Chlorine Dioxide Mold and the Libraries

[Guest guest]

Hi All,

Look what I found on chlorine dioxide. It seems that Jim was right

about the selective toxicity of chlorine dioxide.

http://palimpsest.stanford.edu/byorg/abbey/an/an24/an24-4/an24-402.html

[Guest guest]

Tovell wrote:

Thanks Sharon, excellent article!

--G.

This is particularly interesting, as a description of the mechanism at

work:

According to Walter Hardy, chlorine dioxide is often confused with

chlorine or hypochlorite (bleach). However, chlorine dioxide uses

chemical processes that are quite distinct against microbial organisms.

Because of hyperactivity with sulfur compounds, chlorine dioxide or

ClO2, has a very selective attack against the full range of microbes,

from viruses to fungi. This selectivity of attack involves the

oxidation of disulfide bonds occurring when sulfur-containing amino

acids are used to crosslink two or more polypeptide strands within a

structural or enzymatic protein. Enzymes must have a specific

three-dimensional structure to catalyze their biochemical reactions.

The destruction of the disulfide bonds causes the enzymes to "denature"

or lose their shape and thus become dysfunctional. This prevents

metabolism and breaks the structural integrity of the microbe.4

Nothing is mentioned in the article about activation with acid. Any

ideas about the optimal way to uise MMS as an external disinfectant, in

the light of Dr. Humble's discovery of the activation procedure?

Should one activate a quantity, then dilute and spray, and if so, at

what dilution?

-----

Original Message -----

From:

Sharon

To:

Sent:

Thursday, December 13, 2007 11:03 PM

Subject:

[sPAM][ ] Chlorine Dioxide Mold and the

Libraries

Hi All,

Look what I found on chlorine dioxide. It seems that Jim was right

about the selective toxicity of chlorine dioxide.

http://palimpsest.stanford.edu/byorg/abbey/an/an24/an24-4/an24-402.html

[Guest guest]

Actually, the article DID say the stuff was activated.

I caught that.

4th paragraph, under the heading, Methods. when it ws used for fogging.....

Kathy

-----Original Message-----From: [mailto: ] On Behalf Of CaseSent: Friday, December 14, 2007 12:25 AM Subject: Re:[ ] Chlorine Dioxide Mold and the Libraries

Nothing is mentioned in the article about activation with acid. Any ideas about the optimal way to uise MMS as an external disinfectant, in the light of Dr. Humble's discovery of the activation procedure? Should one activate a quantity, then dilute and spray, and if so, at what dilution?

.. __________ NOD32 2721 (20071213) Information __________This message was checked by NOD32 antivirus system.http://www.eset.com

[Guest guest]

Kathy Wenger wrote:

Message

Actually, the article DID say the stuff was

activated.

I caught that.

4th paragraph, under the heading, Methods. when

it ws used for fogging.....

Ah yes, I missed that, since I searched for the word "acid".

I wonder, though, what "active, stabilised chlorine dioxide" means.

My understanding is that the MMS preparation is activated, unstable

sodium chlorite, emitting chlorine dioxide gas.

Kathy

Re:[ ] Chlorine Dioxide Mold

and the Libraries

Nothing is mentioned in the article about activation with acid. Any

ideas about the optimal way to uise MMS as an external disinfectant, in

the light of Dr. Humble's discovery of the activation procedure?

Should one activate a quantity, then dilute and spray, and if so, at

what dilution?

..

__________ NOD32 2721 (20071213) Information __________

This message was checked by NOD32 antivirus system.

http://www.eset.com

[Guest guest]

Bump

>

> Hi All,

>

> Look what I found on chlorine dioxide. It seems that Jim was right

> about the selective toxicity of chlorine dioxide.

>

> http://palimpsest.stanford.edu/byorg/abbey/an/an24/an24-4/an24-

402.html

>

[Guest guest]

That is so interesting that it got pulled. I wonder why? I am not

making any money on the distribution of this article therefore I

believe it's okay to post here.

http://palimpsest.stanford.edu/byorg/abbey/an/an24/an24-4/an24-

402.html

Volume 24, Number 4

Dec 2000

Controlling Mold on Library Materials with Chlorine Dioxide: An Eight-

Year Case Study

By Pat L. Weaver-Meyers, Wilbur A. Stolt, and Barbara Kowaleski

The University of Oklahoma Libraries uses chlorine dioxide in

solution as a wet wipe on moldy books, as a fumigant and in

atmosphere-activated gas packs to control mold. Descriptions of the

three delivery forms and results are provided. Chlorine dioxide

toxicity is compared to some other commonly used preservation

treatments.

Librarians and archivists have long recognized the many and varied

enemies to paper. Insects, fungi, the environment, and people can be

culprits in the destruction of books, archives and manuscripts. All

present significant and unique challenges to preservationists. This

article focuses on the problems associated with mold growth at the

University of Oklahoma Libraries and the results of using chlorine

dioxide in aqueous and gaseous form.

Articles discussing mold stress the importance of controlling the

environment to succeed in the battle against mold. Modern facilities

with sealed windows and computer-controlled heating, cooling and

ventilation systems have created much better environments for the

preservation of library materials. Yet, problems do occur when

environmental controls fail.1

Review of the Web site http://palimpsest.stanford.edu/bytopic/mold/

maintained at Stanford by CoOL, Conservation Online, includes a

thorough review of current recommendations on mold control. Emphasis

is placed on vacuuming with HEPA filters. In Nyberg's Invasion

of the Giant Spore, available at this site, fumigation is not

recommended because of human health concerns. However, Nyberg's

analysis of fumigation agents does not include any mention of

chlorine dioxide.

Chlorine dioxide has a long history of use as a disinfectant and is

accepted by the U.S. Environmental Protection Agency (EPA) Drinking

Water Division in water treatment applications. Compared to phenols,

bleach, glutaraldehyde, quaternary ammonium compounds and other

disinfectants, chlorine dioxide is the most effective biocide on hard

surfaces.2 In addition, it has been found to be 1,075 times more

potent than ethylene oxide as a gas sterilant.3 However, it has not

been discussed in the library literature as an alternative to

ethylene oxide or other gaseous fumigants. Also, it has not been

compared to phenol compounds (components of Lysol) as an effective

aqueous wipe for books. This oversight may be due to the relatively

recent research findings about chlorine dioxide gas and due to a

common assumption that chlorine dioxide and bleach are the same.

According to Walter Hardy, chlorine dioxide is often confused with

chlorine or hypochlorite (bleach). However, chlorine dioxide uses

chemical processes that are quite distinct against microbial

organisms. Because of hyperactivity with sulfur compounds, chlorine

dioxide or ClO2, has a very selective attack against the full range

of microbes, from viruses to fungi. This selectivity of attack

involves the oxidation of disulfide bonds occurring when sulfur-

containing amino acids are used to crosslink two or more polypeptide

strands within a structural or enzymatic protein. Enzymes must have a

specific three-dimensional structure to catalyze their biochemical

reactions. The destruction of the disulfide bonds causes the enzymes

to " denature " or lose their shape and thus become dysfunctional. This

prevents metabolism and breaks the structural integrity of the

microbe.4

Although further testing of chlorine dioxide in gaseous form is

needed, according to its current assessment by the U.S. Occupational

Safety and Health Agency (OSHA) and other agencies, to date no

mutagenic effects have been substantiated.5 Standards for both

aqueous and gas forms can be found at

http://www.epa.gov/iris/toxreviews/0496.pdf . These standards

recommend worker exposure to the gas of .1ppm over eight hours. Short-

term exposures can be as high as .3ppm. Aqueous solutions of chlorine

dioxide have been more thoroughly tested because of its use in water

treatment. It is frequently preferred in water treatment because it

does not result in the formation of trihalomethanes, like chlorine

does. In addition, recent uses of chlorine dioxide include the

treatment of foods. Many studies exist and are documented by the EPA

in the previously mentioned Web site about oral and skin exposure to

chlorine dioxide. To date, OSHA recommended exposures to chlorine

dioxide have been found to be relatively safe.

Background

The University of Oklahoma Libraries' main library building, the

Bizzell Library, is a structure composed of three separate additions

built in 1932, 1958, and 1982. The 1932 addition contains steel stack

construction with suspended glass flooring and is known as " the

decks " (see Photograph 1).

The 1958 addition contains several offices and closed collection

spaces. The materials affected by mold outbreaks in recent years have

been materials contained in the 1932 decks and in a closed collection

space in the 1958 addition. The materials contained in these spaces

include older library materials still classified in Dewey and

government documents materials. A vintage air handling systems

specific to that addition services the decks. A separate air handling

system services the 1958 addition, including a closed collection

area. Humidity in the closed collection area has fluctuated more than

relative humidity in the rest of the 1958 addition. Although air

conditioning specialists have investigated these fluctuations, no

explanation has been found for the frequent changing conditions in

the closed collection area. The air in this area, because of the

closed and infrequently used space, is often stagnant. Shelving,

broken furniture, and unprocessed gift collections are stored with

older materials in this area.

Changing humidity conditions in the decks have resulted from several

mechanical failures in the air handling system and were also the

result of roof damage that caused extensive leaks in 1991. Several

mold outbreaks have occurred in the decks and the closed collection

area. Although rapid repair of air handling equipment and

stabilization of humidity levels was always the first choice, mold

control could not be consistently achieved for a variety of reasons.

Consultation with microbiologists led the Libraries to select

chlorine dioxide as an antifungal agent with high biocidal activity

and relatively low toxicity. Chlorine dioxide used in conjunction

with humidity stabilization proved effective.

Methods

The University of Oklahoma Libraries began using chlorine dioxide as

a solution to wipe moldy books in 1991. This choice was made because

of concern about the long-term effects of other fungicides on stack

management workers. When mold broke out in the decks after extensive

roof damage in 1991, student workers were used to clean affected

volumes. Although the process was initially begun using a thymol

solution, concerns about the long-term carcinogenic effects of the

treatment led to consultations with microbiologists. Chlorine dioxide

was recommended as an agent that would be relatively safe for workers

treating materials, with no residual complications for library users.

It was also determined to be more effective in mold control than

phenols.

The relative safety of chlorine dioxide made it easier to clean and

dry books without moving them from the stack area to a workroom.

Since the outbreak spread throughout several floors, among numerous

volumes, teams could work more effectively and rapidly in the stacks.

Concern about exposure to library users was deemed unnecessary and no

areas of the library had to be closed. Wipe-down procedures were

similar to other libraries' treatments and consisted of wiping down

the book covers and edges with the solution and allowing items to be

fanned and air dried. If the mold growth infected the insides and

spines, pipe cleaners were soaked in the solution and used to treat

the interiors of the book spines. Shelves were also wiped with the

solution. Workers wore plastic gloves, but no further safety

precautions were recommended.

Chlorine dioxide is not bleach, but is an oxidizing and bleaching

agent that has been used in the paper industry for many years. It is

also used in both water and food treatment. In its use as a water-

based solution to wipe moldy books, the concentrations of <.02% have

little effect on hardback books. After repeated wipings, only slight

bleaching in the fold on book spines has been noted. Items wiped once

showed no visible change and most items wiped numerous times showed

no visible change. Further analysis of the invisible effect of the

solution on the long-term deterioration of the paper or bindings was

not done. Simple vacuuming of paper items, as suggested by others, is

probably preferable to wetting. However, numerous volumes of

congressional hearings were treated with no observable damage.

Wipe down of materials in the decks continued for several months.

However, mold did reappear. Repeated checks of the air handling

systems revealed some problems that were resolved, but erratic

performance of the system still left the decks vulnerable. Further

consultation with microbiologists resulted in a decision to fog the

deck area. Fogging was accomplished with a hand-held fogger. The

operator walked the aisles spraying the stacks and floors with a

<.02% solution of activated, stabilized chlorine dioxide. The intake

and outtake vents of the air handling system were fogged as well, in

the hope of reducing spore contamination in the ducts. Fogging took

place while the library was closed, but closure of the stacks during

regular hours was deemed unnecessary due to the lack of residual

exposure problems and lack of residual odor when dried.

Since the fogging, approximately five years have passed and no

further mold outbreaks have occurred in the decks. Although air

regulation may be more stable, outages of the system continue to

occur. A recent campus-wide air conditioning failure did not result

in a mold outbreak in the decks. However, that same campus-wide

problem caused a very substantial problem in the 1958 addition.

The closed collection area in the 1958 addition, as described

earlier, also serves as a general storage area (see Photograph 2).

It is a closed stack area with a small collection of older materials

or materials deemed highly collectible. This area has had repeated

mold infestations that have been treated quickly and effectively with

a wiping solution. This area has never been fogged, because the

collection is so small that control is normally easily maintained.

However, in the summer of 1997 during a campus-wide air conditioning

failure, control of mold in this area became impossible.

Moving materials out of the closed stack was not deemed advisable,

because of concern about contaminating other areas with a high mold

spore count. Since air conditioning was not working throughout the

building, limiting exposure in the major portion of the collection

was most important. After several weeks of daily treatment of volumes

in this area, and repair of the air handling system, mold continued

unabated. Consultants suggested that the mold spore count was so high

in the collection that ordinary control measures (humidity control

and temperature control) would not work. The plethora of stored

furniture, boxes, shelves, and other items made it impossible to

clean the area and provided too many opportunities for the mold

population to reinfect the treated book shelves a few feet away.

Although fogging would probably have worked, a newly available

alternative was provided by Engelhard Corporation as a test.6 This

product, a self-activating packet (Aseptrol™) that reacts with

humidity in the air, was used. The packet is a loose powder sachet,

which will begin releasing chlorine dioxide in 90 minutes after

exposure to ambient relative humidity. This sachet will release 1/2-2

vppm of chlorine dioxide per gram of material in a one gallon volume

with 10cc/minute of continuous air changeover. The sachet will

continue to release at a constant rate for 15 days before exhausting

at 85% relative humidity and over 30 days at 31% humidity.7

Approximately three packets were hung with wire ties between shelves

(see Photograph 3).

Regular inspection of the collections revealed a slight chlorine-like

odor, but no other effects were noted. However, mold continued to

grow until three additional packets were hung. Once a total of six

packets were hung in an area with approximately 12,000 sq. feet,

total control of mold growth was achieved. No further mold

infestations have occurred in the following six months. Exposure to

workers was limited because the collection is closed. Exposure rates

are controlled by the humidity. Relative humidity in the area did not

reach 85%, which means that the release rates were slower than the

maximum rate available from the packets. No odor could be detected

elsewhere in the libraries (odor threshold for chlorine dioxide

is .1ppm). As a result, no limitations were placed on public use of

the rest of the collections even through the closed collection shared

an air handling system that serviced the entire addition.

The gas packets proved to be highly effective and required the least

staff hours to deploy. It took about five minutes to open the

packages and hang the packets. The method was preferable to fogging,

because it dispersed the chlorine dioxide without wetting the floors

or materials. This kept humidity fluctuations down. Further, the gas

packets continued to disperse chlorine dioxide in response to the

relative humidity and were able to penetrate all the nooks and

crannies of the storage area. Because the packets disperse chlorine

dioxide faster as relative humidity increases and decrease dispersion

rates as the humidity lowers, it is ideal for situations in which

humidity control is known to fluctuate. A further advantage is that

control does not require constant monitoring and intervention.

Conclusion

Although environmental control is the best way to control mold

infestations, air-handling systems do fail. Vacuuming, the current

recommended technique, reduces mold spore levels and removes mycelium

residue from books. However, it does not kill mold spores. It is also

rather labor intensive. More importantly, exposure to high levels of

mold represents a human health hazard.8 Our experience with chlorine

dioxide's inhibition of future mold growth after fogging (five years)

and after use of gas packets (six months, to date) suggests a strong

sporicidal activity.

These results, coupled with recent findings that confirm chlorine

dioxide's relative safety, suggest that preservationists should

reexamine fumigation. New substances and more test results make it

appropriate to look at fumigation again and consider adjusting the

current recommended procedures with regard to human health hazards.

In particular, the health hazards of uncontrolled mold may outweigh

the use of " safe " fungicides.

Further research on chlorine dioxide's effect on the long-term

deterioration of paper needs to be undertaken to assure treatment is

as safe as visual observation of our treated collections has

suggested. However, in disaster recovery situations that require

immediate, safe control of mold growth, chlorine dioxide gas packs or

fogging can help contain an outbreak before air-handling systems can

be repaired. The current research reviewed in this article suggests

that the risks of long-term human health effects, either mutagenic or

carcinogenic, for the use of chlorine dioxide are low. The use of

this substance, particularly with the gas packet technology, is

attractive. Convenience, low labor costs and its potential to avert

disastrous mold outbreaks make this strategy worth serious

consideration.

References

1. , " Mold—The Silent Enemy, " The New Library Science 4

(August 1985): 1-21.

2. Ralph S. Tanner, " Comparative Testing and Evaluation of Hard-

surface Disinfectants, " Journal of Industrial Microbiology 4 (1989):

145-154.

3. K. Jeng & Archie G. Woodworth, " Chlorine Dioxide Gas

Sterilization Under Square-Wave Conditions, " Applied and

Environmental Microbiology 56 (February 1990): 514-519.

4. Walter O. Hardy, An Introduction to Chlorine Dioxide (North

Kingstown, RI: Engelhard Corp., 1997).

5. See the following Web site and search for chemical name, chlorine

dioxide, to get a fact sheet on worker exposure and a summary of

recent animal studies

(http://www.epa.gov/enviro/html/emci/chemnet/index.html.)

6. Engelhard Corporation, 554 Ten Rod Road, North Kingstown, RI

02852, (800) 477-6071, ext. 11, is the sole source of Aseptrol™ gas

packets. Current costs for packets are $2.47 for a packet that covers

200 cubic feet and $8.90 for a packet covering 1,000 cubic feet.

[Note: Engelhard no longer supplies the Aseptrol packets, but they

are now available through boating supply stores for use in boat

houses, campers, boats, and summer homes. The distributor, Starbrite,

will not sell them for general use, because they have not been

approved for this by the EPA and other agencies. However, they will

give you the name of a marine supply store near you if you call them

at 1-800-327-8583 and ask for a place near you that carries

their " mildew control bags. " -Editor]

7. Aseptrol Technology Profile Summary Sheets: Chlorine Dioxide for

Use in DRY Applications (North Kingstown, RI: Engelhard Corporation,

1997).

8. See Web site http://palimpsest.stanford.edu/bytopic/mold/for

article: " Mold as a Threat to Human Health. "

Reprinted by permission from The Journal of Academic Librarianship,

Nov. 1998, p. 455-458.

Pat L. Weaver-Meyers

Direction of Information Management and Delivery

University of Oklahoma Libraries

Norman, OK 73019-0528

Wilbur A. Stolt, Director of Public Services

University of Oklahoma Libraries

Barbara Kowaleski, Stack Management Supervisor

University of Oklahoma Libraries

I went to the site and the info has been withdrawn -did

you get a copy?

> >

>

> >

> >

>

[Guest guest]

hi all, just found this...same thing different name

http://www.shagbarkbantams.com/oxine.htm been used for years on

animals..no harm,etc............oxine is our friend mms...garyc

[Guest guest]

Works OK when you copy and paste the " 402.html " that is not active and add

the hyphen that is missing when the link is activated.

Cheers, Doug

Re: [ ] Re: Chlorine Dioxide Mold and the

Libraries

> Sharon wrote:

>> Bump

>>

>> I went to the site and the info has been withdrawn -did you get

>> a copy?

>>

>

>>

>>

>

>

[Guest guest]

Murray wrote:

Works OK when you copy and paste the "402.html" that is not active and add the hyphen that is missing when the link is activated.

Yes, and more people should use TinyUrl when trying to send long URLs.

http://tinyurl.com/yvsrr

http://tinyurl.com

Add TinyURL to your browser's toolbar

Once this is on your toolbar, you'll be able to make a

TinyURL at the

click of a button. By clicking on the toolbar button, a TinyURL will be

created for the page you are currently at.

[Guest guest]

Sharon wrote:

Bump

I went to the site and the info has been withdrawn -did you get a copy?

[Guest guest]

It would be nice for folks to post both the regular and the tiny url,

as I was told the tiny urls don't last forever. Therefore, once they

expire the regular url would be available in the archives still.

In Christ,

Ava

> > Works OK when you copy and paste the " 402.html " that is not

active and add

> > the hyphen that is missing when the link is activated.

> >

>

> Yes, and more people should use TinyUrl when trying to send long

URLs.

>

> http://tinyurl.com/yvsrr

>

>

> http://tinyurl.com

>

>

> Add TinyURL to your browser's toolbar

>

> TinyURL Toolbar.Once this is on your toolbar, you'll be able to

make a

> TinyURL at the click of a button. By clicking on the toolbar

button, a

> TinyURL will be created for the page you are currently at.

>

[Guest guest]

gdc4now64836 wrote:

> hi all, just found this...same thing different name

> http://www.shagbarkbantams.com/oxine.htm been used for years on

> animals..no harm,etc............oxine is our friend mms...garyc

>

It's described as a 2% chlorine dioxide gas suspended in an aqueous

solution.

How do you suppose that compares with MMS, which I've not seen described

in those terms, but rather as a 28% solution of 80% sodium chlorite.?

If one could ascertain how this compares with MMS, then all the ratios

in the article would be useful....

[Guest guest]

it was my understanding that when you make a dose ...wait 3 min....add

water or juice to dilute...you get a 1% gaseous solution of clo2...at

least that's what I remember from one of the pdf's I downloaded from

humble.......he wanted to be real safe and keep it at 1%......the site

I posted before said thay used a 2% solution and it was still very

safe....that's all I was trying to get across....garyc

[Guest guest]

gdc4now64836 wrote:

it was my understanding that when you make a dose ...wait 3 min....add water or juice to dilute...you get a 1% gaseous solution of clo2...at least that's what I remember from one of the pdf's I downloaded from humble.......he wanted to be real safe and keep it at 1%.....

Unless it is specified how much water is added to dilute it, it is

impossible to say what % the final solution is.

..the site I posted before said thay used a 2% solution and it was still very safe....

Actually, what they said is "Oxine Concentrate is a 2%

chlorine dioxide gas suspended in an aqueous solution. It is diluted

with water to varying degrees depending on how you would like to use it"

....which is somewhat different. So we still don't know how the Oxine

differs from the MMS...

that's all I was trying to get across....garyc

[Guest guest]

scmillers wrote:

> It would be nice for folks to post both the regular and the tiny url,

> as I was told the tiny urls don't last forever. Therefore, once they

> expire the regular url would be available in the archives still.

>

" How long will my tiny url last?

Tiny urls are never deleted so there is no lasting or expiration time.

Also Tiny urls cannot be edited once created so if you made a mistake

just create a new one. "

http://www.tiny.mn/faqs.php

http://tinyurl.com/2vy92w

[Guest guest]

I was told my a knowlegeable moderator that they do not last (but

don't know the time limit), I went to http://tinyurl.com/ and could

not find the answer.

Never heard of www.tiny.mn (another tiny url) until your post.

Thanks for the information.

In Christ,

Ava

> > It would be nice for folks to post both the regular and the tiny

url,

> > as I was told the tiny urls don't last forever. Therefore, once

they

> > expire the regular url would be available in the archives still.

> >

>

> " How long will my tiny url last?

> Tiny urls are never deleted so there is no lasting or expiration

time.

> Also Tiny urls cannot be edited once created so if you made a

mistake

> just create a new one. "

>

> http://www.tiny.mn/faqs.php

>

> http://tinyurl.com/2vy92w

>

[Guest guest]

scmillers wrote:

I was told my a knowlegeable moderator that they do not last (but don't know the time limit), I went to http://tinyurl.com/ and could not find the answer.

Rerally? Try looking at the first sentence at http://tinyurl.com

"By entering in a URL in the text field below, we will create a tiny

URL that will not break in email postings and never

expires."

[Guest guest]

Well now, if it'd been a snake it would have biten me...LOL. After

reading it on the site, I went into some group archives that use the

tinyurls to see if they were still working or if they were not...found

some over a year old that are still working. I'll have to let the

other moderator know. Thanks for the info.

In Christ,

Ava

> > I was told my a knowlegeable moderator that they do not last (but

> > don't know the time limit), I went to http://tinyurl.com/ and could

> > not find the answer.

> >

>

> Rerally? Try looking at the first sentence at http://tinyurl.com

>

> " By entering in a URL in the text field below, we will create a tiny

URL

> that /*will not break in email postings*/ and /*never expires*/. "

>