AERIAS

Chemical Characterization of Building Dust Following The World Trade Center Collapse Marilyn S. Black, PhD Donald R. Cortes Air Quality Sciences, Inc.

AERIAS Third Annual National Symposium 2003

An ISO 9001 Registered, ISO 17025 Accredited, & AIHA EMLAP Accredited IAQ Firm 2211 Newmarket Parkway, Marietta, GA 30067 770-933-0638 Fax 770-933-0641

Aerias Third Annual National Symposium, 2003

Cortes, Black/1

CHEMICAL CHARACTERIZATION OF BUILDING DUST FOLLOWING THE WORLD TRADE CENTER COLLAPSE
Donald R. Cortes, PhD Chemical Laboratory Director Air Quality Sciences Atlanta, Georgia Marilyn S. Black, PhD Chief Scientist and CEO Air Quality Sciences Atlanta, Georgia

ABSTRACT
According to preliminary data released by Mount Sinai Medical Center, 57 percent of the World Trade Center (WTC) emergency responders had pulmonary symptoms or abnormal pulmonary function 10 months to one year after September 11, 2001. Many of the symptoms are thought to be due to exposure to airborne particles during and immediately after the event. Particulates have been analyzed for composition (e.g., asbestos, vitreous fibers, and gypsum) by the Centers for Disease Control and Preventions (CDC) Agency for Toxic Substances and Disease Registry (ATSDR), and the US Environmental Protection Agency (EPA) has investigated the toxicological effects of WTC-derived fine particulate matter. In addition, university researchers have analyzed WTC dust for carcinogenic polycyclic aromatic hydrocarbons. Air Quality Sciences, Inc. conducted volatile organic chemical (VOC) analysis of dust collected from carpet in a building across the street from the WTC towers. The building was full of debris originating from the WTC towers collapse. Volatile organic compounds associated with dust are often bound to the surface, and the mixture and type of dust VOCs are typically different than those that are found in the air. Volatile organic compounds on dust can present a significant inhalation risk as well. Chemical analysis of dust is found to be helpful in cases where traditional indoor air quality sampling does not give enough information to explain unexplained sick building syndrome (SBS) symptoms, and also is as an indicator of past VOC exposures.

CHEMICAL CHARACTERIZATION OF DUST

Typical indoor air investigations involve the sampling and analysis of volatile organic compounds (VOCs) and microbial contaminants. While these tests can provide the data needed to understand the source of many indoor air quality (IAQ) problems, sometimes additional testing is required to provide a more complete picture when traditional testing does not explain symptoms of the inhabitants. We have previously reported on the use of dust analysis in resolving indoor air quality complaints.1

2005 Air Quality Sciences, Inc.

Aerias Third Annual National Symposium, 2003

Cortes, Black/2

Dust can contain chemical information helpful or critical to investigations. First, toxicology of dust itself can be important. Recently, investigation on the toxic effects of particles has been a subject of great interest, in part due to statistical studies that demonstrate a clear connection between outdoor fine particle exposure and mortality.2 Researchers are working to understand the mechanism of particle toxicity. Churg et al. found that ambient particulate matter is retained in the walls of the small airway and causes remodeling, resulting in chronic obstructive pulmonary disease.3 Fine particles have been linked to inflammatory damage in the lungs due to high alveolar macrophage response. Nel et al. found that ultrafine particles are 10 to 50 times as potent in causing free radical damage in the lungs as larger particles4.

Whether the size of the particles or the chemicals associated with the larger relative surface-areas of these particles have a greater influence on particle toxicity is not clear. While Holian et al. found no macrophage response to ash from Mt. Saint Helens, they did find that airborne dust from St. Louis and Washington, DC caused apoptosis of suppressor macrophages, which suggests that it is the association of industrial chemicals with the particles that makes them toxic.5 Costa and Dreher found that when particles are associated with certain metals, strong inflammation of the lung cells is observed.6 Gavett similarly found that metal-laden dust collected from and industrial community caused greater aggravation of asthmatic constrictions than dust from a farm village with clean air.7

We previously reported on the use of dust analysis in a situation where traditional IAQ sampling did not explain symptoms expressed by building inhabitants.1 Symptoms included eye, nose and throat irritation and skin rashes. Airborne contamination was virtually absent when tested using traditional VOC sampling and analysis. However, chemical analysis of dust indicated unusually

2005 Air Quality Sciences, Inc.

Aerias Third Annual National Symposium, 2003

Cortes, Black/3

high levels of amine compounds, which are known to be potent sensory irritants that act on trigeminal and pulmonary receptors.8-11

Aside from direct health implications of particles and associated chemicals, dust analysis is important to IAQ investigations in other ways. Chemicals with very low vapor pressures can be difficult or impossible to detect in air, yet can be observed when performing dust analysis.12 In addition, dust can be an indicator of past exposure.13 For example, nicotine in dust is a useful indicator of cigarette smoking after airborne indicators (such as 3-ethenyl pyridine) have dissipated.1

CHARACTERIZATION OF DUST CREATED BY COLLAPSE OF WORLD TRADE CENTER BUILDINGS

The shear volume of dust created by the collapse of the World Trade Center (WTC) has created interest in the toxic effects of the resulting airborne and settled particles. According to preliminary data released by Mount Sinai Medical Center, 57 percent of WTC emergency responders had pulmonary symptoms or abnormal pulmonary function 10 months to one year after September 11, 2001. Many of the symptoms are thought to be due to exposure to airborne particles during and immediately after the event. Hence, the US Environmental Protection Agency (EPA) has published a study on the toxicological effects of fine particulate matter from the World Trade Center collapse.14

New York City Department of Health and Mental Hygiene and the Agency for Toxic Substances and Disease Registry (ATSDR) reported on exposures to airborne and settled surface dust in residential areas near Manhattan.15 Lioy et al. provided what might be the most comprehensive chemical evaluation to date of the settled dust/smoke aerosol in lower Manhattan.16 However, it

2005 Air Quality Sciences, Inc.

Aerias Third Annual National Symposium, 2003

Cortes, Black/4

is difficult to directly connect current health symptoms with chemical data. This is complicated by the fact that there may also be delayed effects due to chemical and particle exposures. Developmental and reproductive effects may be just beginning to emerge. Researchers from Mount Sinai Medical Center studied 182 pregnant women who were near the WTC site within three weeks of the collapse.17 The babies were twice as likely to be smaller than normal during their stage in the pregnancy. The authors suggested high exposure to polycyclic aromatic hydrocarbons (PAH), or particles may have mediated this. Time will tell if childhood development problems will increase as a result of these exposures.

METHODOLOGY
Dust was collected from carpet, which was removed from a high-rise building on Liberty Street. This building was directly across the street from the World Trade Center collapse site. To collect the dust, polycarbonate filter cassettes (0.45 m) attached to a high-flow vacuum pump were used. The dust from the carpet was analyzed for chemical, particle and microbiological content. Particle characterization and microbial content were conducted using light microscopy. Chemical analysis was performed using thermal desorption gas chromatography/mass spectrometry.

CHEMICAL CHARACTERIZATION RESULTS

Table 1 is a survey of total volatile organic compound (TVOC) levels in dust from five different types of locations. While the number of compounds found in samples from the World Trade Center dust (n) is about the same as in the other samples, the average TVOC concentration is more than twice as high than the other locations. This is due in part to the selection of dust samples from the WTC site all exhibiting high TVOC concentrations, while the other sites had dust containing a wider range of TVOC concentrations.

2005 Air Quality Sciences, Inc.

Aerias Third Annual National Symposium, 2003

Cortes, Black/5

Table 1. Survey of TVOC Levels in Dust

Scenario
Office Building University Building Residence Warehouse/Movie Set

n*
4-142 50-93 84-102 69

x
(g/g) 532 1042 1690 680

Range (g/g) 5-2813 222-1862 69-4035 --

*Indicated is n, the range in the number of compounds found in dust from the indicated location; x, the average TVOC concentration of the samples, and the range in TVOC of the samples.

Table 2 lists the top 20 chemicals, by concentration, associated with the WTC dust. Leading the list is perflourooctanesulfonate. The presence of this compound at high concentration in dust is not surprising. Perfluorooctanesulfonate homologues have been used in many consumer products, including Scotchguard, and fire extinguishers. (3M voluntarily changed its formulation of Scotchguard shortly after its environmental ubiquity was discovered). 2,3Dihydro-3,5-dihydroxy-6- methyl-4H-pyran-4-one (#2), as well as maltol (#7) are both combustion products of cellulose. Fatty acids are often associated with particles in the industrial environment, and the high concentration of carboxylic acids may be their combustion products. Formic acid (#14) is a very common combustion emission product. 2-Furanmethanol (#4) is sometimes found in building product emissions, but its position on this list indicates it is may also be a combustion product. Other compounds, including 1-butanol, 1-dodecanol, diethylene glycol, and 3-methyl-2-butanol are usually associated with building products and materials. It is unclear what the original sources of the amine compounds were. Amine compounds can cause respiratory irritation at low-level gas-phase concentrations, and we have observed that low amine concentrations, when associated with particles, can cause significant irritation as well.

2005 Air Quality Sciences, Inc.

Aerias Third Annual National Symposium, 2003

Cortes, Black/6

Table 2. Top Twenty Chemicals Associated with WTC Dust

Rank 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 Chemical Perfluorooctanesulfonate 4H-Pyran-4-one, 2,3-dihydro-3,5-dihydroxy-6-methylNonanoic acid 2-Furanmethanol Hexanoic acid Acetic acid Maltol 1-Dodecanol 1-Butanol (N-Butyl alcohol) 1,3-Propanediamine, N-methylOctanoic Acid Cyclopropane, 1,2-dimethyl Diethylene glycol (2,2'-oxybisethanol) Formic acid (Methanoic acid) Hexanoic acid, 2-ethyl Decanoic acid Hexane, 2-methyl 2-Butanamine Heptanoic acid 3-Methyl-2-butanol g/g 509.4 276.7 200.0 168.9 161.3 159.7 141.7 141.4 139.5 128.1 116.2 115.0 111.2 97.9 77.7 77.1 76.7 76.2 73.5 72.8

Examples of compounds that are associated with building products and materials are given in Table 3. Chemicals such as 1-dodecanol and caprolactam are often associated with carpet, while propylene glycol and 2-ethyl-1-hexanol often are associated with adhesives. 2,6-Di-tert-butyl-4methylphenol (BHT) is a preservative used in cushion, while methyl methacrylate, vinyl acetate and phenol are found in plastic-type materials and resins. 2,2,4-Trimethyl-1,3-pentanediol monoisobutyrate (Texanol) usually comes from paint. Hexanal is usually high in wood products and nonylphenol is often used as a non-ionic surfactant. Table 4 lists dust composition as determined by particle characterization. The constituents determined by microscopic

2005 Air Quality Sciences, Inc.

Aerias Third Annual National Symposium, 2003

Cortes, Black/7

examination confirm the presence of sources of the compounds found using chemical analysis, and thus demonstrate the utility of the chemical dust analysis in describing the history of the particles.

Table 3. VOCs Found in Emissions from Building Materials and Products that were Found in WTC Dust
Chemical 1,2-Propanediol (Propylene glycol) 1-Dodecanol 1-Hexanol, 2-ethyl 2,2,4-Trimethyl-1,3-pentanediol monoisobutyrate (Texanol) 2,6-Di-tert-butyl-4-methylphenol (BHT) Acetate, vinyl (Acetic acid ethenyl ester) Hexanal Methyl methacrylate Phenol Phenol, nonyl -Caprolactam (2H-Azepin-2-one, hexahydro) g/g 9.4 44.6 37.5 39.2 35.0 5.4 23.1 7.8 35.0 8.6 39.1

Table 4. Particle Composition as Determined Using Light Microscopy

Composition Calcite-cement Chrysotile asbestos fibers Construction debris Cotton fibers Glass fibers Gypsum plaster Hair Low temperature combustion materials Paint Plant fragments Amount Primary Trace Primary Primary Primary Primary Trace Primary Primary Trace

2005 Air Quality Sciences, Inc.

Aerias Third Annual National Symposium, 2003

Cortes, Black/8

Pollen grains Rust Skin cells Soil minerals Starch Starch granules Synthetic fibers

Trace Trace Trace Primary Trace Primary Primary

The list of chemicals found on WTC dust was examined for compounds that might reflect exposures to toxic compounds. Dust often is associated with chemicals of known toxicity and sensory irritation. For example, Table 5 lists compounds that are considered by the State of California to be known carcinogens or known teratogens.19

While levels of these compounds in the gas-phase have been established to minimize risk, little research has been performed to establish the toxicity of these compounds when they are associated with particles. Table 5. Chemicals Associated with Dust Known to the State of California to Cause Cancer or Reproductive Harm19
Chemical 1,4-Dioxane 2-Methoxybenzamine 2-Methoxyethanol Benzene Bromomethane Carbon disulfide Chloroethane Chloromethane Cyclohexanol Furan Known to the State of California to Cause Cancer Cancer Reproductive toxicity Cancer, Reproductive toxicity Reproductive toxicity Reproductive toxicity Cancer Reproductive toxicity Reproductive toxicity Cancer

2005 Air Quality Sciences, Inc.

Aerias Third Annual National Symposium, 2003

Cortes, Black/9

Iodomethane Pyridine

Cancer Cancer

The following compounds that have sensory irritation properties20: 1-Butanol 2- Butoxyethanol 2-Methylpropanal 2-Propenal Acetic acid Acetone Benzaldehyde Ethanol Ethyl acetate Hexanal Pentanal Propanal Propanoic acid

Table 6 lists three low molecular weight halogenated compounds that are associated with low minimal risk levels (MRLs) published by the Agency for Toxic Substances and Disease Registry.21 Finding these compounds in dust is unusual, but exposure levels due to dust inhalation would be very low on the basis of the indicated dust concentrations. However, trace levels of chemicals found on dust may be a historical indicator of a high airborne level of these compounds. Because low molecular weight halogenated organics are known to result from combustion of many types of materials, their presence warrants further investigation.

Table 6. Selected Toxic Compounds Found on WTC Dust and Corresponding Minimum Risk Levels (MRLs)21
Selected halomethanes Dust Concentration (g/g) Acute (1-14 days) Methane, chloro Methane, bromo 4.6 3.1 0.5 (Neurological) 0.05 Inhalation MRL (ppm) Intermediate (15 364 days) 0.2 (Hepatic) 0.05 Chronic (>364 days) 0.05 Neurological) 0.005

2005 Air Quality Sciences, Inc.

Aerias Third Annual National Symposium, 2003

Cortes, Black/10

(Neurological) Ethane, chloro 0.2 15 (Developmental)

(Neurological)

(Neurological)

The EPA posted an external review draft Exposure and Human Health Evaluation of Airborne Pollution from the World Trade Center Disaster on its website. Grab samples were taken for VOCs on Liberty Street, very near the location that these dust samples were contained. They indicated levels in the low double-digit parts-per-million (ppm) range for chloromethane, two weeks to three weeks after the collapse of the WTC. These levels are much higher than the MRLs for this compound. While it is tempting to conjecture about potential human exposures and health effects, the EPA data is not in final form and not available for citation. In addition, this location was within a personnel restricted zone set up by the EPA, so extrapolation to areas inhabited by humans will require meteorological information and diffusion/transport modeling. However, this example demonstrates the usefulness of dust as an indicator of past exposures, and as a trigger for further investigation.

REFERENCES
1. Cortes, DR, Worthan, AG, and Black, MS. Role of Dust Analysis is Complaint Resolution of Indoor Air Quality. 8th International Conference on Indoor Air Quality and Climate, Monterey, California, June 30-July 5, 2002. 2. Laden, F, Neas, LM, Dockery, DW, Schwartz, J. Association of fine particulate matter from different sources with daily mortality in six US cities. Environ. Health Perspect, 2000; 108:941-947. 3. Churg, A, Brauer, M, Carment Avila-Casado, M, Fortoul, T, and Wright, JL, Chronic Exposure to High Levels of Particulate Air Pollution and Small Airway Remodeling, Environmental Health Perspect, 2003 111: pp 714-718. 4. Li, N, Sioutas, C, Cho, A, Schmitz, D, Misra,C, Sempf, J, Wang, M, Oberley, T, Froines, J and Nel, A. Ultrafine Particulate Pollutants Induce Oxidative Stress and Mitochondrial Damage Environ Health Perspect, 2003, 111:455-460.

2005 Air Quality Sciences, Inc.

Aerias Third Annual National Symposium, 2003

Cortes, Black/11

5. Holian, A, Hamilton, R, Morandi, MT, Brown, SD and Li, L. Urban Particle-induced Apoptosis and Phenotype Shifts in Human Alveolar Macrophages Environ Health Perspect, 1998, 106:127-132. 6. Costa, DL, and Dreher, KL. Bioavailable transition metals in particle matter mediate cardiopulmonary injury in healthy and compromised animal models. Environ Health Perspect, 1997, 105:1053. 7. Gavett, SH et al., in press. Metal composition of ambient PM2.5 influences severity of allergic airways disease in mice. Envrion Health Perspect. 8. Gagnaire, F, Azim, S, Simon, P, Cossec, B, Bonnet, P and De Ceaurriz, J. (1993). Sensory and Pulmonary Irritation of Aliphatic Amines in Mice: a Structure-Activity Relationship Study. Journal of Applied Toxicology, Vol 13(2), pp129-135. 9. Nielsen, GD, Vinggaard, AM, 1988. Sensory Irritation and Pulmonary Irritation of C3-C7 n-Alkylamines: Mechanisms of Receptor Activation. Pharmacology & Toxicology, Vol 63, pp 293-304. 10. Nielsen, GD, Yamagiwa, M, 1989. Structure-Activity Relationships of Airway Irritating Aliphatic Amines. Receptor Activation Mechanisms and Predicted Industrial Exposure Limits. Chem.-Biol. Interactions, Vol 71, pp 223-244. 11. Schaper, M, 1993. Development of a Database for Sensory Irritants and Its Use in Establishing Occupational Exposure Limits. Am. Ind. Hyg. Assoc. J. Vol 54(9) pp 488544. 12. Papadopoulos, A., Karayannic, M., and Knoeppel, H., Survey Analysis of Organic Compounds Extracted from 16 House Dust Samples Collected in Northern Italy and Northwestern Greece, Proceedings of the 8 th International Conference on Indoor Air Quality and Climate - Indoor Air 99, Vol 4, pp 107-112. Edinburgh: Indoor Air 99. 13. Cizdziel J, and Hodge, V. 2000. Attics as archives for house infiltrating pollutants: trace elements and pesticides in attic dust and soil from southern Nevada and Utah. Microchemical Journal. Vol 64, pp 85-92. 14. Toxicological Effects of Fine Particulate Matter Derived from the Destruction of the World Trade Center, EPA report 600/R-02/028, December 2002. 15. Final Technical Report of the Public Health Investigation to Assess Potential Exposures to Airborne and Settled Surface Dust in Residential Areas of Lower Manhattan. New York City Department of Health and Mental Hygiene and Agency for Toxic Substances and Disease Registry, U.S. Department of Health and Human Services. September 2002. 16. Lioy, PJ, Weisel, CP, Millette, JR, Eisenreich, S, Vallero, D, Offenberg, J, Buckley, B, Tuprin, B, Zhong, M, Cohen, MD, Prophete, C, Yang, I, Stiles, R, Chee, G, Johnson, W, Porcja, R, Alimokhtari, S, Hale, RC, Weschler, C, Chen, LC. Characterization of the Dust/Smoke Aerosol that Settled East of the World Trade Center (WTC) in Lower
2005 Air Quality Sciences, Inc.

Aerias Third Annual National Symposium, 2003

Cortes, Black/12

Manhattan after the Collapse of the WTC 11 September 2001. Environ Health Perspect., 2002 110:703-714. 17. Berkowitz, GS, Wolff, MS, Janevic, TM, Holzman, IR, Yehuda, R, Landgrigan, PJ, The World Trade Center Disaster and Intrauterine Growth Restriction, Journal of the American Medical Association, August 6, 2003, 290:595-596. 18. Winberry, Jr. W, Forehand L, Murphy N, et al. 1990 Compendium of Methods for the Determination of Air Pollutants in Indoor Air, EPA Report 600/4-90/010, Research Triangle Park, NC: Atmospheric Research and Development. 19. California Proposition 65, Safe Drinking Water and Toxic Enforcement Act of 1986, www.oehha.org/prop65.html, accessed September 12, 2003. 20. Schaper, M, 1993. Development of a Database for Sensory Irritants and Its Use in Establishing Occupational Exposure Limits. Am. Ind. Hyg. Assoc. J. Vol 54(9) pp 488544. 21. Agency for Toxic Substances and Disease Registry, Minimal Risk Levels (MRLs) for Hazardous Substances, www.atsdr.cdc.gov/mrls.html, accessed September 11, 2003.

2005 Air Quality Sciences, Inc.