skin can have a systemic toxic effect on the body. Incertain instances dermal exposure is the principal route of exposure, especially for chemicalswhich are relatively non-volatile. For example, biological monitoring results of coke ovenworkers coupled with air monitoring of the workers’ exposure demonstrated that 51 percent ofthe average total dose of benzo[a]pyrene absorbed by coke oven workers occurred via skinSection II / Chapter 2 - Page 8

contact (VanRooij et al., 1993). Studies of workers in the rubber industry suggest that exposureto genotoxic chemicals present in the workplace is greater via the skin than via the lung(Vermeulen et al., 2003).Dermal exposures will contribute significantly to overall exposure for those chemicals with lowvolatility and high dermal penetration, such as many pesticides. One indicator of the volatility ofa chemical is the Vapor Hazard Ratio (VHR). The VHR is the ratio between the vapor pressure(at a given temperature and pressure) and the airborne exposure limit for a chemical; the lowerthe VHR, the less significant the airborne exposure to vapor and the greater the potential fordermal penetration.A common indicator of dermal absorption potential is the relative solubility of a material inoctanol and water, often called the octanol-water partition coefficient (Kow). This partitioncoefficient is often expressed in the logarithmic form as Log Kow. Chemicals with a log Kowbetween -0.5 and 3.0 are the most likely to penetrate the skin (Ignacio and Bullock, 2006).Chemicals must have some degree of lipid (fat) solubility to absorb into the stratum corneum. Topenetrate into the layer of skin, they must have some degree of solubility in water.Note also that skin penetration may be increased under conditions of high humidity. Whentemperatures are elevated, sweating may contribute to increased skin absorption. Wearingineffective or compromised gloves, for example, may actually increase dermal penetration.Proper selection and maintenance of chemical protective gloves, as required by the PPE standard(OAR 437-002-0134), are essential to ensure effective protection. Section II.E providesadditional information regarding glove permeability.Chemicals for which dermal exposures are recognized as making a significant contribution tooverall worker exposure include pesticides, formaldehyde, phenolics, coal tar, creosote, andacrylamide in grouting operations.Appendix A lists chemicals with systemic toxicity for which skin absorption is recognized asmaking a significant contribution to occupational exposure. This list includes only chemicals thathave OSHA PELs or ACGIH TLVs and a “skin designation” or “skin notation,” and is notintended to be a comprehensive list. This exposure may occur by contact with vapor, aerosols,liquid, or solid materials, and includes contact with the skin, mucous membranes and the eyes.Where high airborne concentrations of vapor or aerosol occur involving a chemical noted fordermal absorption, the issue of exposed skin should be considered carefully. Note also thatcertain chemicals, such as dimethyl sulfoxide (DMSO) are known to facilitate dermal absorptionof other chemicals.For chemicals which are absorbed through the skin and which are hazardous, the levels ofexposure on the skin must be maintained below a level at which no adverse effects would beobserved. One of the simplest ways of determining this amount is to estimate the amount of ach

Section II / Chapter 2 - Page 2 SECTION II: CHAPTER 2 SURFACE CONTAMINANTS, SKIN EXPOSURE, BIOLOGICAL MONITORING AND OTHER ANALYSES Chapter Revision Information: This chapter was previously identified as Section 1, Chapter 2 in Oregon OSHA’s circa 1996 Technical Manual. The Section number was modified from Section

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