The 9/11 Carbon Nanotubes

Carbon Nanotubes (CNT) Found in 9/11 Lungs and Dust of WTC Responders.
Is this related to the nano-thermitic material also found in the WTC dust?

Wu M, Gordon RE, Herbert R, Padilla M, Moline J, Mendelson D, Litle V, Travis WD, Gil J. Case report: Lung disease in World Trade Center responders exposed to dust and smoke: carbon nanotubes found in the lungs of World Trade Center patients and dust samples. Environ Health Perspect. 2010 Apr;118(4):499-504.
http://ehp03.niehs.nih.gov/article/fetchArticle.action?articleURI=info:doi/10.1289/ehp.0901159
William D. Travis from the Memorial Sloan-Kettering Cancer Center, New York, New York, USAThe rest from the: Mount Sinai School of Medicine, New York, New York, USA

http://en.wikipedia.org/wiki/Carbon_nanotube

From the Abstract:

CASE PRESENTATION: Carbon nanotubes (CNT) of various sizes and lengths were noted. CNT were also identified in four of seven WTC dust samples.

DISCUSSION: The finding of CNT in both WTC dust and lung tissues is unexpected and requires further study.

Material and Methods
Identification of carbon nanotubes (CNT) was based on comparison with a positive control sample provided by A. Shvedova from the National Institute for Occupational Safety and Health (NIOSH) and on the images and descriptions found in two publications (Lam et al. 2006; Poland et al. 2008). Seven DS collected at different sites of the WTC (generously provided by R. Nolan, Environmental Sciences, City University of New York) were also observed by analytic electron microscopy for the presence of structures, particularly CNT.

Results
Table 1.
Summary of findings in pathology and minerologic/asbestos fiber burden analyses.
http://ehp03.niehs.nih.gov/article/slideshow.action?uri=info:doi/10.1289/ehp.0901159&imageURI=info:doi/10.1289/ehp.0901159.t001

Patient A. Pathologic summary: UIP-like (UIP, usual interstitial pneumonitis), HP-like (HP, hypersensitivity pneumonia). Mineralogic and asbestos fiber burden analysis: silicates (AS, aluminum silicate; MS, magnesium silicate) 165,600/g and CNT 110,400/g.

Patient B. Pathologic summary: UIP-like, NSIP-like (NSIP, nonspecific interstitial pneumonitis). Mineralogic and asbestos fiber burden analysis: AS and MS: 165,600/g; CNT: 3,450/g, and no asbestos fibers.

Patient C. Pathologic summary: NSIP-like (cellular > fibrosing). Mineralogic and asbestos fiber burden analysis: CA (CA, chrysotile asbestos): 36,800/g; AS and MS: 184,000/g; CNT: 230,000/g.

Patient D. Pathologic summary: Mild chronic bronchiolitis; occasional peribronchiolar and submucosal fibrosis. Mineralogic and asbestos fiber burden analysis: CA: 5,520/g; AS and MS: 27,600/g; S (CS, calcium sulfate): large amount; CNT: 11,040/g.

Electron microscopy mineralogic findings. Four of the seven WTC dust samples contained CNT. The lung specimens of three of the patients with interstitial disease (Patients A, B, and C) contained CNT (Figure 3A) virtually identical to those of the dust samples (Figure 3B) and of the positive control sample (Figure 3C). CNT seen were all single-walled and of various lengths. They were mostly ropelike under electron microscopy... The nanotubes identified in patient lung samples appear mostly in single or pairs. Most CNT seen in the CNT-positive control and WTC dust samples were stacks of single nanotubes, thus appearing to be variable in thickness. No CNT were found in the lungs of either the 40 construction workers (not exposed to the WTC dust *) or the 20 negative control samples.

Figure 3
http://ehp03.niehs.nih.gov/article/slideshow.action?uri=info:doi/10.1289/ehp.0901159&imageURI=info:doi/10.1289/ehp.0901159.g003
Electron micrographs of CNT. These appear as tangled long transparent hairlike ropes and stacks of single-walled CNT. All three representative graphs were taken at a magnification of 100K. Single CNT in each graph are indicated by thin arrow. The arrowheads depict metal particles. Bar = 100 nm. (A) Digested patient lung tissue. (B) WTC dust sample. (C) Control sample from NIOSH.

The lungs of these (9/11 WTC) patients contained large amounts of silicates, and three of them showed nanotubes.

* Additional data on those 40 construction workers used as controls: As a comparison, we reexamined for the presence of CNT in 40 samples taken from unrelated workers from diverse construction trades suspected for asbestos-related disease. These patients were known to have been exposed to asbestos, and most of these 40 patients had a high lung burden of asbestos fibers. Less than 10%, however, had platy aluminum and magnesium silicates similar to those seen in WTC patients. Furthermore when they were seen in the control samples, they were present in small quantities (< 1,000/g wet weight of lung).

Discussion
In this case report, we describe seven previously healthy WTC responders who developed lung disease after sustaining heavy first- and second-day exposures to WTC dust and debris. We summarize our findings as follows:

a) CNT were found in some WTC-exposed patients with persistent lung disease with confirmation by positive controls and in the WTC dust. This finding was present in responders with extensive interstitial/parenchymal abnormalities (three of four patients) and in one of two patients with small airway disease, but not in the patient with nonnecrotizing granulomas.**

b) We found a higher amount of aluminum silicate and magnesium silicate in all four patients with diffuse interstitial/parenchymal abnormalities compared with those with small airway disease and granuloma. Chrysotile asbestos fibers were also found in four of seven patients in quantities modestly higher than background levels of asbestos in the New York City population. In interpreting these findings, however, it should be noted that mineralogic analysis of the lungs can be biased because of sampling variability within the lung itself.

Electron microscopic mineralogic analysis revealed CNT in WTC responders with extensive interstitial/parenchymal abnormalities (three of four patients) and in one of two patients with small airway disease, but not in the patient with nonnecrotizing granulomas. **

** However, CNT were not found in Patient G who had granulomas, perhaps because of inadequate sampling of the tissue.

Nanomaterials such as CNT have many potential applications in electronics, computer, and aerospace industries because of their desirable electrical, mechanical, and thermal properties (Lam et al. 2004). CNT are hydrophobic carbon cylinders with a diameter of a few to 200 nm and variable length depending on their degree of aggregation (Florito et al. 2006; Li et al. 2007; Mercer et al. 2008; Murr et al. 2005; Shvedova et al. 2008a; Tian et al. 2006). There are single-walled carbon nanotubes (SWCNT), consisting of one such cylinder, and multiwalled carbon nanotubes (MWCNT), composed of cylinders concentrically stacked and in the form of ropes with a common long axis. They can either be commercially synthesized or can develop spontaneously over flames and high temperatures in the presence of carbon and a metal catalyst.

CNT of commercial origin, common now, would not have been present in substantial numbers in the WTC complex before the disaster in 2001. However, the high temperatures generated during the WTC disaster as a result of the combustion of fuel in the presence of carbon and metals would have been sufficient to locally generate large numbers of CNT. This scenario could have caused the generation of CNT that we have noted in the dust samples and in the lung biopsy specimens ****.

**** Really? How high needs to be the temperature for the generation of CNT? And is "fuel" really capable to reach those temperatures?

[Experimental studies, both in vitro and in animals, show the potential toxicity of some types of CNT (Florito et al. 2006; Li et al. 2007; Mercer et al. 2008; Murr et al. 2005; Shvedova et al. 2008a, 2008b; Tian et al. 2006). They are believed to be proinflammatory, fibrosing, and capable of inducing granulomas when inhaled in mouse models (Mercer et al. 2008). Shvedova et al. (2008b) observed that inhalation of SWCNT resulted in a 4-fold increase in fibrosis, along with collagen deposition, in the peribronchial and interstitial areas in the lungs of mice when compared with exposure by aspiration of SWCNT. CNT introduced into the abdominal cavity of mice can cause asbestos-like pathogenicity (Poland et al. 2008). Very recently, the Berkeley group has shown that oxidative stress can be induced by zero-valent iron (Fe) nanoparticles and Fe(II) in human bronchial epithelial cells (Keenan el al. 2009), which may contribute to the chain reaction of oxidative damages.]

[There is evidence that CNT may contribute to granuloma formation, although this may depend on the type of CNT present. In a study by Lam et al. (2004), granuloma formation and interstitial inflammation was observed in four of nine mice who were administered a high dose (0.5 mg) of CNT compared with mice administered a low dose (0.1 mg) of CNT. Similar findings were also observed in a study conducted by Muller et al. (2005), where granulomas, completely or partially blocking the bronchial lumen, were observed in the bronchi of rats 60 days after intratracheal instillation of MWCNT. Additionally, ground MWCNT, administered to rats via intratracheal instillation, were better dispersed in the parenchyma and also produced granulomas in the interstitial tissue (Muller et al. 2005). Shvedova et al. (2005) showed that epitheloid granulomas, which were rapid, progressive, and dose dependent, were observed at sites where SWCNT aggregates were deposited after pharyngeal aspiration of SWCNT in mice. Furthermore, diffuse interstitial fibrosis with alveolar thickening was also observed in areas distant from the site where SWCNT aggregates were deposited (Shvedova et al. 2005). In most of these studies, carbon black particles used as reference particles did not produce any granulomas (Lam et al. 2004; Muller et al. 2005; Shvedova et al. 2005).]

Mediastinal granulomas were described in prior studies by other WTC-exposed individuals (Izbicki et al. 2007).

The etiology of the conditions described in WTC responders cannot be fully elucidated, because our analysis does not include toxic soluble gases. In this case report we identified the presence of unexpected CNT, silicates, and other elements, but it remains unclear whether any of these compounds may have caused the lung pathology. The combination of compounds may have increased the likelihood that individuals would develop pulmonary impairment. Further surveillance of individuals with these exposures should provide us with additional answers.

The finding of carbon nanotubes in four of seven WTC patients in concentrations ranging from 3,450/g to 230,000/g of wet weight and in four of seven dust samples collected from the WTC site, although unique and important, cannot be construed as evidence for WTC exposure. Likewise, their absence should not be used as evidence of lack of exposure. A retrospective check of specimens in unrelated asbestos cases evaluated over the past 20 years was negative for CNT. Recently, however, small numbers of CNT have been identified in control specimens from the tri-state area (New York, New Jersey, Connecticut) at minimal concentrations (Gordon R, unpublished data). These might originate in the combustion engines of automobiles (Lam et al. 2006).

Conclusion
The predominant finding of interstitial lung disease on pathology and presence of similar materials in most of the mineralogic samples including CNT and platy silicates suggests that WTC exposure may have contributed to the development of lung disease.

Related references:
1-
http://ammtiac.alionscience.com/pdf/AMPQ6_1.pdf
2001-2002
Nanoenergetics: An Emerging Technology Area of National Importance
Dr. Andrzej Miziolek. Weapons and Materials Research Directorate
US Army Research Laboratory.

Functionalized Carbon Nanotubes for Energetic Applications."In particular, the high electron density that characterizes the nanotube structure as well as the high conductance along the tube wall may lead to more robust and reliable ignition behavior. Long-term storage stability is one of the key elements of a successful propellant formulation. In this regard, there is hope that carbon nanotubes could be used to encapsulate nanoscale energetic ingredients..." (p. 46)


2-
Energetic Materials as a Potential Cause of the 9/11 First Responder Illnesses
Kevin Ryan
2011
Foreign Policy Journal
http://www.pulmonaryfibrosis.org/node/518

Less understood, and requiring further study, are unusual illnesses of the immune system commonly observed in the WTC first responders. These include various types of interstitial lung disease, such as eosinophilic pneumonia, granulomatous pneumonitis, and bronchial obliterans [“bronchiolitis obliterans”, according to Jeff King]. Environmental triggers for these illnesses include aluminum silicates, which have been found in the lungs of WTC first responders at high levels in “unusual platy configurations.” [2]

Carbon nanotubes
In 2010, researchers reported the presence of carbon nanotubes in the lungs of WTC first responders.[15] Carbon nanotubes are high-tech nanostructured materials, which exhibit unique properties like ballistic conduction. The health effects of carbon nanotubes have been shown to be similar to the health effects produced by exposure to asbestos.[16]
Carbon nanotube formation requires three basic components: a source of carbon, a source of heat, and the presence of certain metals. In particular, formation of the single walled carbon nanotubes (SWCNTs) found in the lungs of first responders requires that the metals be present.[17] All of these requirements were met at the WTC site on, and for months after, September 11, 2001.
The three most effective metals for the synthesis of SWCNTs are iron, nickel and cobalt. Both iron and nickel were present in high concentrations near Ground Zero, as shown by aerosol testing done by a team from the University of California, Davis.[18] Iron oxide and nickel oxide are common oxidants in thermite mixtures.
Airborne carbon compounds were certainly present in abundance at Ground Zero in the form of particulate matter resulting from the fires. Heat was also in abundance, as extremely high temperatures were present on 9/11 and afterward at Ground Zero. These temperatures were at least 1,000 degrees Fahrenheit, hotter than first reported by government scientists, and were far higher than temperatures seen in a normal structure fire.
The molten metal and vaporized silicates that have been reported in the WTC dust can only be explained by the presence of an exothermic reaction like the thermite reaction.[19] Large quantities of carbon nanotubes might have been formed at Ground Zero due to the high temperature environments created by the thermite reaction and the airborne metal catalysts that were also present.
A second possible explanation for the carbon nanotubes in the lung tissue of the first responders is that the carbon nanotubes were components of actual energetic materials that were used in the destruction of the buildings. Carbon nanotubes have been used as energetic modifiers,[20] to improve stabilization of explosives,[21] and to enhance ignition properties.[22]

Conclusion
... The finding of carbon nanotubes in the lungs of first responders suggests two possible explanations. The nanotubes might have been formed in the unusual environment at Ground Zero, where extremely high temperatures and the presence of airborne metallic species gives yet more evidence for the presence of thermitic materials. Alternatively, the nanotubes might have been components of energetic materials. In either case, the presence of carbon nanotubes in the lungs of WTC first responders suggests the use of energetic materials and should be studied in more depth. These facts and research findings warrant further study of the correlation between environmental testing results, first responder health study results, and the use of energetic materials at the WTC.

References:
[2 and 15] Wu M, Gordon RE, Herbert R, Padilla M, Moline J, Mendelson D, Litle V, Travis WD, Gil J. 2010. Case Report: Lung disease in World Trade Center responders exposed to dust and smoke: Carbon nanotubes found in the lungs of World Trade Center patients and dust samples, Environmental Health Perspectives 118 (4).
[16] Van Noorden R. 2008. Carbon nanotubes behave like asbestos. Chemistry World. Available: http://www.rsc.org/chemistryworld/News/2008/May/20050802.asp [accessed 19 January 2011].
[17] Height JH. 2003. Flame synthesis of carbon nanotubes and metallic nanomaterials. Dissertation submission to Massachusetts Institute of Technology, Department of Chemical Engineering.
[18] Ryan KR, Gourley JR, Jones SE. 2009. Environmental anomalies at the World Trade Center: evidence for energetic materials. The Environmentalist 29 (1):56-63; doi: 10.1007/s10669-008-9182-4 [Online 4 August 2008]
[19] Jones SE, Farrer J, Jenkins GS, Legge F, Gourley J, Ryan K, Farnsworth D, Grabbe C. 2008. Extremely High Temperatures during the World Trade Center Destruction, Journal of 9/11 Studies 19. Available: http://journalof911studies.com/articles/WTCHighTemp2.pdf [accessed 19 January 2011].
[20] Ramaswamy AL, Kaste P. 2003. Combustion modifiers for energetic materials. 34th International Annual Conference of ICT; Karlsruhe; Germany; 24-27 June 2003. 1-13.
[21] Patent issued to Raytheon Company, WO/2008/082724. Improved Explosive Materials by Stabilization in Nanotubes. World Intellectual Property organization. Available: http://www.wipo.int/pctdb/en/wo.jsp?WO=2008/082724 [accessed 19 January 2011].
[22] Manaa MR, Mitchell AR, Garza RG, Pagoria PF, Watkins BE. 2005. Flash Ignition and Initiation of Explosives−Nanotubes Mixture. J. Am. Chem. Soc. 127(40):13786–13787.

In the original website, we read an important answer:
http://www.foreignpolicyjournal.com/2011/02/04/energetic-materials-as-a-potential-cause-of-the-911-first-responder-illnesses/comment-page-2/#comments
By
Hans de Jonge
http://www.youtube.com/watch?v=xgqag1dQFyI
February 12, 2011 - 1:49 pm
Excellent article. The known substances who were in the air give the range of diseases mentioned. There is still a range of energetic substances not looked for: the radioactive ones. The collected dust in the hands of dr. Steven Jones could also be analyzed on radioactive isotopes. This could explain some found illnesses like fast cancer developement.. For isotope analysis one need a special instrument, the Thermal Ionization Mass Spectrometer. Radioactive isotopes could be emitted by the possible underground nuclear explosions that destroyed the inner core of Builings WTC 1, 2 and 7