Journal of Occupational and Environmental Hygiene, 3: 18 ISSN: 1545-9624 print / 1545-9632 online Copyright c 2006 JOEH, LLC DOI:

10.1080/15459620500430581

Potential Uses of Petrochemical Products Can Result in Signicant Benzene Exposures: MSDSs Must List Benzene as an Ingredient
Melvyn Kopstein
Rockville, Maryland

According to 29 CFR1910.1200 (Hazard Communication Standard [HCS]), a material safety data sheet (MSDS) must list a carcinogen as an ingredient if its concentration in a product is 0.1% or more by weight. However, according to the HCS, when the concentration of a carcinogen in a product is less than 0.1% (by weight) it may not be necessary to list it as an ingredient on the MSDS. The standard stipulates that if potential uses of the product can result in exposures to the carcinogen that exceed the Occupational Safety and Health Administration R (OSHA) permissible exposure limit or the ACGIH threshold R limit value (TLV ), then it must be listed. This article focuses on the failure of MSDSs to report benzene as a listed ingredient in products that incorporate petroleum-derived ingredients such as toluene and hexane. In the United States, approximately 238,000 people are occupationally exposed to benzene each year. Only rarely is benzene listed as an ingredient on MSDSs even though it often comprises more than 0.1% of petroleum solvents and, when its concentrations in petroleum-derived products are much less than 0.1%, inhalation exposures to benzene can be much higher that its OSHA PEL of one part per million (ppm) by volume (v/v) and ACGIH TLV of one-half ppm (v/v). As a consequence of benzenes omission from MSDSs as a listed ingredient, employers are frequently unaware of their requirement to implement 29 CFR 1910.1028 (Benzene Standard) and of the need to address employee exposures to benzene in the workplace. This article demonstrates that benzene should be listed as an ingredient on MSDSs, even at concentrations in benzene-containing products that are between one and two orders of magnitude below OSHAs 0.1% threshold. An exposure assessment methodology is presented that is applicable to employees whose conditions of exposure are similar to those in the published study. These workers make up a similar exposure group. The information and methodology presented here are germane to preparation of accurate MSDSs for benzene-containing products, employers who must comply with 29 CFR 1910.1028, and retrospectively estimating exposures to benzene. Keywords benzene, exposure, model, MSDS, solvent, warning

Address correspondence to: Melvyn Kopstein, 12007 Hitching Post Lane, Rockville, MD 20852; e-mail: melvynk@earthlink.net.

enzene is widely recognized to be a human carcinogen.(1) It is estimated that 238,000 people are occupationally exposed to benzene in the United States.(2) Historically, exposures to benzene in the workplace have come from the use of many different types of petroleum-derived solvents. Many occupational environments have inadequate ventilation and present conditions of exposure that are conducive to benzene inhalation exposures exceeding the Occupational Safety and Health Administration (OSHA) permissible exposure limit (PEL) and the American Conference of Governmental Industrial Hygiene R R (ACGIH ) threshold limit value (TLV ) computed on an 8-hour time-weighted average (TWA) basis. Conditions of exposure include parameters such as concentration of benzene in the product, ventilation in the work setting, air temperature, solvent temperature, other ingredients in the solvent and their effect on ideal liquid behavior, perpendicular distance from a breathing zone to the evaporating liquid, and the amount of time spent performing a task involving the use of the benzenecontaining solvent. One of the most important conditions of exposure is the amount of benzene in a given solvent used by a worker. To comply with the requirements of 29 CFR1910.1200, the Hazard Communication Standard (HCS), a material safety data sheet (MSDS) must provide accurate information about a products ingredients, including its composition and properties. It must also include appropriate health warnings and instructions for safe use. MSDSs are known to have serious deciencies in terms of listing carcinogenic chemicals as ingredients.(34) Material safety data sheets for petroleum-derived solvents rarely include (a) benzene as an ingredient, (b) warnings about the health risks associated with benzene exposures, and (c) necessary precautions to prevent dangerous levels of exposure. Failure on the part of manufacturers to list benzene as an ingredient on MSDSs is an example of serious inaccuracies documented in the literature regarding the listing of hazardous ingredients in MSDSs. Reasons for this failure include:

Journal of Occupational and Environmental Hygiene

January 2006

(a) litigation concerning past exposures to benzene-containing products, (b) expense to eliminate small amounts of benzene from petrochemicals, and (c) formulators of chemical products who rely on the accuracy of information concerning chemical composition and health and safety matters furnished by upstream suppliers (often large chemical or oil companies) for ingredients used in their product recipes. Manufacturers often use common names such as light aliphatic solvent naphtha as listed ingredients on MSDSs. Unfortunately, solvent products with common names and common name ingredients used in product formulations do not have standard and well-understood properties. For example, almost any petrochemical product may be described as a petroleum distillate. A product MSDS may provide information, such as vapor pressure, boiling range, percentage aromatics, and molecular weight, from which important clues may be gleaned about the products compositionincluding benzene content. The use of common names as listed ingredients is confusing to employers and employees and may even be confusing to industrial hygienists and other scientists involved with health and safety matters if they do not have specic training in the properties of petrochemicals. Since no later than 1977, the National Institute of Occupational Safety and Health (NIOSH) has taken the position that the use of common names should be avoided in favor of listing chemical substances by their complete names according to recognized nomenclature.(5) Through analytical testing, manufacturers can easily determine whether benzene should be listed as an ingredient on MSDSs (i.e., contains benzene in concentrations in excess of 0.1% by weight). Scientic literature cited in this investigation demonstrates that analytical testing is warranted for many petrochemicals used in product formulations. Even if product testing shows that benzene is present in concentrations less than 0.1% by weight, to ascertain whether benzene must be included as a listed ingredient on the product MSDS, the product manufacturer must still determine whether potential uses of the product could result in benzene exposures that exceed its TLV or PEL. It is not necessary for a manufacturer to conduct air monitoring (which can be expensive and time-consuming) for a wide range of potential uses of its product to determine whether benzene must be listed as an ingredient on the MSDS. Exposure models can be invaluable in estimating workplace exposures.(67) To facilitate compliance with the HCS, manufacturers may choose to use exposure models in the evaluation of exposures to benzene or other carcinogenic ingredients of a chemical product deriving from potential uses of that product. The HCS does not permit a manufacturer to rely on exposure modeling to demonstrate that benzene (or any carcinogen) is not required to be listed as a product ingredient. However, there is no reason for manufacturers not to rely on an exposure model in determining that benzene should be a listed product ingredient. Four well-known types of exposure models available for manufacturers and industrial hygienists to use (and which apply to specic conditions) are: (1) well-mixed, (2) box, (3)
2

turbulent diffusion, and (4) molecular diffusion (for when a stagnant air condition exists). Two important requirements in selecting an exposure model are: (1) that it is consistent with conditions of exposure, and (2) the existence of enough information to reliably estimate model parameters. It is necessary to have reliable estimates of model parameters such as the size of the near eld, emissions rate, eddy diffusivity, air change rate, and rate of ow into and out of near eld in order to achieve a solution of the unsteady state partial differential or steady state mass balance equations.(78) Since historical personal air sampling data are rarely available, it is often necessary to retrospectively estimate exposures to benzene. Examples where this need exists include epidemiology studies and litigation. If enough information is available, then exposure models may be employed in retrospective assessments. Similar exposure groups (SEGs) are groups of workers having the same general exposure prole because of the similarity and frequency of the tasks they perform, the materials and processes they work with, and the similarity of the way they perform the tasks.(9,p.42) The utilization of existing exposure monitoring data is an accepted method to estimate past exposures to benzene experienced by individuals with comparable conditions of exposure (and for which no monitoring data are available).(1013) Coupled with reliable information about the benzene content of its product, a manufacturer can likewise utilize monitoring data for similar conditions of exposure to estimate workplace exposures and to facilitate determination of whether benzene should be a listed ingredient on the products MSDS. The objectives of this article are: (a) to demonstrate that widely available petroleum-derived solvents have long been known to contain enough benzene to cause serious exposures; (b) for workers using benzene-containing products under conditions of exposure similar to those for which benzene exposure data were experimentally determined and published, compute expected airborne benzene exposure levels as a function of benzene concentration in a petrochemical product; and (c) to demonstrate that in order to comply with 29 CFR1910.1200, which is OSHAs Hazard Communication Standard (HCS), a product MSDS must include benzene as an ingredientand include appropriate warnings and instructionseven when the concentrations of benzene in the product are well below the 0.1% threshold corresponding to when the MSDS must list benzene as an ingredient. METHODS Scientic Literature The scientic literature cited in this investigation (a) provides an extensive up-to-date database regarding the concentrations of benzene in many solvents commonly used in the workplace; (b) demonstrates that benzene compositions of commonly used petroleum-derived products have remained high from 1955 to 2005; (c) shows that MSDSs for many petrochemical solvents have been required to list benzene as an
January 2006

Journal of Occupational and Environmental Hygiene

ingredient because they have consistently contained benzene at concentrations that exceed 0.1%; (d) conrms that even when a product contains benzene at concentrations much less than 0.1%, its MSDS may be required to list benzene as an ingredient; (e) sets forth thermodynamic constraints and technical challenges in reducing benzene levels in solvents; (f) provides published breathing-zone concentrations of benzene from the use of a petroleum-derived solvent containing benzene at an initial concentration of 58 ppm (w/w) under known and commonly encountered conditions of exposure; (g) provides a validated methodology for performing retrospective benzene exposure assessments using SEGs; and (h) presents evidence that MSDSs are often incomplete, inaccurate, and have many serious deciencies, such as failing to disclose hazardous product ingredients. Similar Exposure Group The accumulation of benzene vapor in a simulated breathing zone was investigated by Fedoruk et al.,(14) in an experimental study conducted in a warehouse using a specially formulated recycled mineral spirits solvent (containing benzene at an initial concentration of 58 ppm by weight). The Fedoruk results are used in this article to estimate benzene exposures experienced by individuals having similar conditions of exposure to benzene-containing products and to demonstrate conclusively that MSDS must list benzene as an ingredient even when present at concentrations well below 0.1% (w/w). Fedoruk et al. followed Environmental Protection Agency (EPA) and NIOSH methods to take air samples that were averaged over 1-hour periods at a point 36 inches from and directly over the solvent. The solvent was in a commonly available parts washer sink located approximately 2 feet from a wall in a large warehouse. The evaporation and dispersion of benzene from the solvent resulted in a 1-hour timeweighted average benzene concentration of 0.5 ppm (v/v) in the simulated breathing zone. The warehouse setting in the Fedoruk study had no overhead fans, two large garage doors that were open during the exposure experiments, and no appreciable airow disturbance in the workspace where the experiments were conducted. No exhaust or other special ventilation was provided. The ventilation discussed in the Fedoruk study was inadequate in terms of being capable of removing benzene-containing vapors from the work area. Occupational environments where petroleumderived products are used under conditions of inadequate ventilation are commonplace. The Fedoruk air monitoring data may be used to estimate benzene exposures to workers who experienced or may experience similarly inadequate ventilation and other conditions of exposure. According to Fedoruk, comparable ventilation conditions would be one important factor in applying the studys results to other workplace environments. The other conditions of exposure in the Fedoruk study that would be important in determining whether a workers exposure scenario was (or is) consistent with those of the Fedoruk investigation are: (a) use of a benzene-containing solvent, (b)

contiguous area of evaporating solvent, (c) worker breathing zone located within the eld directly above the evaporating solvent, (d) air temperature, (e) solvent temperature, and (f) vertical distance from evaporating solvent to breathing zone. Exposure Estimation Benzene exposures to individuals using mineral spirits, hexane, or other benzene-containing products, and whose conditions of exposure are comparable to those described in the Fedoruk study, are calculated as a function of product benzene content. The methodology employed herein is consistent with the use of SEGs to compute benzene exposures as reported in the literature(1013) and with the Fedoruk nding that benzene concentrations in the simulated breathing zone are roughly proportional to benzene content of the solvent.(14) The procedure consists of rst calculating the ratio of the benzene content of a petroleum-derived solvent to the average benzene content of the specially formulated solvent used in the Fedoruk study during the 1-hour period in which exposure data were taken. This calculation yields a proportionality constant referred to herein as an exposure factor. The airborne benzene concentration at a distance of 36 inches (used by Fedoruk as the surrogate breathing zone) above the benzenecontaining product is obtained by simply multiplying the Fedoruk exposure monitoring result (benzene concentration reported in ppm by volume) by this exposure factor. If the other conditions of exposure are similar to Fedoruk et al., but the distance from the breathing zone to the evaporating liquid is less than 36 inches, then the benzene concentration in the breathing zone would be higher than the concentration calculated by this method. Since benzene is one of the most volatile constituents in the solvent used in the Fedoruk investigation, its relative concentration in the evaporating product diminishes with time. Using Fedoruks estimate that benzene concentration in mineral spirits diminishes at a rate of approximately 10% per hour, the average concentration of benzene in Fedoruks solvent during the 1-hour experiment was approximately 55.2 ppm (w/w).(14) This average concentration is used in the present investigation to calculate exposure factors. When the volatility of a petroleum-derived product (e.g., industrial-grade hexane) approximates that of benzene, there is no decrease in benzene concentration in that product as it evaporates. For a product that is more volatile than benzene (e.g., gasoline) the concentration of benzene in the product increases as evaporation proceeds. The described methodology may be used to determine the benzene concentration in petroleum-derived products at which the TLV and PEL concentrations are pierced for conditions of exposure comparable to those in the Fedoruk study. If a workers conditions of exposure are more severe than in the Fedoruk study, then the results provided should be interpreted as lower limits of exposure. For instance, if (a) the workers breathing zone is closer to the evaporating solvent than the 36-inch distance in the Fedoruk study, (b) the temperatures of the workplace air and/or of the evaporating solvent are higher
January 2006 3

Journal of Occupational and Environmental Hygiene

than discussed by Fedoruk, or (c) the evaporating liquid is a non-ideal liquid exhibiting positive deviations from Raoults law, then the exposures to benzene would be higher than the levels reported by this investigation. In those situations, exposure estimates obtained using this investigations methodology would represent lower limits of exposure. RESULTS Benzene Concentrations in Petrochemicals The cited scientic literature provides representative benzene compositions for many commonly used solvents and demonstrates that the amount of benzene in these solvents has remained relatively unchanged from 1955 to the present. This information should be (and should have been) taken into account in the preparation of MSDSs. Table I includes data from products manufactured in foreign and domestic reneries. A signicant percentage of rened petroleum products consumed in the United States is produced in foreign countries. For instance, in 2001, the United States imported more than 12% of its total requirements for rened petroleum products (almost 20 million barrels per day).(32) Imports accounted for more than 37% (895,000 barrels per day) of nongasoline petroleum products, including petrochemicals, naphthas, white spirits, and blending components used each day in the United States. There is no evidence that solvents produced in foreign reneries contain more or less benzene than similar products produced in U.S. reneries. MSDSs do not indicate where petroleum-derived product ingredients were manufactured. According to OSHAs HCS, importers of chemical products are responsible for evaluating the properties (including ascertaining which chemicals must be listed as ingredients) of those products and preparing accurate MSDSs. The scientic literature includes additional references regarding benzene in petroleum-derived solvents and in products manufactured in the United States and in foreign countries. In one study, benzene was present at an average concentration of 4100 ppm (w/w) in a sample of 134 petroleum distillates.(20) In 1980, the U.S. Consumer Product Safety Commission(33) reported on 63 consumer products that had less than 1000 ppm (w/w) benzene, and 7 others that contained benzene at concentrations of between 1000 ppm (w/w) and 2500 ppm (w/w). In 1999, The Merck Manual reported that benzene is a constituent of model airplane glue, toluene, xylene, and hydrocarbons.(34) A 1987 study found that 76.4% of solvents tested and 19.1% of thinners tested contained benzene at concentrations in excess of 10,000 ppm (w/w), with a mean concentration of 28,800 ppm (w/w).(1) Since benzene does not add functionality to general purpose solvents, its presence in solvents may be considered to be a persistent contaminant. Thermodynamic constraints make it difcult and expensive to separate benzene from many aliphatic and aromatic hydrocarbons found in solvents. For instance, a major reason for the high benzene content in industrialgrade hexane (which contains dened ranges of constituents including n-hexane, methyl cyclopentane, various hexane
4

TABLE I. Product

Benzene Content of Petrochemicals Benzene Content (ppm) 15,000(5) 30,000(5) 500(15) Less than 1000(16) Less than 10,000(17) 28,100(18) 10,000 to 60,000(19) 42,000(20) 15,000 to 93,000(21) 1000(22) 6,000 to 70,000(23) 15,000(23) Greater than 10,000(24) Greater than 10,000(24) Greater than 10,000(24) Greater than 10,000(24) Greater than 10,000(24) Greater than 10,000(24) Greater than 10,000(24) 1000(25) 700(25) 1000(25) Less than 1000(26) Less than 200(26) Less than 20(26) 15,000(27) 1000(27) 1000(27) 1000(28) 1000 to 10,000(29) 37,000(30) 1000 to 10,000(30) 1000(30) 300 to 887(30) 1000 to 2000(30) 10,000(30) Less than 10,000(31)

Rubber solvent Petroleum benzine Highly puried n-hexane Commercial hexanes Stoddard solvent Commercial hexane A A n-Hexane Spot remover 32 Naphtha solvents Stoddard solvent 8 Naphtha solvents Hexane B Petroleum naphtha Stoddard solvent VM&P naphtha Rubber solvent Varsol 1 Varsol 3 Varsol 18 Stoddard solvent 140 Flash aliphatic solvent VM&P naphtha Stoddard solventC Stoddard solvent D Stoddard solvent E Rubber solvent VM&P naphtha Stoddard solvent VM&P naphtha Alkyd paint Hexane Toluene Xylene Ethyl benzene Mineral spirits Shell rubber solvent VM&P naphtha
A Hexane B Characterized

A (commercial hexane) dened by EPA.(26) as having a low benzene content. C Type 1: Hydrodesufurized (contains less than 25% aromatics). D Type 2: Solvent extracted (contains less than 5% aromatics). E Type 3: Severely hydrotreated (contains less than 1% aromatics).

isomers, and n-hexane)(35) is the existence of azeotropes involving benzene and several of the constituents.(36) It is necessary to employ techniques such as solvent extraction, azeotropic distillation, and severe hydrotreatment to signicantly reduce the benzene content of high purity reagentgrades of chemicals, such as n-hexane and toluene. Reagent grades of chemicals are much more expensive to produce than their solvent grade counterparts. The scientic literature does not indicate the existence of new or commercially viable unit
January 2006

Journal of Occupational and Environmental Hygiene

operations or separation techniques employed in reneries to reduce the amount of benzene in industrial-grade and general purpose solvents below the levels shown in Table I. Innovative research strives to overcome the technical and economic challenges of removing benzene from petrochemicals such as hexane.(37) Workplace Exposure Fedoruk et al.(14) reports that benzene concentrations in a simulated breathing zone were roughly proportional to benzene content of the solvent and alludes to Raoults law in demonstrating that this nding is consistent with thermodynamic principles. For example, doubling the concentration of benzene in an ideal liquid will double the concentration of benzene in the vapor phase at the liquid-vapor interface. The roughly proportional nding in the Fedoruk study is also consistent with mass transfer principles. In the above example, if the concentration of benzene in the vapor at the liquid-vapor interface doubles, then the rate of mass transfer of benzene away from the interface and toward the simulated breathing zone will approximately double. That is due to the fact that the equilibrium concentration of benzene vapor at the interface will be much higher than its concentration in the air distant from the interface, and the mass transfer concentration gradient will be approximated by benzenes concentration at the interface. The Fedoruk investigation involved the use of a solvent in an entirely foreseeable manner that would be viewed as a potential use under OSHAs HCS. Using the described methodology, exposures to benzene for conditions comparable to the Fedoruk study were estimated as a function of benzene content in petroleum-derived solvents. Table II sets forth the results of the exposure estimates from this investigation. The results establish (a) the specially formulated solvent used by Fedoruk, containing benzene at average concentration of only 5.52% of the level at which benzene must be listed on the MSDS as an ingredient, must still list benzene as an ingredient because TABLE II. Benzene Exposure Petroleum-Derived Products Average Benzene Content of Petroleum Derived Solvent in ppm (w/w) 55.2 110.4 552 1000 D 5000
A Fedoruk published result: ACGIH R

from

Use

of

1-Hour Time-Weighted Average Benzene Concentration in ppm (v/v) for Fedoruk Conditions of Exposure14 0.5 A 1.0 B 5.0C 9.1 45.3
TLV
R

exposures can easily exceed ACGIHs TLV for benzene; (b) for potential uses of petroleum-derived products (and depending on the amount of time spent performing a task), OSHAs PEL and short-term exposure limit (STEL) and ACGIHs TLV for benzene are easily exceeded at concentrations of benzene much less than 1000 parts per million (w/w). According to Raoults law, at a given temperature the partial pressure from an ideal liquid mixture component (e.g., benzene) equals the product of the vapor pressure of that pure component and its mole fraction in the mixture. Nonideal liquids exhibit either positive or negative deviations from Raoults law. Negative deviations from Raoults law occur when intermolecular forces increase after a mixture is formed (e.g., mixtures of chloroform and acetone or of nitric acid and water). For products comprised solely of petroleumderived ingredients, deviations from ideal liquid behavior are manifested by positive deviations (intermolecular forces decrease after a mixture is formed) from Raoults law.(38) Positive deviations from Raoults law are exhibited by many commercial products that are mixtures of nonpolar petrochemicals and relatively polar ingredients, such as acetone and alcohols. For such products, the concentration of benzene at the liquid-vapor interface will be higher than predicted by Raoults law.(38) A higher benzene concentration at the vapor-liquid interface will increase the rate of mass transfer of benzene vapor toward a breathing zone as well as resultant exposures. For instance, products having industrialgrade hexane and isopropanol as ingredients are used to clean negatives in the printing industry. This mixture exhibits a positive deviation from Raoults law and will give rise to higher exposures to benzene than predicted by the methodology set forth in this investigation. Exposure concentrations will also increase from the estimates summarized in Table II as (a) the temperature of the air and/or liquid product increase, and (b) as the distance between the breathing zone and the evaporating liquid decreases (employees can be much closer to evaporating solvent as they bend over to perform tasks such as cleaning lm negatives and equipment parts). The magnitudes of positive deviations from Raoults law can be signicant. They must be determined experimentally and will depend on the composition and relative amounts of the mixture ingredients. Manufacturers of chemical products must take this important property into consideration when anticipating benzene exposures that may arise from potential uses of their benzene-containing products. Hazard Communication Standard OSHAs Hazard Communication Standard (HCS) contains unambiguous language requiring the listing of carcinogens.(39) If the components of a mixture could be released in concentrations which would exceed an OSHA PEL, an ACGIH TLV, or could present a health risk to employees, information on these components must be included on the MSDS regardless if their nal concentration in the mixture is less than 1% (or 0.1% for carcinogens). For instance, TDI is a sensitizer at very small concentrations and despite its low concentration in a
January 2006 5

for benzene and MSDS must list benzene as ingredient. B OSHA PEL for BenzeneMSDSs must list benzene as an ingredient. C OSHA short-term exposure limit for benzene. D MSDS for a product containing benzene at this level must list benzene as an ingredient.

Journal of Occupational and Environmental Hygiene

mixture, can be off gassed in quantities which may present a health risk that must be noted on the MSDS.(40) This investigation demonstrates that (under conditions of exposure similar to those in the Fedoruk investigation) a petrochemical solvent containing benzene at a small fraction of 0.1% can easily release benzene in concentrations exceeding OSHAs PEL and ACGIHs TLV. Furthermore at a solvent concentration in excess of 552 ppm w/w, the airborne concentrations of benzene at a distance of 36 inches above the solvent can be expected to exceed OSHAs short-term exposure limit of 5 ppm. For a work environment with similar conditions of exposure, the 1-hour time-weighted benzene exposures for a solvent that contains benzene at the OSHA threshold of 0.1% would be 9.1 ppm. If an employee spent just 1 hour per day engaged in a task using a petroleum-derived product containing 0.1% benzene, and the rest of his workday in a benzene-free environment, he would experience an 8-hour TWA in excess of OSHAs PEL for benzene. Furthermore, after just one-half hour his daily exposure to benzene would exceed ACGIHs TLV. Fedoruk et al.(14) correctly cited the OSHA requirement to list benzene as an ingredient on MSDSs if product use could result in exposures exceeding the OSHA PEL or in a health risk. From the results of this investigation (and since it is entirely foreseeable that potential occupational uses would involve higher air and solvent temperatures as well as shorter distances between the evaporating solvent and a workers breathing zone) it is apparent that benzene should be listed on MSDSs as an ingredient at concentrations less than 58 ppm (w/w). Given the universe of potential uses of petroleum-derived solvents, manufacturers should list benzene as product ingredient (even at very low concentrations) as a rule rather than as an exception. DISCUSSION

Some commonly encountered solvents include: mineral spirits, Stoddard solvent, VM&P naphtha, toluene, xylene, hexane, heptane, trimethyl benzene, lactol spirits, lacquer thinner, and rubber solvent. These solvents, as well as many common name products, appear as ingredients in product mixtures. Some common names appearing on MSDSs as ingredients include: light aliphatic solvent naphtha, aromatic petroleum distillates, combustible petroleum hydrocarbons, aliphatic hydrocarbon, petroleum naphtha, aromatic hydrocarbon mixture family, super high ash naphtha, light aromatic solvent naphtha, proprietary mixture, naphthol spirits, aromatic 100, Stoddard-type aliphatic solvent, aliphatic petroleum distillates, 100% light hydrotreated naphtha, C6 parafns, C6 cycloparafns, petroleum distillates, and 100% hydrotreated light distillate. Since all may contain benzene, the MSDS for any product mixture that lists one or more of the solvents as ingredients may also be required to list benzene as a hazardous ingredient. Table I can be used to compute a weighted average benzene content of a product, if the products MSDS includes the relative proportions of each ingredient. Manufacturers of products that are formulated from different ingredients must also provide MSDSs. OSHAs HCS allows formulators to rely on information on MSDSs from upstream suppliers of the ingredients for information such as chemical composition. If the MSDS for the formulated product comprises MSDSs received from upstream suppliers of the different ingredients physically grouped together, then those suppliers are responsible for the accuracy of the MSDS of the formulated product with respect to the ingredient(s) they supplied. However, if a consolidated product MSDS is prepared by the downstream formulator, then the formulator is responsible for the accuracy of the MSDS with respect to composition, warnings, and other information required by the HCS. CONCLUSIONS

orkers must be informed when products they use contain carcinogens such as benzene. OSHAs Hazard Communication Standard requires that this information be communicated by way of MSDSs. If the manufacturer or other entity whose name appears on a benzene-containing solvent MSDS fails to list benzene as an ingredient, and if that entity is unable to demonstrate that its product will not release benzene in amounts sufcient to cause exposures that exceed OSHA and ACGIH limits, then that product is in violation of the Hazard Communication Standard. Employers require complete and accurate information regarding benzene in MSDSs in order to be aware of the need to comply with 29 CFR1910.1028 and to know when it is necessary to provide adequate ventilation and other protection such as gloves and respirators to their employees. A consequence of an MSDS that is defective (because it does not communicate the required information regarding benzene content and appropriate warnings) is that employers whose employees use that product have failed to meet the requirements of 29 CFR1910.1028.

wide range of petroleum-derived solvents contain benzene. If a manufacturer does not provide information about the benzene content of its product, then it is appropriate to estimate the benzene content of the product from the scientic literature. These estimates can be used in retrospective exposure assessments, epidemiology studies, in determining whether benzene must be listed as an ingredient on MSDSs, and in complying with the requirements of OSHAs Benzene Standard (29 CFR 1910.1028). This investigation employs a methodology involving similar exposure groups to calculate exposures to benzene from the occupational use of petroleum-derived products. The results are relevant to individuals (a) whose use of products occurs (or occurred) in occupational settings where exhaust ventilation or other suitable engineering controls are not (or were not) provided, and in which ventilation is (or was) inadequate in terms of removing benzene-containing product vapors, and (b) having conditions of exposure similar to the Fedoruk investigation. Many of the 238,000 people estimated to
January 2006

Journal of Occupational and Environmental Hygiene

experience exposures to benzene in the United States each year work with benzene-containing products under conditions of inadequate ventilation that bear similarities to the conditions of exposure described in the Fedoruk investigation. The exposure calculation methodology used in this investigation is applicable to individuals who fall within this similar exposure group. It has been demonstrated by Fedoruk, and in the present study, that a concentration of benzene much less than 1000 ppm (w/w) in a petroleum-derived product may be sufcient to cause benzene exposures that exceed OSHAs PEL and ACGIHs TLV. Despite this fact, very few MSDSs list benzene as an ingredient and provide the necessary warnings and instructions for safe use. Manufacturers must do a better job of communicating the amounts of benzene in solvents and in providing appropriate warnings and instructions for safe use to employers.

REFERENCES
1. U.S. Department of Health and Human Services, Public Health Service, Agency for Toxic Substances and Disease Registry (ASTDR): Toxicological Prole for Benzene. Atlanta, Ga.: ASTDR, 1997. 2. Verma, Y., and S.V.S. Rana: Biological monitoring of exposure to benzene in petrol pump workers and dry cleaners. Ind. Health 39:320333 (2001). 3. Frazier, L.M., B.W. Beasley, K.S. Gyanendra, et al.: Health information in material safety data sheets for a chemical that causes asthma. J. Gen. Intern. Med. 16:8993 (2001). 4. Welsh, M.S., M. Lamesse, and F. Karpinski: The verication of hazardous ingredients disclosures in selected material safety data sheets. Appl. Occup. Environ. Hyg. 15:409420 (2000). 5. U.S. Department of Health, Education, and Welfare (DHEW), Public Health Service (PHS), Centers for Disease Control (CDC), and National Institute for Occupational Safety and Health (NIOSH): NIOSH Criteria for a Recommended StandardOccupational Exposure to Alkanes (C5 to C8 ). DHEW (NIOSH) Pub. No. 77-151. Washington, D.C.: DHEW, PHS, CDC, NIOSH, March 1977. 6. Goldstein, B.: Benzene toxicity. Occup. Med. State of the Art Reviews. 3(3):JulySeptember 1988. 7. Keil, C.: A tiered approach to deterministic models for indoor air exposures. Appl. Occup. Environ. Hyg. 15:145151 (2000). 8. Jayjock, M.A., J.R. Lynch, and D.I. Nelson: Risk Assessment Principles for the Industrial Hygienist. Fairfax, Va.: AIHA Press, 2000. 9. Mulhausen, J.R., and J. Damiano: A Strategy for Assessing and Managing Occupational Exposures. Fairfax, Va.: AIHA Press, 1998. 10. Rinsky, R.A., A.B. Smith, R. Hornung, et al.: Benzene and leukemia. N. Engl. J. Med. 316:10441050 (1987). 11. Glass, D.C., C.N. Gray, D.J. Jolley, et al.: Leukemia risk associated with low-level benzene exposure. Epidemiology 14:569577 (2003). 12. Glass, D.C., C.N. Gray, G.G. Adams, et al.: Validation of exposure estimation for benzene in the Australian petroleum industry. Toxicol. Ind. Health 17:113127 (2001). 13. Glass, D.C., G.G. Adams, R.W. Manuell, et al.: Retrospective exposure assessment for benzene in the Australian petroleum industry. Ann. Occup. Hyg. 44:301320 (2000). 14. Fedoruk, M., R. Bronstein, and B. Kerger: Benzene exposure assessment for use of a mineral spirits-based degreaser. Appl. Occup. Environ. Hyg. 18:764781 (2003). 15. International Program on Chemical Safety (IPCS): Environmental Health Criteria 122, n-Hexane. Geneva: World Health Organization, United Nations Environment Program, International Labor Organization, and the World Health Organization, 1991.

16. ASTM: Specication for Commercial Hexanes (D 1836-02). [Standard] West Conshohocken, Pa.: ASTM International, 2002. 17. Agency for Toxic Substances and Disease Registry (ASTDR): Case Studies in Environmental Medicine, Stoddard Solvent Toxicity. ATSDR Pub. No. ATSDR-HE-CS-2001-0004. Atlanta, Ga.: ATSDR, 2000. 18. Kirk-Othmer Encyclopedia of Chemical Technology: Hexanes. 3rd ed., New York: John Wiley & Sons, Inc., 1983. 19. Occupational Safety and Health Administration (OSHA): Occupational Safety and Health Guidelines for n-Hexane. [Online] Available at http://www.osha.gov/SLTC/healthguidelines/n-hexane/recognition. html (Accessed May 12, 2005). 20. Kasahara, M., H. Suzuki, Y. Takeuchi, et al.: n-Hexane, benzene and other aromatic components in petroleum distillates in Japan. Ind. Health 25:205214 (1987). 21. Pagnotto, L., H. Elkins, H. Brugsch, et al.: Industrial benzene exposure from petroleum naphtha: I. Rubber coating industry. Am. Ind. Hyg. Assoc. J. 22:417421 (1961). 22. Carpenter, C.P., E.R. Kinkead, D.L. Geary Jr., et al.: Petroleum hydrocarbon toxicityAnimal and human response to vapors of Stoddard solvent studies. Toxicol. Appl. Pharm. 32:263281 (1975). 23. Elkins, H., and L. Pagnotto: Benzene content of petroleum solvents. AMA Arch. Ind. Health 13:5154 (1956). 24. U.S. Department of Transportation, United States Coast Guard: Commandant Instruction 6260.25, Implementation of the Benzene Occupational Exposure Standard. Washington, D.C.: U.S. Coast Guard, 1993. 25. U.S. Department of Health, Education, and Welfare (DHEW), Centers for Disease Control (CDC), National Institute for Occupational Safety and Health (NIOSH): NIOSH Criteria for a Recommended StandardOccupational Exposure to Rened Petroleum Solvents. DHEW (NIOSH) Pub. No. 77-192. Washington, D.C.: DHEW, CDC, NIOSH, July 1977. 26. International Program on Chemical Safety (IPCS): Environmental Health Criteria 187, White Spirit (Stoddard Solvent). Geneva: United Nations Environment Program, International Labor Organization, and the World Health Organization, 1996. 27. International Agency for Research on Cancer (IARC): Some Organic Solvents, Resin Monomers and Related Compounds, Pigments and Occupational Exposures in Paint Manufacture and Painting. IARC Monographs on the Evaluation of Carcinogenic Risks to Humans, Volume 47. Lyon, France: IARC, 1989. p. 51. 28. Carpenter, C.P., E.R. Kinkead, D.L. Geary, et al.: Petroleum hydrocarbon toxicity studiesAnimal and human response to vapors of VM&P naphtha. Toxicol. Appl. Pharmacol. 32:282297 (1975). 29. National Institutes of Health (NIH), National Library of Medicine (NLM): Home Maintenance (product category), Household Products Database. Rockville, Md.: NIH, NLM, June 25, 2001. 30. Mehlman, M.: Benzene: A haematopoitic and multi-organ carcinogen at any level above zero. Eur. J. Oncol. 9:1536 (2004). 31. Occupational Safety and Health Administration (OSHA): Occupational Safety and Health Guidelines for VM&P Naphtha. [Online] Available at http://www.osha.gov/SLTC/healthguidelines/vmpnaphtha/ recognition.html (Accessed April 14, 2005). 32. U.S. Department of Energy (DOE): International Energy Annual 2001. DOE/EIA-0219(2001). Available at http://www.eia.doe.gov/iea. Washington, D.C.: Energy Information Administration, DOE, 2003. 33. U.S. Consumer Product Safety Commission: CPSC Seeks Data on Levels of Benzene Found in Various Consumer Products. News from CPSC, Release #80-013. Washington, D.C.: U.S. Consumer Product Safety Commission, Ofce of Information and Public Affairs, April 16, 1980. 34. Beers, M.H., and R. Berkow (eds.): The Merck Manual of Diagnosis and Therapy, 17th ed. Whitehouse Station, N.J.: Merck and Co., 1999. p. 2627. 35. Commercial Hexane and Methylcyclopentane: Test Rules, Federal Register 53:24 (5 February 1988) pp. 33823395.

Journal of Occupational and Environmental Hygiene

January 2006

36. Lide, D. (ed.): Handbook of Chemistry and Physics. 75th ed. Cleveland, Ohio: CRC Press, 1995. Table 1, pp. 6-2146-228. 37. Cunha V., R. Nobrega., and A. Habert: Fractionation of benzene/nhexane mixtures by pervaporation using polyurethane membranes. Braz. J. Chem. Eng. 16:297308 (1999). 38. Elkins, H., E.M. Comproni, and L. Pagnotto: Industrial benzene exposure from petroleum naphtha. II. Pertinent physical

properties of hydrocarbon mixtures. Am. Ind. Hyg. Assoc. J. 24:99102 (1963). 39. Hazard Communication, Code of Federal Regulations Title 29 Part 1910.1200 d)(5)(iv). 1994. 40. Occupational Safety and Health Administration (OSHA): Inspection Procedures for the Hazard Communication Standard. Directive CPL 0202-038CPL 2-2.38D, March 20, 1998.

Journal of Occupational and Environmental Hygiene

January 2006