Indoor Acrylonitrile Summary Information

Lori Miyasato, RD

Acrylonitrile (AN) is an extensively used chemical. Nevertheless, very little is known about acrylonitrile emissions in the indoor environment. Only a few studies have examined residential AN concentrations, and most of those have found low or undetectable levels; however, two studies reported higher levels in a small percentage of homes. Most of the research carried out on human exposures to this chemical has dealt with occupational exposures (e.g. in acrylonitrile production and processing plants), and a large proportion of these studies was conducted outside of the United States. Another area that has received attention relates to AN as a component of environmental tobacco smoke (ETS); thus, AN emissions have been documented within various ETS studies.

The paragraphs below summarize relevant findings from a quick review of readily accessible studies. Additionally, although very limited information is available about indoor exposures to acrylonitrile, it is such a ubiquitous chemical that the list of its potential indoor sources (based on content or manufacturing information, not emissions data) is extensive. Thus, a sample listing of products containing or made using acrylonitrile and Web resources for locating additional products are provided at the end of this summary. However, it is important to note that, although many products contain or are made using AN, only a few or none may be notable emitters of AN: AN may be tightly bound in most or all of these products. Also, note that the information presented below is simply a summary of what was found quickly…it is not intended to be a complete survey.

Indoor Concentrations

A study carried out in a public housing development in Boston, Massachusetts examined various environmental factors for nine families having asthmatic children (Brugge et al. 2003). Volatile organic compounds (VOCs) were collected using passive thermal desorption tubes containing carbotrap B; acrylonitrile was found to exceed the U.S. EPA IRIS program RfD in fewer than 4% of the samples. Fewer than 12% of samples presented a cancer from acrylonitrile greater than 10 -6. However, specific concentrations were not provided in this paper.

In 1990, Sheldon et al. (1992) measured various toxic air contaminants, including acrylonitrile, in homes in Woodland, California. Acrylonitrile was detectable (i.e., >2.1 µg/m 3) only in 4 of 47 samples; of these, the mean concentration was 9.1 µg/m 3 and the maximum was 27 µg/m 3.

A 1998 report by the Agency for Toxic Substances and Disease Registry (ATSDR) provided VOC measurements for three locations within the mail sorting room at the Toms River General Post Office, Toms River, New Jersey. Samples were taken on two

Page 1 of 9 days, with two eight-hour samples collected each day. On November 17, 1997, all acrylonitrile concentrations fell below 1.14 µg/m 3. However, on December 4, 1997, higher levels were detected (all measurements in µg/m 3): 8.3, 6.84, and <0.58 for the 7:00 am – 3:00 pm collection period, and 5.5, 2.6, and 2.11 for the 3:00 pm – 11:00 pm sampling period. The study noted that acrylonitrile could have been given off by adhesive materials and used in the building. The report also stated that the AN levels measured during this study were well below the OSHA permissible exposure limit, the NIOSH recommended exposure limit, and the ACGIH threshold limit value for occupational exposures.

A study of indoor and outdoor levels of VOCs conducted in 1990 near Toronto, Canada reported that acrylonitrile was not detected in overnight samples (duration up to 16 h) in four residences, nor were detectable levels present during working hours in an office building, with samples from three offices and a laboratory (detection limit 0.9 µg/m 3 for all locations) (Bell et al. , 1991).

Therefore, although there is the potential for high levels of exposure (as in the Woodland study) if appropriate sources are present, the limited data indicate that indoor concentrations of acrylonitrile generally are very low.

Environmental Tobacco Smoke (ETS) (Note: SSD has the most recent ETS info)

A study of nonsmoking Californians’ exposure to environmental tobacco smoke (ETS) conducted in three areas of the state (Los Angeles, Pittsburgh/Antioch, and Woodland) estimated that, over a 24-hour period, the arithmetic mean increment of acrylonitrile exposure due to ETS was 0.49 µg/m 3 (Miller et al. 1998).

Another study, by Nazaroff and Singer (2004), examined ETS exposures of U.S. nonsmokers living with smokers; this study focused on hazardous air pollutants (HAPs) present in ETS. Estimates generated in this study, based on material-balance modeling, indicated that the lifetime cancer from ETS-generated acrylonitrile was substantial: approximately 2-500 per million. More specifically, the authors listed the following acrylonitrile exposure/intake estimates for nonsmokers living with smokers: exposure relevant emission factor=195 µg/cigarette; exposure concentration=0.5-1.2 µg/m 3; and inhalation intake=6-14 µg/day.

Acrylonitrile also is present in mainstream tobacco smoke (MTS), the smoke exhaled by a smoker which combines with sidestream smoke (from the burning end of the cigarette) to form ETS (National Cancer Institute 2005). Pankow et al. (2004) tested two commercial brands of cigarettes to study emissions of 26 volatile organic compounds. These authors calculated the following total (gas and particle) delivery levels and K(p) values (concentration in the particle phase divided by concentration in the gas phase) for AN: for Camel cigarettes: 10 ng per cigarette and 4.4 ng/µg, respectively; for Marlboro cigarettes: 10 ng per cigarette and 4.6. ng/µg, respectively.

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Daisey et al. (1994) measured emissions of 23 VOCs in the sidestream smoke of six commercial brands of cigarette popular in California. Experiments were conducted in a room-sized environmental chamber. The average emission rate for acrylonitrile was found to be 99 µg/cigarette.

Singer et al. (2002) investigated the effects of smoking rate, ventilation rate, and furnishing level on the emissions of 26 gas-phase organic compounds present in ETS. Experiments were conducted in a model room to simulate conditions that would be found in offices and residences. The researchers determined that the three factors had little or no effect on exposure-relevant emission factors for acrylonitrile.

Occupational Exposure

Numerous studies have examined occupational exposures to acrylonitrile and the associated risks (for reviews, see e.g. Starr et al. 2004, Scélo et al. 2004). As the focus of this synopsis is indoor, non-occupational sources of acrylonitrile, a summary of the occupational literature will not be provided here. However, findings from several occupational studies are presented below in order to illustrate some of the acrylonitrile sources and emission levels that have been identified in workplaces, as well as some of the health effects.

In order to determine the nature of chemical exposures faced by workers in the processing industry, Forrest et al. (1995) quantified emissions resulting from the processing of various materials. One situation involved the injection molding of acrylonitrile-butadiene-styrene (ABS). Acrylonitrile, or 2-propenitrile, was detected during the purging process (using Tenax with the thermal desorption technique) at a concentration of 0.02 mg/m 3. Measurements of high impact (HIPS) during the sheet extrusion process revealed an acrylonitrile level of 0.01 mg/m 3 (using Tenax adsorbent tubes).

Another study, by Contos and colleagues (1995), attempted to quantify VOCs emitted during thermal extrusion processing of acrylonitrile butadiene styrene (ABS) composite resins. The VOC samples were analyzed using gas chromatography and an in-line continuous VOC analyzer. The resins tested were an automotive composite resin, a general molding composite and a duplicate general molding composite, a refrigeration composite, and a pipe composite. Acrylonitrile was detected in the emissions of extruded ABS for all of these resins: 3.00 µg/L, 3.84 µg/L, 4.33 µg/L, 4.74 µg/L, and 5.67 µg/L, respectively. Emissions factors were 5.75 µg/g, 7.79 µg/g, 7.3 µg/g, 9.75 µg/g, and 10.4 µg/g, respectively.

A cohort study assessing acrylonitrile exposure and cancer mortality from 1960 to 1996 was conducted on workers at the BP Chemicals, Inc. chemical manufacturing plant in Lima, Ohio (Marsh et al. 1999). The average intensity of exposure (cumulative AN exposure divided by the product of number of days worked and estimated daily

Page 3 of 9 exposure) for AN-exposed workers decreased over time: 4.50 ppm from 1960-1966; 3.92 ppm from 1967-1978; 1.27 ppm from 1979-1988; and 0.13 from 1989-1996. The AN levels were found not to be significantly related to excess stomach, lung, breast, prostate, brain, or hematopoietic system cancer mortality, although there was a nonsignificant trend toward increasing lung cancer risk with increased AN exposure.

Acrylonitrile also is widely utilized in the production of fabrics. Kiefer and Moss (1997) measured VOCs released during the cutting of fabrics and polymers with a 25 W CO 2 continuous beam laser. These researchers found the highest VOC levels produced during the cutting of felt fabrics; the fewest VOCs, at the lowest relative concentrations, were emitted from woven fabrics. Acrylonitrile was one of the chemicals released from fabric cutting.

Fiber production also can expose workers to acrylonitrile. Wood et al. (1998) investigated the relationship between cancer risk and acrylonitrile exposure from 1944- 1991 at two Orlon-producing plants. These authors found that cancer mortality was lower than expected compared to the U.S. population and all DuPont employees.

Potential Exposure from Consumer Products

As mentioned above, little information exists about indoor sources of acrylonitrile. Nonetheless, consumer products containing acrylonitrile or polymers of acrylonitrile are numerous and therefore would be valuable subjects of further study. One potential source of exposure is from household products, including food storage containers. A study examining acrylonitrile diffusion into food-simulating liquid (water) from acrylonitrile-butadiene-styrene (ABS) polymers showed a linear relationship between the proportion of AN present in the polymer and the amount that diffused into the liquid (Lickly et al. 1991). ABS polymers containing less than 12 µg/g of AN did not show detectable levels of migration (<31 ng/cm 2). Diffusion coefficients showed a linear relationship with the inverse of the absolute temperature.

References

Agency for Toxic Substances and Disease Registry (ATSDR). 1998. Health Consultation: Air Surveillance, Toms River General Post Office, Toms River, Ocean County, New Jersey. Prepared by: Exposure Investigation and Consultation Branch, Division of Health Assessment and Consultation, Agency for Toxic Substances and Disease Registry http://www.atsdr.cdc.gov/HAC/PHA/tomsrivergpo/tom_p1.html#T1

Bell RW, Chapman RE, Kruschel BD, Spencer MJ, Smith KV, Lusis MA. 1991. The 1990 Toronto Personal Exposure Pilot (PEP) Study . Report prepared for Atmospheric Research and Special Programs Section, Air Resources Branch, Ontario Ministry of the Environment. Toronto, Ontario, Queen’s Printer for Ontario (ARB-207-90).

Page 4 of 9 Brugge D, Vallarino J, Ascolillo L, Osgood N-D, Steinbach S, Spengler J. 2003. Comparison of multiple environmental factors for asthmatic children in public housing. Indoor Air 2003 , 13 :18-27.

Contos DA, Holdren MW, Smith DL, Brooke RC, Rhodes VL, Rainey ML. 1995. Sampling and analysis of volatile organic compounds evolved during thermal processing of acrylonitrile butadiene styrene composite resins. J. Air & Waste Manage. Assoc. 45 :686-694.

Daisey JM, Mahanama KRR, Hodgson AT. 1994. Toxic Volatile Organic Compounds in Environmental Tobacco Smoke: Emission Factors for Modeling Exposures of California Populations. Final Report, Contract No. A133-186, California Air Resources Board, Research Division, Sacramento, California.

Forrest MJ, Jolly AM, Holding SR, Richards SJ. 1995. Emissions from processing thermoplastics. Ann. Occup. Hyg., 39 :35-53.

Lickly TD, Markham DA, Rainey ML. 1991. The migration of acrylonitrile from acrylonitrile/butadiene/styrene polymers into food-simulating liquids. Food Chem. Toxic. 29 (1):25-29.

Marsh GM, Gula MJ, Youk AO, Schall LC. 1999. Mortality among chemical plant workers exposed to acrylonitrile and other substances. American Journal of Industrial Medicine 36 :423-436.

Miller SL, Branoff S, Nazaroff WW. 1998. Exposure to toxic air contaminants in environmental tobacco smoke: an assessment for California based on personal monitoring data. J Expo Anal Environ Epidemiol. Jul-Sep 1998; 8(3):287-311.

National Cancer Institute. 2005. Cancer Facts: Secondhand Smoke: Questions and Answers. http://cis.nci.nih.gov/fact/10_18.htm#1

Nazaroff WW, Singer BC. 2004. Inhalation of hazardous air pollutants from environmental tobacco smoke in US residences. J Expo Anal Environ Epidemiol. 14 (Suppl 1):S71-7.

Pankow JF, Luo W, Tavakoli AD, Chen C, Isabelle LM. 2004. Delivery levels and behavior of 1,3-butadiene, acrylonitrile, benzene, and other toxic volatile organic compounds in mainstream tobacco smoke from two brands of commercial cigarettes. Chem Res Toxicol. Jun 2004; 17 (6):805-13.

Report on , Eleventh Edition. U.S. Department of Health and Human Services, Public Health Service, National Program. http://ntp.niehs.nih.gov/ntp/roc/toc11.htm

Page 5 of 9 Scélo G, Constantinescu V, Csiki I, Zaridze D, Szeszenia-Dabrowska N, Rudnai P, Lissowska J, Fabiánová E, Cassidy A, Slamova A, Foretova L, Janout V, Fevotte J, Fletcher T, Mannetje A, Brennan P, Boffetta P. 2004. Occupational exposure to , acrylonitrile and styrene and lung cancer risk (Europe). Cancer Causes and Control 15 :445-452.

Sheldon L, Clayton A, Jones B, Keever J, Perritt R, Smith D, Whitaker D, Whitmore R. 1992. Indoor Pollutant Concentrations: Final Report, Contract No. A833-156. Prepared for Research Division, California Air Resources Board, Sacramento, CA.

Singer BC, Hodgson AT, Guevarra KS, Hawley EL, Nazaroff WW. 2002. Gas-phase organics in environmental tobacco smoke. 1. Effects of smoking rate, ventilation, and furnishing level on emission factors. Environ Sci Technol. Mar 1 2002; 36 (5):846-53.

Starr TB, Gause C, Youk A, Stone R, Marsh GM, Collins JJ. 2004. A for occupational acrylonitrile exposure using epidemiology data. Risk Analysis 24 :587- 601.

Wood SM, Buffler PA, Burau K, Krivanek N. 1998. Mortality and morbidity of workers exposed to acrylonitrile in fiber production. Scand. J. Work. Environ. Health , 24 (Suppl. 2):54-62.

Other Acrylonitrile Websites (U.S. agencies and others)

Acrylonitrile. Concise International Chemical Assessment Document (CICAD) Vol:39 (2002) 45 p. Environmental Health Directorate of Health Canada/ Commercial Chemicals Evaluation Branch of Environment Canada; Priority Substances Program under the Canadian Environmental Protection Act (CEPA) http://www.inchem.org/documents/cicads/cicads/cicad39.htm

Acrylonitrile Summary, U.S. EPA Air Toxics Website, 107-13-1. Created 1992; revised 2000. http://www.epa.gov/ttn/atw/hlthef/acryloni.html

Acrylonitrile. NICNAS: Priority existing chemical assessment report Vol:10 (2000) 71 p. Department of Health and Ageing, Australian Government. http://www.nicnas.gov.au/publications/CAR/PEC/PEC10/PEC10index.asp

Environmental Hazard Assessment: Acrylonitrile. Toxic Substances Division. Department of the Environment, London Vol:TSD/11 (1993) 37 p http://toxnet.nlm.nih.gov/cgi-bin/sis/search/f?./temp/~JXKhSV:12

Acrylonitrile (CASRN 107-13-1). 1983. U.S. EPA Integrated Risk Information System. http://www.epa.gov/iris/subst/0206.htm

Page 6 of 9 A recommended standard for occupational exposure to acrylonitrile. 1978. NIOSH Criteria Documents http://www.cdc.gov/niosh/78-116.html

Some Uses of Acrylonitrile

Acrylic (fiber-forming polymer at least 85% acrylonitrile by weight) Sweaters Fleece fabrics Socks Furniture Carpet Blankets Upholstery fabrics Craft yarns replacement Luggage Vehicle covers

Modacrylic fiber (fiber-forming polymer 35-85% acrylonitrile by weight) Deep-pile coats, trims & linings Simulated fur Wigs and hair pieces Children’s sleepwear Career apparel Fleece and non-woven fabrics; knit-pile fabric backings Blankets Carpets Flame-resistant draperies and curtains Scatter rugs Stuffed toys

Acrylonitrile-Butadiene-Styrene (ABS) Kitchen utensils Carbonated beverage bottles Kitchen appliances (e.g. food mixers) Filters Refrigerator linings Rigid containers – tubs, trays, boxes Automotive products Pipes & fittings Telecom Toys (e.g. Lego blocks) Computers Furniture Cabinets and cases (e.g. TV cabinets, food mixers, telephone sets, vacuum cleaners)

Page 7 of 9 Projector and camera housings Audio visual equipment appliance housings for baths, shower trays Luggage Construction material Plating for sanitary ware Plating for automotive or radiator grills, wheel covers, headlight bezels Interior and exterior trim and knobs Plating for radio and TV parts, shavers, light fixtures, appliance housings Fire retardant for switchers, personal computer housings, TV cabinets, oven doors, air conditioner housings, carpet cleaner housings, smoke detectors

Styrene-Acrylonitrile (SAN) Cigarette lighters Plastic drinking glasses Soup tureens Plates Coffee filters Toothbrush handles Trays Containers Covers TV screens Lenses Instrument lenses in automotive Cassette tape cases Light and reflector moldings Medical equipment Kitchen mixing bowls and basins Fittings for refrigerators Outer casings of thermally insulated jugs Tableware Cutlery Coffee filters Jars Food storage containers (e.g. processed meat containers) Toothbrushes Bathroom fittings Cosmetic packaging Outer covers for printers, calculators, instruments, lamps Scales Battery housings Winding cores Writing and drawing equipment Cylindrical impellers for air conditioners

Page 8 of 9 Adiponitrile Chemical used to make

Acrylonitrile Methylacrylate Medical and pharmaceutical packaging Bottles for chemicals Packaging for personal care, hygiene and cosmetic products Food packaging

Acrylonitrile-Butadiene Rubber (NBR) Automotive (hoses, gaskets, seals, grommets) Shoe soles Floor mats

Web Sites – Acrylonitrile and Acrylonitrile-containing Products http://cpf.jrc.it/smt/monomers/pm12100.htm http://globalspec.com/ProductFinder/FindProducts?query=styrene%20acrylonitrile&frmtr k=topnav http://www.apparelsearch.com/glossary_m_1.htm http://www.azom.com http://www.bpf.co.uk/bpfindustry/plastics_materials.cfm http://www.costumegallery.com/Textiles/acrylic.htm http://www.dsm.com/en_US/html/dfi/acn_prod_acrylo2.htm http://www.envirotools.org/factsheets/contaminants/acrylonitrile.shtml http://www.fibersource.com/f-tutor/modacrylic.htm http://www.iisrp.com/WebPolymers/07NBR-18Feb2002.pdf http://www.plasticsindustry.org/industry/defs.htm

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