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Innovations

Titanium Dioxide:
Environmental White Knight?

T
itanium dioxide (TiO2) is a multi- Hydroxyl radicals are very strong oxidizers break down the cell wall and outer mem-
faceted compound. It’s the stuff that and will attack all kinds of organic materials, brane, allowing cell contents to leak out and
makes toothpaste white and paint including those that make up living cells.” TiO2 particles to enter, thereby causing cell
opaque. TiO2 is also a potent photocatalyst Toto Frontier USA, based in Long damage and death. Hydroxyl radicals are
that can break down almost any organic Beach, California, is using TiO2 to make highly reactive and thus short-lived.
compound, and a number of companies are self-cleaning ceramic tiles for use in hospitals, Superoxide ions, while longer-lived, cannot
seeking to capitalize on TiO2’s reactivity by public restrooms, and other settings where penetrate the cell membrane because of their
developing a wide range of environmentally cleanliness is vitally important, as well as on negative charge. Therefore, both must inter-
beneficial products. hard-to-reach rooftops, where simple sun- act immediately with the outer surface of an
light and rainwater can help prolong the life organism unless the TiO 2 particle has
Tile Tales of the roof. The tiles are made by applying a already penetrated the cell. Research at the
During the late 1970s, scientists began to one-micron layer of TiO2 to ceramic blanks National Renewable Energy Laboratory
realize that the propensity of TiO2 to absorb immediately as they exit the kiln. (Toto has shows that the process works equally well on
energy from the UV end of the solar spec- filed a patent for their specially developed bacterial and fungal spores. Tests performed
trum and then react with water vapor to “short fire” kiln, which makes the process by Toto and presented at a July 2000 Air
produce oxygen could be used to create sur- more economically competitive, although and Waste Management Association sympo-
faces that were, for all practical purposes, Harvey Malloy, director of sales and market- sium indicate that the TiO2-treated tiles
self-cleaning. According to Daniel Blake, ing for the company, admits that the tiles achieve a 99.9% bacterial kill rate within one
principal scientist at the Department of still cost 10–20% more than regular ceramic hour for such strains as penicillin-resistant
Energy’s National Renewable Energy tiles.) The result is a photocatalytic coating Staphylococcus aureus and Escherichia coli.
Laboratory in Golden, Colorado, when that bonds with the tile and remains in place Another useful property of TiO2 is that
TiO2 is exposed to UV light of a wavelength for the normal life of the tile itself. This coat- it is superhydrophilic—the surface of a tile
below 385 nanometers in the presence of ing has several intriguing properties. treated with it attracts water rather than
Reuther/EHP, Greenwell/EHP

water vapor, two highly reactive substances First, it can break down organic matter repelling it. In the September 1999 issue of
are formed: hydroxyl radicals [OH] and a into carbon dioxide (CO2) and water. When Ceramic Industry, Malloy explained the
superoxide ion [O2-1]. Says Blake, “These organic matter lands on a TiO2-coated tile importance of this property: “Generally,
are highly reactive chemical species. and water is applied, the hydroxyl radicals water droplets form on the surface of a

A 174 VOLUME 109 | NUMBER 4 | April 2001 • Environmental Health Perspectives
Innovations • Environmental White Knight?

ceramic tile at a contact angle of 43 degrees. interior tile applications. “If we make the The initial Noxer block design involved
These tiles are considered hydrophobic. claim that the tile is antibacterial, we could a 200 millimeter (mm) by 100 mm block
Over time, contaminants collect on the sur- be going outside of what is allowable under with a 5–7 mm thick surface layer contain-
face of the tile in droplets and remain on the current Environmental Protection Agency ing TiO2 mounted on a cement mortar base
surface after the water evaporates. Water standards,” he says. Current standards to a total thickness of 60 mm. In tests by
dropped on the surface of a photocatalytic require a specific kill level within a certain Mitsubishi, the block was set in a reaction
superhydrophilic tile has been shown to amount of time. TiO2 achieves the kill level vessel and exposed to a mixture of air and 1
spread and form at a contact angle of only 7 but in a longer period of time. However, part per million (ppm) NOx to simulate
degrees in exterior applications and 25 while slower than an agent like alcohol or vehicle emissions. A hole in the box allowed
degrees in interior applications.” This means bleach, TiO2 is also less harmful to the envi- for the addition of UV light, and a variety of
surface wetting and rinsing is more uniform; ronment, so it would be useful where a high humidities were tested. According to
water slides under and floats away organic kill rate needs to be maintained over a long Mitsubishi, when the surface of the Noxer
surface contaminants. These tiles are signifi- period of time. slab is irradiated, oxygen is created, which
cantly easier to maintain in interior applica- oxidizes NOx in the air into nitric acid ions.
tions because they don’t require the use of Road Warrior These ions can then be washed away by
bleaches and detergents, wrote Malloy, and Some of the 400 miles of pavement in the rainfall or neutralized by the alkaline com-
they allow for the creation of exterior ceram- Westminster borough of London may soon position of the concrete.
ic facades and roofs that are self-cleaning have a role that goes far beyond smoothing Results of these tests showed an 80%
with rainwater. footpaths and roadways. Japan’s Mitsubishi NOx removal rate based on an intensity of
These surfaces are in fairly wide use Materials Corporation has developed a UV light of 1–12 watts per square meter
throughout Japan and are being marketed in paving stone it calls “Noxer” that uses the (W/m2) (the UV intensity of direct sun-
Europe as well, but they have not yet reached catalytic properties of TiO2 to remove nitro- light in summer is 20–30 W/m2, compared
the U.S. market. Malloy says Toto is working gen oxide (NOx) from the air, breaking it to 1 W/m2 on a cloudy winter day). The
on two products for the U.S. market includ- down into more environmentally benign blocks functioned best under humidity con-
ing a self-cleaning exterior facade and interior substances that can then be washed away by ditions of 10–80%, with an inverse relation-
tile surfaces. However, he says, there are regu- rainwater. NOx is produced in abundance ship between NOx removal and humidity.
latory roadblocks to cross first, especially for through vehicle emissions. According to Mitsubishi spokesperson

Environmental Health Perspectives • VOLUME 109 | NUMBER 4 | April 2001 A 175
Innovations • Environmental White Knight?

Yoshihiko Murata, in use outdoors the NOx dealing with NOx as it comes out of the treatment for the TiO2 crystals that would
removal rate varies depending on the con- exhaust. NOx is a product of high-tempera- accelerate the reaction by four to six times.
centration of NOx in the air. The company ture combustion, and it’s something we The Bio-KES system is currently being
is currently conducting tests using computer have to deal with one way or another. If you used primarily by commercial florists. KES
simulations of pollution and actual street tried to do it in a tunnel with the proper Science & Technology is also developing
measurements. lighting spectrum it might work, but on the models for use in sea/land cargo containers
The Noxer blocks will be manufactured pavement? Seems like a hard way to make and in truck and train transportation.
for testing by Marshalls (the United your point.”
Kingdom’s largest manufacturer of land- Diverse Decontaminator
scape, building, and drainage materials for A Fresh Application Still other researchers are working on ways
the construction industry and domestic In addition to cleansing the air outside, to use TiO2’s properties to benefit the envi-
home improvement markets) as a concrete TiO2 is being used to treat the air in fruit, ronment. Barreto has developed an experi-
base topped by a one-centimeter layer of a vegetable, and cut flower storage areas to mental method of removing the gasoline
mixture of TiO2, zeolite, and sand, crushed prevent spoilage and increase the products’ additive methyl-tert-butyl ether (MTBE,
quartz, or ground glass. Marshalls will use shelf life. The Kennesaw, Georgia–based used as an octane enhancer) from water by
the same manufacturing processes and KES Science & Technology has commer- bubbling oxygen into the contaminated
machinery as for their traditional products, cialized the work of Marc Anderson, a pro- water and adding TiO2, a process that con-
but company PR manager Rachel Brown fessor of environmental engineering and verts both MTBE and another additive,
says, “In principle, there’s no reason why the materials science at the University of tert-butyl alcohol, to CO2 with a 90% effi-
Noxer technology could not be adapted for Wisconsin at Madison to create an enclosed ciency rate in as little as four hours. MTBE
walling, tunnels, curbs, and so on to reduce system that uses the photocatalytic proper- is a potential human carcinogen, and con-
the effects of vehicular emissions in the envi- ties of TiO2 to remove ethylene from the cerns have been raised about its potential
ronment.” In addition to the proposed air. Ethylene is a naturally occurring gaseous for acute effects from exposures by inhala-
Westminster trials, Noxer blocks are also growth hormone produced by plant tissue tion and long-term exposures from drink-
being tested in Osaka and Chiba, Japan. that in concentrations as low as 1 ppm trig- ing water. Barreto’s technology is still
“NOx removal using TiO2 coatings and gers the ripening of fruits and vegetables. under study and has not yet been commer-
additions to paving materials and large-scale Ethylene is also produced from other cially developed.
panels on road sides and the like is a very sources including internal combustion Researchers at Robert Gordon University
practical approach,” says Blake. “It’s pas- engines, certain fungi, and cigarette smoke. in Aberdeen, Scotland, have experimented
sive, in the sense that it relies on natural Originally developed for use aboard the with degrading microcystins (toxins pro-
sunlight and air movement, and no lamps space shuttle, the Bio-KES system breaks duced by cyanobacteria that are linked with
or fans are required; thus, it’s simple to down ethylene into CO 2 and water. liver cancer and can cause death in immuno-
implement. Adverse effects of the system According to Anderson, the University of suppressed people) by simply stirring in
seem unlikely because the quantity of the Wisconsin was active in producing plant TiO2 and exposing the water to UV light.
NOx is very low to begin with, and it’s dis- growth chambers for shuttle experiments. Results show a complete degradation of the
tributed over large areas.” He says, “We had to develop a way to toxin microcystin-LR in less than 20 min-
Reynaldo Barreto, remove the ethylene from the air because utes. Says Blake, “[This application] is quite
a chemistry professor otherwise it would retard growth and spoil interesting because the TiO 2 will work
at Purdue University the plants. Conventional filtration would under ambient sunlight. This has the poten-
in West Lafayette, just remove particulates from the air, but we tial for applications where one could use
Indiana, agrees it is needed a way to break down this gaseous solar ponds [artificially created, enclosed
an interesting idea, substance in an efficient manner while pro- bodies of water that use ambient light as part
but, he says, “I think ducing no hazardous by-products.” The of a treatment process] or other means to
we’d be better off Bio-KES system has been used successfully treat large areas or quantities of water where
on six shuttle missions since 1993. the processing rate didn’t have to be on the
The system draws air through small order of millions of gallons a day.”
borosilicate tubes (4 mm in diameter by 12 Research suggests that TiO 2 may be
mm long) that have been lined with a useful in other applications to remove

Reuther/EHP (photos clockwise from top: Greenwell/EHP; Taglia e Incolla; PhotoDisc; PhotoDisc)
TiO2 coating. Each system can handle vol- organic contaminants from water. In exper-
umes up to 10,000 cubic feet and contains iments at Sandia National Laboratories in
48 eight-watt UVA bulbs and six eight- which contaminated water was flowed
watt UVC bulbs. According to KES through glass pipes lined with TiO2 while
Science & Technology, the combined being exposed to UV light, researchers were
action of UV light able to reduce concentrations of tri-
and TiO 2 oxidizes chloroethylene (TCE) from 1.2 ppm to less
ethylene into CO2 than 50 parts per billion in only 5 minutes.
and water vapor at (The project never reached commercializa-
a rate of more than tion, however.) Michael Prairie, a principal
32 milliliters of eth- investigator at Sandia, was lead investigator
ylene gas per hour. on a number of TiO2 research projects at
University of Wis- Sandia in the early 1990s, including using
consin researchers TiO 2 to remove explosives residue from
are working on a water, work that he says was eventually

A 176 VOLUME 109 | NUMBER 4 | April 2001 • Environmental Health Perspectives
Innovations • Environmental White Knight?

dropped because the kinetics were too slow
or the reaction didn’t reach completion.
“We tried piggybacking photocatalysis with The Road to Greener Blacktop
biodegradation in a two-step process and
had some success there,” he says, “but it just What’s black and white and green all over? Asphalt pavement! Covering 94% of paved U.S.
doesn’t seem to work well enough on large roads, asphalt pavement is completely recyclable, and research in recent years has yielded many
groups of compounds. . . . And we’ve done ways to enhance asphalt mixes and save landfill space by incorporating both the pavement itself
some work on metals reduction using and waste materials that otherwise would be landfill-bound. About 18 million tons of asphalt
TiO2—which seems to work best with mer- pavement occupying some 10 million cubic yards of space is sent to landfills each year. Without
cury—where you could use it as a treatment the recycling already being done today, that volume would climb to nearly 52 million cubic yards.
or for metals recovery.” Asphalt pavement is composed of 95% crushed rock aggregate and 5% asphalt cement, a
sticky petroleum refining by-product that holds it all together. According to the National Asphalt
A Chink in the Armor? Pavement Association, about 80% of the asphalt pavement taken up each year—some 73 million
tons—is recycled and reused in highway applications. Asphalt pavement can be stockpiled and
One concern raised about the use of TiO2 is
recycled later by milling into gravel-size chunks, heating, and adding more liquid asphalt cement
the formation of potentially harmful inter-
and aggregate as needed. Or it can be recycled on the spot using techniques known as hot in-
mediate products during the breakdown of place and cold in-place recycling, which basically involve digging up and crushing the pavement,
organic substances. The 1979 report mixing it with fresh asphalt emulsion, and laying it back down, all in one pass.
Bioassay of Titanium Dioxide for Possible Among the many recyclables that can be added to asphalt pavements are rubber tires and
Carcinogenicity NTIS# PB288780/AS (CAS waste toner. According to the Rubber Pavements Association, asphalt pavement supplemented
No. 13463-67-7) states that TiO 2 itself with ground rubber tires provides a quieter ride and a strong surface with less material. Rubber-
shows no evidence of carcinogenicity. But modified asphalt pavement currently eats up about 10 million scrap tires per year, says Doug
Carl Koval, a chemist at the University of Carlson, director of government relations for the association. Industry figures indicate that 273
Colorado in Boulder, and others have raised million scrap tires were being generated annually as of 2000. Carlson says that if 25% of total
the concern that the reactions produced by lane miles of urban U.S. roads were surfaced with rubber asphalt pavement annually, nearly all the
TiO2 may create substances more danger- nation’s discarded tires could be removed from the waste stream.
ous than the original pollutant. Studies at the Center for Transportation Research at the University at Texas at Austin show that
Says Koval, “When illuminated TiO2 is toner from spent cartridges and manufacturing waste can fortify asphalt pavements, making a
used to decompose organic compounds, a “stiffer” mix that holds up well in hot areas. Toner, made of styrene polymers and carbon, is con-
large number of intermediate compounds are sidered environmentally benign. In September 2000 the Texas Department of Transportation,
usually formed. In some cases, these interme- which sponsored the studies, patented preferred methods for creating toner-modified asphalt.
diate compounds can be more hazardous The 1998 Transportation Equity Act for the 21st Century promotes recycling in U.S. road con-
than the compound being decomposed.” For struction. Under the act, the Recycled Materials Resource Center was established at the University
example, he says, the breakdown of TCE of New Hampshire in Durham. Director T. Taylor Eighmy says the center is developing standards
and procedures for optimizing various recycling techniques. For more guidance, the United States
yields trichloroacetic acid (a substance almost
is turning to several European countries that already have experience with sustainable road build-
as toxic as TCE) and, in the gaseous phase,
ing. In 1999 a delegate of U.S. engineers, scientists, and paving specialists met with representa-
phosgene (a chemical warfare agent). tives from Sweden, Denmark, Germany, The Netherlands, and France to learn more about the
However, he says, this doesn’t mean that all policies, programs, and techniques being used successfully in those countries. –Susan M. Booker
applications using TiO2 would be dangerous.
“In situations where this type of process was
being proposed for outdoor use, I see no photocatalytic device and the way it is con- of TiO2 has pluses and minuses that make it
problems with it, because similar things occur structed and operated.” attractive for some applications and not for
naturally in the atmosphere, and it would be All that being said, in the realm of envi- others. The photocatalytic chemistry of
unlikely that concentrations of the hazardous ronmental cleanup technology is TiO 2 TiO2 is very intriguing. It works in water or
chemical would reach toxic levels. . . . indeed the white knight riding to the rescue air, it uses light instead of heat, and it is
However, [in an indoor setting] who knows or something less? Says Blake, “There is no such a simple concept. Engineering it with
what would be formed if TiO2 photocatalysis single technology that can address the very the right balance of economics and perfor-
were used to decompose plasticizers, bacteria, wide range of contamination problems in mance is the challenge.”
and so on, and what the health effects might the environment. Most workers in the field
be from inhaling such compounds?” recognize that the photocatalytic chemistry Lance Frazer
Certainly there is cause for caution, agrees
Anderson. “But given time and control over
the process,” he adds, “these daughter prod- Su g g e s t e d R e a d i n g
ucts do break down into environmentally
benign substances, a process which can be Fujishima A, Hashimoto K, Watanabe T. TiO2 photocatalysis: fundamentals and
monitored using a gas chromatograph.” And, applications. Tokyo: BKC, Inc., 1999.
says Blake, “All oxidization processes have Maness PC, Smolinski S, Blake DM, Huang Z, Wolfrum EJ, Jacoby WA. Bactericidal
the potential to produce partial oxidization activity of photocatalytic TiO2 reaction: toward an understanding of its killing
products. It comes down to a question of the mechanism. Appl Environ Microbiol 65(9):4094–4098 (1999).
fraction of the target compounds that are
converted to the intermediate products and Malloy H. Environmentally friendly ceramic tile. Ceram Ind 149(10):37–42 (1999).
how much of those produced are released Watanabe T, Kojima E, Norimoto K, Saeki Y. Fabrication of TiO2 photocatalytic tile
into the air or water. The amount released and practical applications. Fourth Euro Ceramics 11:175–180 (1995).
Tart/EHP

will be a function of the efficiency of the

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