Marilyn S. Black and Donald R. Cortes- Chemical Characterization of Building Dust Following The World Trade Center Collapse

8/3/2019 Marilyn S. Black and Donald R. Cortes- Chemical Characterization of Building Dust Following The World Trade Center Collapse

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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.




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

C HARACTERIZATION OF DUST C REATED BY C OLLAPSE OF W ORLDT RADE C ENTER 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





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.

M ETHODOLOGY

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 µm) 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.

C HEMICAL C HARACTERIZATION R ESULTS

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.







Table 2. Top Twenty Chemicals Associated with WTC Dust

Rank Chemical µg/g

1 Perfluorooctanesulfonate 509.4

2 4H-Pyran-4-one, 2,3-dihydro-3,5-dihydroxy-6-methyl- 276.73 Nonanoic acid 200.0

4 2-Furanmethanol 168.9

5 Hexanoic acid 161.3

6 Acetic acid 159.7

7 Maltol 141.7

8 1-Dodecanol 141.4

9 1-Butanol (N-Butyl alcohol) 139.5

10 1,3-Propanediamine, N-methyl- 128.1

11 Octanoic Acid 116.2

12 Cyclopropane, 1,2-dimethyl 115.0

13 Diethylene glycol (2,2'-oxybisethanol) 111.2

14 Formic acid (Methanoic acid) 97.9

15 Hexanoic acid, 2-ethyl 77.7

16 Decanoic acid 77.1

17 Hexane, 2-methyl 76.7

18 2-Butanamine 76.2

19 Heptanoic acid 73.520 3-Methyl-2-butanol 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-4-

methylphenol (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





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 Materialsand Products that were Found in WTC Dust

Chemical µg/g

1,2-Propanediol (Propylene glycol) 9.4

1-Dodecanol 44.6

1-Hexanol, 2-ethyl 37.5

2,2,4-Trimethyl-1,3-pentanediol monoisobutyrate (Texanol) 39.2

2,6-Di-tert-butyl-4-methylphenol (BHT) 35.0

Acetate, vinyl (Acetic acid ethenyl ester) 5.4

Hexanal 23.1

Methyl methacrylate 7.8

Phenol 35.0

Phenol, nonyl 8.6

ε -Caprolactam (2H-Azepin-2-one, hexahydro) 39.1

Table 4. Particle Composition as DeterminedUsing Light Microscopy

Composition Amount

Calcite-cement Primary

Chrysotile asbestos fibers Trace

Construction debris Primary

Cotton fibers Primary

Glass fibers Primary

Gypsum plaster Primary

Hair Trace

Low temperature combustion materials Primary

Paint Primary

Plant fragments Trace





Pollen grains Trace

Rust Trace

Skin cells Trace

Soil minerals Primary

Starch TraceStarch granules Primary

Synthetic fibers 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 theState of California to Cause Cancer or Reproductive Harm 19

Chemical Known to the State of California toCause

1,4-Dioxane Cancer

2-Methoxybenzamine Cancer

2-Methoxyethanol Reproductive toxicity

Benzene Cancer,

Reproductive toxicity

Bromomethane Reproductive toxicity

Carbon disulfide Reproductive toxicity

Chloroethane Cancer

Chloromethane Reproductive toxicity

Cyclohexanol Reproductive toxicity

Furan Cancer





Iodomethane Cancer

Pyridine Cancer

The following compounds that have sensory irritation properties 20:

• 1-Butanol • Ethanol

• 2- Butoxyethanol • Ethyl acetate

• 2-Methylpropanal • Hexanal

• 2-Propenal • Pentanal

• Acetic acid • Propanal

• Acetone • Propanoic acid

• Benzaldehyde

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 MinimumRisk Levels (MRLs) 21

Selectedhalomethanes

Dust Concentration(µg/g) Inhalation MRL (ppm)

Acute(1-14 days)

Intermediate (15– 364 days)

Chronic(>364 days)

Methane, chloro 4.60.5

(Neurological)0.2

(Hepatic)0.05

Neurological)

Methane, bromo 3.1 0.05 0.05 0.005





(Neurological) (Neurological) (Neurological)

Ethane, chloro 0.215

(Developmental) — —

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.

R EFERENCES

1. Cortes, DR, Worthan, AG, and Black, MS. Role of Dust Analysis is ComplaintResolution of Indoor Air Quality. 8 th International Conference on Indoor Air Quality andClimate, 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, ChronicExposure 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 MitochondrialDamage Environ Health Perspect, 2003, 111:455-460.





5. Holian, A, Hamilton, R, Morandi, MT, Brown, SD and Li, L. Urban Particle-inducedApoptosis and Phenotype Shifts in Human Alveolar Macrophages Environ HealthPerspect, 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 HealthPerspect, 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-ActivityRelationship Study. Journal of Applied Toxicolog y, Vol 13(2), pp129-135.

9. Nielsen, GD, Vinggaard, AM, 1988. Sensory Irritation and Pulmonary Irritation of C3-C7n-Alkylamines: Mechanisms of Receptor Activation. Pharmacology & Toxicology, Vol63, pp 293-304.

10. Nielsen, GD, Yamagiwa, M, 1989. Structure-Activity Relationships of Airway IrritatingAliphatic Amines. Receptor Activation Mechanisms and Predicted Industrial ExposureLimits. Chem.-Biol. Interaction s, Vol 71, pp 223-244.

11. Schaper, M, 1993. Development of a Database for Sensory Irritants and Its Use inEstablishing Occupational Exposure Limits. Am. Ind. Hyg. Assoc. J. Vol 54(9) pp 488-544.

12. Papadopoulos, A., Karayannic, M., and Knoeppel, H., Survey Analysis of OrganicCompounds 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: traceelements 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 theWorld Trade Center, EPA report 600/R-02/028, December 2002.

15. Final Technical Report of the Public Health Investigation to Assess Potential Exposuresto Airborne and Settled Surface Dust in Residential Areas of Lower Manhattan. NewYork City Department of Health and Mental Hygiene and Agency for Toxic Substancesand 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 theDust/Smoke Aerosol that Settled East of the World Trade Center (WTC) in Lower





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, TheWorld 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 theDetermination of Air Pollutants in Indoor Air, EPA Report 600/4-90/010, ResearchTriangle 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 inEstablishing Occupational Exposure Limits. Am. Ind. Hyg. Assoc. J. Vol 54(9) pp 488-

544.21. Agency for Toxic Substances and Disease Registry, Minimal Risk Levels (MRLs) for

Hazardous Substances, www.atsdr.cdc.gov/mrls.html, accessed September 11, 2003.

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Marilyn S. Black and Donald R. Cortes- Chemical Characterization of Building Dust Following The World Trade Center Collapse