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09/11/2003

Pinholes and Perchlorates

Last week I mentioned the fact that the word plumbing derives
from the Latin word for lead, plumbum. Pb, the chemical
symbol for lead, is also derived from the same word. Many older
homes still have plumbing containing lead and one is advised to
allow the water to run for a while before drinking so as to flush
out any lead that might have dissolved overnight. In newer and
in replumbed older homes, a popular plumbing choice is copper.

Now it seems that there is trouble in copper land, especially in
copper-piped homes in central Maryland. According to an article
by Louisa Wray Dalton in the August 18 issue of Chemical and
Engineering News (C&EN), residents of central Maryland are
suffering a rash of pinhole leaks in their copper plumbing. A
pinhole leak may not sound serious but the article cites the case
of one resident who, after spending some $13,000 on repairs, had
to replumb her whole house! Could this be a harbinger of a
nationwide epidemic of pinhole leaks? Marc Edwards, of
Virginia Polytechnic Institute and state University, thinks we
may be in the midst of a “catastrophic” pinhole problem in the
U.S. Edwards, a corrosion researcher, gets continuing calls
concerning pinhole leaks from residents in states ranging from
Alaska to Florida.

I paid a visit to the Web site of the Washington Suburban
Sanitary Commission, the water utility that supplies about a half
million customers in the Maryland area. This water company
takes pinhole leaks quite seriously. On the site you can read a
letter, dated December 18, 2002, from the commission to
Christie Whitman, then head of the Environmental Protection
Agency (EPA), expressing their concern about the problem. In
fact, the letter suggests that an EPA regulation meant to clean up
our water may inadvertently be one of the causes of pinhole
leaks. The letter points out that these leaks not only can result in
costly repairs but also can be a source of mold and of increases in
the cost of or even cancellation of home insurance policies.

There is nothing unusual about water pipes corroding. However,
the typical corrosion is of a uniform variety in which the
corrosion product or products form a film or coating that blocks
or drastically slows down further corrosion. In a recent column
we touched on an example of beneficial corrosion, the oxidation
of aluminum. Aluminum oxidizes (corrodes) to form a very thin
aluminum oxide film that is super protective and tough, blocking
further oxidation. Otherwise, aluminum, being quite reactive,
would just keep corroding away and aluminum objects ranging
from baseball bats to airplanes would be useless.

Pinhole corrosion is another matter. You might have just a
pinhole or two in a hundred feet of piping. And duplicating
pinhole corrosion in the lab is not easy. According to the C&EN
article, Edwards and his students spent 8 years trying. Finally,
last year, he and a student, Jason Rushing, found a set of three
conditions that did the trick with a vengeance. If chlorine,
commonly added to water to keep bacteria at bay, is present
between 0.5 and 2 milligrams per liter and if aluminum is also
present at between 10 and 500 parts per billion and if the pH is
between 8.2 and 10, experimental copper tubes corroded like
crazy. For those not familiar with pH, this range corresponds to
alkaline solutions.

The alkaline part is somewhat surprising. Typically, acidic
conditions are associated with corrosion and, in the past, water
utilities encountering corrosion problems tended to deliberately
make the water more alkaline. How does the EPA enter the
picture? Back in 1991, EPA formulated a so-called “Lead and
Copper Rule” designed to cut down leaching of copper and lead
into the drinking water. The rule was targeted at uniform
corrosion, not pinhole leaks and in some cases the rule mandates
raising the pH.

Water also contains “natural organic material” (NOM). The
EPA also ruled that the water utilities should make an effort to
get rid of NOM. Why? The organic material can react with
chlorine in the water to form carcinogenic compounds. The only
problem is that NOM tends to coat the pipes and block corrosion.
How do you get rid of NOM? One approach is to precipitate it
out using a coagulant. But a popular coagulant used in the water
industry contains aluminum! So, in attempting to better the
environment and make our water more fit to drink, we’ve added
chlorine and aluminum and raised the pH. Everything leads to
the conditions Edwards and student found to promote pinhole
corrosion!

How to correct the problem? Many water utilities are adding a
known corrosion inhibiter, orthophosphate. If you’re worried
about the addition of another chemical to your drinking water,
take heart. You’re already imbibing roughly a thousand or so
milligrams of orthophosphate a day from all manner of foods
ranging from soft drinks to cereals to cured meats to dairy
products. The water company in Maryland is talking the adding
of a milligram of orthophosphate per liter of water. If you drink
a couple liters a day, it’s only a couple milligrams of phosphate,
a tiny fraction of your current intake. Ironically, after adding the
phosphate to the drinking water, the company is required to take
it out of wastewater to the tune of about $300,000 a year!
Nothing is simple these days.

If pinhole leaks don’t concern you, perhaps you should be
concerned about the lettuce you’re eating and what’s in the water
in the lower Colorado River. Another article, by Cheryl Hogue
in the same issue of C&EN, is titled “Rocket-Fueled River” and
deals with perchlorates. Perchlorates are a class of compounds
that have many uses, notably in rocket fuels, matches, flares,
airbag inflators, etc. I used lithium perchlorate as an electrolyte
in my lithium battery studies at Bell Labs.

Here we’re concerned with perchlorate that originated from two
plants outside Las Vegas that were involved in manufacturing
perchlorate salts during the latter half of the 20th century. One
of the plants blew up in 1988, killing 2 and injuring 300 people.
Perchlorate can be dangerous! It is estimated that the operations
of these plants have resulted in plumes of shallow groundwater
contaminated with over 20 million pounds of perchlorate in some
18 billion gallons of water – big numbers indeed!

Today, hundreds of pounds of perchlorate flow every day into
the lower Colorado River. Among the cities that get a goodly
share of their water from the lower Colorado are Phoenix,
Tucson and San Diego. The water is also used to irrigate large
areas of California that grow the lettuce and other vegetables
shipped all across the country. Perchlorate has been found in the
lettuce grown in these areas. Chances are good that we’ve all
eaten some of that lettuce.

How much of a health problem does perchlorate pose? To date,
there are no federal standards. It is known that perchlorate can
interfere with the uptake of iodine, thus affecting thyroid
functioning. This can be a problem for fetuses and newborns.
Members of the Torrez Martinez Indian (Native American) tribe
on a reservation in the lower part of California are prone to
hypothyroidism, which means that the thyroid doesn’t produce
the normal amounts of hormones. These individuals are at
increased risk in the presence of perchlorates and, needless to
say, are not happy with the contamination of their water supply.

Efforts are being made to address the perchlorate pollution
problem but at the current rate of remediation, it will take over
two decades to clean it up. Meanwhile, the EPA has to come up
with safe levels for perchlorates in our water. From pinhole
leaks to perchlorates, the EPA is under the gun. Our state of
New Jersey’s former governor, Christie Whitman, should be
breathing a sigh of relief that she no longer has the responsibility
for either the EPA or, in these times of budget deficits, our state!

Allen F. Bortrum



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Dr. Bortrum

09/11/2003

Pinholes and Perchlorates

Last week I mentioned the fact that the word plumbing derives
from the Latin word for lead, plumbum. Pb, the chemical
symbol for lead, is also derived from the same word. Many older
homes still have plumbing containing lead and one is advised to
allow the water to run for a while before drinking so as to flush
out any lead that might have dissolved overnight. In newer and
in replumbed older homes, a popular plumbing choice is copper.

Now it seems that there is trouble in copper land, especially in
copper-piped homes in central Maryland. According to an article
by Louisa Wray Dalton in the August 18 issue of Chemical and
Engineering News (C&EN), residents of central Maryland are
suffering a rash of pinhole leaks in their copper plumbing. A
pinhole leak may not sound serious but the article cites the case
of one resident who, after spending some $13,000 on repairs, had
to replumb her whole house! Could this be a harbinger of a
nationwide epidemic of pinhole leaks? Marc Edwards, of
Virginia Polytechnic Institute and state University, thinks we
may be in the midst of a “catastrophic” pinhole problem in the
U.S. Edwards, a corrosion researcher, gets continuing calls
concerning pinhole leaks from residents in states ranging from
Alaska to Florida.

I paid a visit to the Web site of the Washington Suburban
Sanitary Commission, the water utility that supplies about a half
million customers in the Maryland area. This water company
takes pinhole leaks quite seriously. On the site you can read a
letter, dated December 18, 2002, from the commission to
Christie Whitman, then head of the Environmental Protection
Agency (EPA), expressing their concern about the problem. In
fact, the letter suggests that an EPA regulation meant to clean up
our water may inadvertently be one of the causes of pinhole
leaks. The letter points out that these leaks not only can result in
costly repairs but also can be a source of mold and of increases in
the cost of or even cancellation of home insurance policies.

There is nothing unusual about water pipes corroding. However,
the typical corrosion is of a uniform variety in which the
corrosion product or products form a film or coating that blocks
or drastically slows down further corrosion. In a recent column
we touched on an example of beneficial corrosion, the oxidation
of aluminum. Aluminum oxidizes (corrodes) to form a very thin
aluminum oxide film that is super protective and tough, blocking
further oxidation. Otherwise, aluminum, being quite reactive,
would just keep corroding away and aluminum objects ranging
from baseball bats to airplanes would be useless.

Pinhole corrosion is another matter. You might have just a
pinhole or two in a hundred feet of piping. And duplicating
pinhole corrosion in the lab is not easy. According to the C&EN
article, Edwards and his students spent 8 years trying. Finally,
last year, he and a student, Jason Rushing, found a set of three
conditions that did the trick with a vengeance. If chlorine,
commonly added to water to keep bacteria at bay, is present
between 0.5 and 2 milligrams per liter and if aluminum is also
present at between 10 and 500 parts per billion and if the pH is
between 8.2 and 10, experimental copper tubes corroded like
crazy. For those not familiar with pH, this range corresponds to
alkaline solutions.

The alkaline part is somewhat surprising. Typically, acidic
conditions are associated with corrosion and, in the past, water
utilities encountering corrosion problems tended to deliberately
make the water more alkaline. How does the EPA enter the
picture? Back in 1991, EPA formulated a so-called “Lead and
Copper Rule” designed to cut down leaching of copper and lead
into the drinking water. The rule was targeted at uniform
corrosion, not pinhole leaks and in some cases the rule mandates
raising the pH.

Water also contains “natural organic material” (NOM). The
EPA also ruled that the water utilities should make an effort to
get rid of NOM. Why? The organic material can react with
chlorine in the water to form carcinogenic compounds. The only
problem is that NOM tends to coat the pipes and block corrosion.
How do you get rid of NOM? One approach is to precipitate it
out using a coagulant. But a popular coagulant used in the water
industry contains aluminum! So, in attempting to better the
environment and make our water more fit to drink, we’ve added
chlorine and aluminum and raised the pH. Everything leads to
the conditions Edwards and student found to promote pinhole
corrosion!

How to correct the problem? Many water utilities are adding a
known corrosion inhibiter, orthophosphate. If you’re worried
about the addition of another chemical to your drinking water,
take heart. You’re already imbibing roughly a thousand or so
milligrams of orthophosphate a day from all manner of foods
ranging from soft drinks to cereals to cured meats to dairy
products. The water company in Maryland is talking the adding
of a milligram of orthophosphate per liter of water. If you drink
a couple liters a day, it’s only a couple milligrams of phosphate,
a tiny fraction of your current intake. Ironically, after adding the
phosphate to the drinking water, the company is required to take
it out of wastewater to the tune of about $300,000 a year!
Nothing is simple these days.

If pinhole leaks don’t concern you, perhaps you should be
concerned about the lettuce you’re eating and what’s in the water
in the lower Colorado River. Another article, by Cheryl Hogue
in the same issue of C&EN, is titled “Rocket-Fueled River” and
deals with perchlorates. Perchlorates are a class of compounds
that have many uses, notably in rocket fuels, matches, flares,
airbag inflators, etc. I used lithium perchlorate as an electrolyte
in my lithium battery studies at Bell Labs.

Here we’re concerned with perchlorate that originated from two
plants outside Las Vegas that were involved in manufacturing
perchlorate salts during the latter half of the 20th century. One
of the plants blew up in 1988, killing 2 and injuring 300 people.
Perchlorate can be dangerous! It is estimated that the operations
of these plants have resulted in plumes of shallow groundwater
contaminated with over 20 million pounds of perchlorate in some
18 billion gallons of water – big numbers indeed!

Today, hundreds of pounds of perchlorate flow every day into
the lower Colorado River. Among the cities that get a goodly
share of their water from the lower Colorado are Phoenix,
Tucson and San Diego. The water is also used to irrigate large
areas of California that grow the lettuce and other vegetables
shipped all across the country. Perchlorate has been found in the
lettuce grown in these areas. Chances are good that we’ve all
eaten some of that lettuce.

How much of a health problem does perchlorate pose? To date,
there are no federal standards. It is known that perchlorate can
interfere with the uptake of iodine, thus affecting thyroid
functioning. This can be a problem for fetuses and newborns.
Members of the Torrez Martinez Indian (Native American) tribe
on a reservation in the lower part of California are prone to
hypothyroidism, which means that the thyroid doesn’t produce
the normal amounts of hormones. These individuals are at
increased risk in the presence of perchlorates and, needless to
say, are not happy with the contamination of their water supply.

Efforts are being made to address the perchlorate pollution
problem but at the current rate of remediation, it will take over
two decades to clean it up. Meanwhile, the EPA has to come up
with safe levels for perchlorates in our water. From pinhole
leaks to perchlorates, the EPA is under the gun. Our state of
New Jersey’s former governor, Christie Whitman, should be
breathing a sigh of relief that she no longer has the responsibility
for either the EPA or, in these times of budget deficits, our state!

Allen F. Bortrum