HOW LEAD CAME TO BE IN FLINT WATER
James Robert Deal, J.D. and
Dr. Richard Sauerheber, Ph.D.
To follow links go to: www.Fluoride-Class-Action.com/Flint
Updated February 10, 2016
Summary: Flint has a lot of lead plumbing – in homes, apartment buildings, commercial buildings, and schools. Chlorine, chloramine, and fluoride all leach lead from plumbing. Terminating the use of chlorine, chloramine, and fluoride would significantly reduce the amount of lead at the tap. Instead of purifying water with chlorine or chloramine, Flint should switch to ozonation at the water plant. To the extent possible, the use of chlorine should be reduced or ideally completely eliminated.
While Flint had the worst lead leaching problem, other cities and towns have the same problem. There were high lead levels in water most recently Cleveland. No water district should be adding acids which leach lead. Any benefit which might come from fluoridation is far outweighed by lead leaching. If it were possible we would eliminate all sources of lead. There is no amount of lead consumption which does no harm to health, especially of the fetus.
To read the full version of this essay visit www.Fluoride-Class-Action.com/Flint.
We commonly read that Flint River water is corrosive and therefore leaches lead, but there is usually no explanation given as to how it came to be corrosive, or how this corrosiveness leaches lead, or how this could have been avoided, or how this could be corrected.
Recall that Flint was using Lake Huron water from Detroit before it decided to cut costs and switch to Flint River water. Flint has now gone back to using Detroit water.
A more accurate statement explanation of what is wrong with Flint River water is that it contains an excessive load of organic matter, perhaps vegetable matter, perhaps animal waste, perhaps even human waste. Lake Huron water, contains much less organic matter, but lead levels are still much too high in Flint. No person should be drinking unfiltered Flint tap water. The lead problem has been reduced but not eliminated.
The heavy load of organic matter in the Flint River was not sufficiently filtered out. The water plant because bacteria were breeding in the organic matter. This produced trihalomethanes at higher than acceptable levels. The chloramine broke down into hypochlorous acid, which made the water acidic, and hypochlorous acid leaches lead from plumbing.
Flint water quality reports indicate that after Flint switched to Flint River water, high levels of disinfection byproducts, trihalomethanes produced when chlorine reacts with organic matter, were found in Flint municipal water, far in excess of their EPA MCL (the maximum contaminant level, also referred to as the action level).
Adding chloramine to the water supply will increase total exposure to lead in drinking water, especially in areas with older housing. Tis exposure can result in increased lead levels in the bloodstream, which may pose a significant health risk.
Fluorosilicic acid was added to Flint water while Fling was using Flint River water. And it is currently being added to water now coming from Lake Huron by way of Detroit. Fluorosilicic acid breaks down into silicic acid, which leaches lead.
A reliable source has told me: Flint water has been fluoridated all along. The Flint water treatment plant was built in the 1950s and has been used for emergency water treatment sourced from the Flint River if the Detroit water ever failed. There were regular tests of the Flint treatment plant every year, to make sure it could take over on a moment’s notice. The Flint water treatment plant had fluoridation equipment, so none needed to be added. When the water source was switched to the Flint River, the first month after the switch no fluoride was added, but for all succeeding months the water was fluoridated. There are detailed daily and monthly records of the fluoridation concentration both before and after fluoridation, as well as the amounts of fluoridating chemicals used. These records prove that the water was fluoridated at all times.
Water systems serving over 70% of the United States population add fluoride, so it is appropriate to discuss the lead leaching aspects of silicic acid.
Three main forms of fluoride are used. Fluorosilicic acid is used by large water systems because it comes as a liquid in tanker trucks and is thus cheaper and easier to transfer. It can be pumped through sealed hoses into sealed tanks. Sodium silicofluoride and sodium fluoride come in bags as a salt. They are used by small water systems to avoid the cost of a pumped system. All three fluorides leach lead. Fluorosilicic acid and sodium silicofluoride are more active at leaching than sodium fluoride because both break down into silicic acid. And both fluorosilicic acid and sodium silicofluoride contain lead, while sodium fluoride usually does not.
When it comes to plumbing, where is the lead? Older cities have cast iron water mains. Plumbers joined the giant pipes together by building wooden molds around each joint and then pouring in molten lead. So cast iron pipes contain lead in contact with water at every joint.
Next, there are lead service lines which run from the main line in the street to the home, apartment, business, or school. Older service lines are almost certainly made with lead. Next, there are brass pipes inside homes and other buildings. The law until recently allowed the use of copper with up to 8% lead in household plumbing.
Flint has been digging up, removing, and replacing existing plumbing. But digging up pipes is an unnecessary expense. The same is true of opening walls to remove old pipes. The cheaper way is to leave old service lines in place and bypass them with new plumbing. Inside the house new PVC lines can be inserted without much trouble, ignoring and bypassing existing plumbing. It is an unnecessary expense to remove old plumbing.
SOMETHING WE CAN DO NOW
Until all the lead in water mains, service lines, and indoor plumbing is removed – which will take decades and may never happen – is there something that can be done in the short term to reduce lead in drinking water? As I said above, we should stop adding chlorine, chloramine, and fluoride to water because they leach lead. Chloramine may be more efficient at leaching lead than chlorine. We should sanitize water with ozonation at water plants and not with chlorine or chloramine. We should develop strategies for completely eliminating the use of chlorine, which is possible, as I will discuss below.
In addition to leaching lead, fluorosilicic acid actually contains lead. It can add as much as .8 ppb lead to finished water. See links to tests done by NSF showing lead in fluoridated drinking water:
Acids lower pH. More acidity means more lead leaching. See the following:
Maas, R., et.al., Effects of fluoridation and disinfection agent combinations on lead leaching from leaded brass parts, Neurotoxicology 28, 2007, 1023-1031.
In water districts which chlorinate and fluoridate, acids must be neutralized. An alkaline is added, such as sodium hydroxide (Drano) or sodium carbonate (soda ash).
The amount of alkalinizer the water districts will add to neutralize the chlorine or chloramine is not not sufficient to neutralize silicic acid, not by a long shot. The pH would have to be raised past 10 to neutralize the silicic acid. Silicic acid has an extremely low dissociation constant, much lower than for chlorine and chloramine and the hypochlorous acid they turn into. See:
Older homes, older businesses, older apartment buildings, and older public buildings contain lead service lines and brass plumbing containing high lead levels. The service line is the connection from the property out to the water main. Plumbers (so named because “plumbus” means lead) used lead to make water pipes because it was soft and easy to work with. In recent times, these lead service lines have become an acute hazard.
Most of the lead added to drinking water is added in the service line and interior plumbing. Thus, many water districts take the position that their responsibility ends at the sidewalk, where the water main ends and the service lines start.
There are three flaws in this argument. First, some lead leaching is happening in the lead soldered water mains, which are the duty of the water district to repair. Second, if the water district is fluoridating, the the fluoride comes with a significant amount of lead. Third, fluoridated and chlorinated or chloraminated water leaches lead from lead soldered water mains, service lines, and brass-lead pipes and faucets.
Newer water faucets generally contain around 8% lead, which was the federal standard for brass which is to be labeled as ”lead free” and approved for use in water lines. For brass sold in California the maximum lead content is a fraction of that. Copper plumbing is soldered together with lead-copper solder. Copper pipe has until recently been 1% lead. Federal regulators have recently adopted the California rule nation wide.
All lead plumbing should be replaced, but that will take years. PVC or CPVC pipe that has passed testing and is marked “NSF-61” or “NSF-PW” could be used instead of brass or copper.
There are technologies which can line the inside of pipes while leaving them in place.
ACTION PLAN FOR LEAD REDUCTION
The first step to take in reducing lead leaching in our water mains and in our plumbing as it now exists is to quit adding chemicals which leach lead. We should minimize or eliminate as much as possible the addition of chlorine, chloramine, and fluorosilicic acid to our drinking water.
Eliminating the fluoride is easy. The challenge is to quit using chlorine or chloramine.
If we reduce or eliminate the use of chlorine or chloramine, how would we sanitize the water? Most water plants use heavy chlorination or chloramination or a combination of the two to kill bacteria at the water plant. Instead we should use ozonation at the water plant. To convert to ozonation would involve bringing in new equipment, but thereafter the operational cost will be low. The utility will not have to buy chlorine. It can simply draw in oxygen from the atmosphere and use electricity to make ozone. Ozone not only kills bacteria; it also removes organic matter and other contaminants. It is a flocculant, causing materials to clump, so they can be filtered out physically. Also chlorine and chloramine produce trihalomethanes, while ozonation does not.
Representatives who sell ozonation equipment say that is common for small amounts of chlorine to be used at the water plant, but only one-tenth as much as before. Chlorine is typically injected every few miles throughout the system to replace chlorine which escapes or is absorbed.
Is it feasible to ozonate water out in neighborhoods? That possibility should be explored. Water should be of highest quality.
We should consider UV light for final purification as water inters each home or building. This would be an expensive option as UV purifiers cost around $400 on Amazon. However, they have no moving parts and should last for a very long time. Offsetting the cost is the complete elimination of added acids to the water. That will mean that the pH can be adjusted much more accurately so as to avoid scaling.
Chloramine is worse than chlorine. In the home chlorine will evaporate from water if the container is left open overnight. It will not escape from water in a sealed container. However, chloramine, a combination of chlorine and ammonia, does not evaporate away, so less needs to be added. Some water systems use it because it is less costly and is more persistent. Although they both contribute to lead leaching.
Once chloraminated water arrives in the home, it is consumed, which is bad for health. Chloramine should never be used to disinfect water. “Human beings and higher animals are less sensitive to ammonia in water, but long-term ingestion of water containing more than 1 mg/l (ppm) ammonia may be damaging to internal organ systems.”
Ammonia is not removed by sewage treatment and so is dumped into rivers. “Ammonia even at dilute concentrations is highly toxic to aquatic animals, and for this reason it is classified as dangerous for the environment.”
I should add that fluoride does not evaporate the way chlorine does. Boiling water removes chlorine but not chloramine or fluoride. Countertop filters do not remove fluoride. Reverse osmosis filters can remove chlorine, chloramine, and fluoride. There are reverse osmosis filters both for under the sink and on the counter.
However, RO filters must be replaced from time to time and may stop working.
For now I will continue using a water distiller. Only a carbon filter – for removing trihalomethanes and other volatile compounds – needs to be replaced each year. You add a small bag of carbon granules in the spout from which the water drips into the receptacle. Distilled water contains no minerals and so draws in carbon dioxide, which makes its pH drop to acidic levels. For that reason some oppose their use. However, minerals can be added back simply by adding tea bags, lemon juice, mint leaves, kale, or even chives. Amazon sells a one gallon distiller for around $220.
When Flint was using Detroit water, there was less organic matter in the water, and so less chlorine or chloramine had to be added to neutralize it. The chlorine or chloramine and silicic acid were leaching lead, but at lower levels. When Flint turned to using Flint River water, there was more organic matter in the water breeding bacteria, and so more chloramine was being added along with the same amount of fluorosilicic acid and therefore silicic acid. More chloramine plus the same amount of fluorosilicic acid and silicic acid, meant more lead leaching. And it meant more trihalomethanes. A simple charcoal filter will remove trihalomethanes.
Now that Flint has returned to using Detroit water, it is adding both fluorosilicic acid chlorine. Detroit uses chlorine instead of chloramine. It is not clear whether Flint is “topping it off” with chorine or chloramine, although less of either will be needed when there is less organic matter in the water. There will continue to be lead leaching, although at lower levels. Flint’s problem has not been resolved. No amount of lead is acceptable.
Fluoridation began in 1945, with Alcoa pushing sodium fluoride from its aluminum smelters. However, once fluoridation got going, the supply of sodium fluoride was soon insufficient. Fluorosilicic acid was cheaper and more abundant, although it was and is more contaminated with heavy metals. The phosphate fertilizer industry had lakes full of waste fluorosilicic acid in Florida (which broke through into the Florida Aquifer, permanently polluting it). They wanted to sell it and make some money.
Producers of super-phosphate fertilizer had been poisoning people, animals, and crops with the fluorosilicic acid coming from their smokestacks. So in the 1970s and 1980s the EPA required that they install wet scrubbers. The scrubbers captured the fluorosilicic acid, but the next question was what to do with it. For a while producers stored it in giant “lagoons” surrounded by toxic silica gypsum piles. These lagoons break through into the aquifer below, as recently happened in Florida.
So in 1983 the EPA approved the use of fluosilicic acid for sale to water districts as a cheap source of fluoride ion and as a way to get rid of the mostly useless waste. See:
Fluorosilicic acid contains significant amounts of lead and arsenic plus measurable amounts of mercury, cadmium, and other poisonous contaminants. It is filth. Consuming a small amount of these contaminants daily from conception until death is not acceptable.
Some 43% of tanker loads of fluorosilicic acid are acknowledged by NSF to contain arsenic. Arsenic is a Type 1 confirmed human carcinogen. No amount of arsenic should be consumed by humans.
Fluorosilicic acid breaks down into silicic acid, sodium, fluoride ion, a small amount of hydrogen fluoride (HF or hydrofluoric acid) at neutral pH. (In the acidic stomach, fluoride ion converts to HF, where the HF level is much higher.) Every 30 tons of fluorosilicic acid breaks down when diluted and adds 10 tons of silicic acid to drinking water, 10 tons of sodium, and 10 tons of fluoride ion and a small amount of hydrofluoric acid. Humans should not be consuming any amount of these contaminants
As mentioned above, silicic acid is difficult to neutralize. It has an extremely low dissociation constant. Alkalinity would have to be increased to pH 10 to neutralize it. If enough sodium hydroxide (Drano) or sodium carbonate (soda ash) were added to neutralize it, the water would be like milk of magnesia. So while chloramine or chlorine can be neutralized, it is not feasible to neutralize silicic acid because of its low dissociation constant. Again see:
Lead has an electrical reduction potential such that it reduces oxygen gas (incorporated in all water from the atmosphere) and forms lead oxide, which coats lead pipes after a brief period of use. Lead oxide salts react with amines to form complexes in water and also can react with silicic acid, since silicic acid remains an intact molecule even at alkaline pH and remains available to react with the lead.
The lead releasing chemical reaction is as follows: PbO + H2SiO4 → Pb2+ + SO42- + H2O. Other lead salts can also be ionized, releasing lead.
Lead levels were highest when Flint switched from using Detroit water and started using Flint River water. Lead levels are still higher now, as Flint uses Detroit water, than when it previously used Detroit water. This is due to several factors:
First, lead-rich pipes were damaged during the Flint River water episode. Any calcium coating inside the lead pipes was removed partially or entirely by the high chloramine and fluoride levels. Lead bearing metal was loosened and so lead continues to leach from damaged pipes.
Second, silicic acid continues to be added to Flint water, and it is very persistent at leaching lead. Again, this is because the alkaline added to neutralize the chloramine is not sufficient to neutralize the silicic acid.
Third, when Detroit water was being used, before Flint switched to Flint River water, it is likely that improper testing was being done for total lead in the water. The test for lead in “first draw” water should be taken before running the water. There is now clear evidence that it is routine for utility departments to “run the water” for a while, thus eliminating the lead which leached and accumulated overnight. Thus “first draw” water was not really “first draw” water. Probably, more accurate first draw tests are being done now than before the Flint River water episode.
Home owners can run the water to flush out the dissolved minerals, but those living in large apartments and working in large buildings cannot run the water long enough to do that. The water lines are too extensive.
The media has reported that if Flint had only spent $100 per day on a certain chemical additive, the entire lead problem could have been avoided. The media is referring to sodium phosphate, which is referred to erroneously as a “corrosion inhibitor”. When sodium phosphate is added, lead becomes bound up as lead phosphate particulates, with the result that a cheap lead meter can no longer detect the presence of lead. Sodium phosphate does not inhibit lead leaching. It only hides it. Lead remains bound to phosphate until it reaches the highly acidic conditions of the human stomach, where lead ion is released.
The least expensive way to test for lead in the field is with a cheap, portable electronic meter which specifically measure lead ion. But such meters do not detect lead precipitates or complexes that are also in the water, such as lead phosphate or lead amines – unless the sample is first treated with a strong acid to dissociate the lead ion.
The University of Virginia did testing of Flint water using atomic absorption spectroscopy or mass spectrometry, which more easily detected lead levels in any form or compound and thus measured for any violation of the MCL or maximum contaminant level for lead.
Reported measurements of lead levels cannot be trusted unless test results are accompanied by test details, such as whether there has been pre-flushing and whether phosphates have been added. The study done by the University of Virginia may merely have detected a problem that had been occurring, albeit to a lesser degree, before the switch to the Flint River, but which was undetected for the reasons spelled out above.
From time to time, school districts discover lead in school drinking water. Lead pipes and old water fountains in schools are replaced, and everyone acts as if everything is okay. However, changing plumbing in schools does nothing for all the other homes, apartments, churches, and other buildings where there are lead service lines, lead plumbing, and lead faucets.
Until lead water mains, lead service lines, and inside lead plumbing can be replaced, the following steps should be taken to reduce lead in drinking water:
First, chloramine should not be used for disinfecting drinking water. It persists and therefore leaches more lead than chlorine. It does not evaporate out of water, and thus we consume it.
Second, the use of chlorine or chloramine should be eliminated or limited by adding ozonation equipment at central water plants and if financially feasible adding smaller ozonation plants throughout the water system or UV disinfection at each home or other building. The reduction or elimination of chlorine or chloramine from water systems will reduce the amount of acid forming chlorine or chloramine to be added and thus reduce lead leaching.
Third, fluoridation should be ended, because silicic acid formed from fluorosilicic acid contains lead and leaches lead.
We humans have a way of ignoring our own health but taking action when the health of our animals is jeopardized. Horses drink a lot of water and their health is seriously compromised when they drink fluoridated water. Congress held hearings on the high incidence of racehorse breakdowns that require euthanization in the U.S. In a recently completed study of racehorse breakdowns in fluoridated Los Angeles, evidence that fluoride as HF in the acidic stomach may have aggravated ulcers, so commonly present in these animals, during racing. See:
Several communities have terminated fluoridation simply because they did not want to ruin their racetrack businesses.
It must be emphasized that the ingestion of fluoride does not actually reduce dental caries. The CDC reported that fluoride in our blood stream does not act on dental caries at all.
Fluoride is not a mineral nutrient or a component of normal blood. Thus, it is recommended that drinking water fluoridation be banned. The FDA ruled in 1963 that fluoride added to water is an uncontrolled use of an unapproved drug. In 1966 the FDA banned the sale of all fluoride compounds intended to be ingested by pregnant women in the U.S.
Fourth, the flushing of water systems using high doses of chlorine or chloramine should be discontinued. High doses “loosen up” the lead and reduce any mineral lining, so that lead leaches more readily.
Fifth, we should consider the feasibility of relining the inside of pipes instead of replacing them.
Sixth, it may be possible to coat the inside of existing plumbing with calcium carbonate. Calcium carbonate, commonly referred to as lime, is alkaline, and in theory it could be used instead of sodium hydroxide (Drano) or sodium carbonate (soda ash) to lower the acidity of water. The challenge would be to find a proper level of calcium carbonate, perhaps in combination with some other chemicals, with the result that the calcium carbonate would line lead pipes and seal the lead in place. It would stay in place as long as the pH were maintained at alkaline levels and so long as lead leaching chemicals such as silicic acid and chlorine or chloramine were not added.
This sixth step, coating the inside of all existing plumbing, is theoretical. The depositing of scale can be a serious problem, and when water is hard water softeners must be used. I would speculate that appropriate levels of calcium carbonate could be added to water and then removed with water softeners just before water enters the hot water heater and the rest of the home. This would presume that pipes within the home are not brass containing lead or copper soldered with lead solder and that brass faucet fittings containing lead are replaced with zero lead brass. Also bear in mind that galvanized pipe in the home absorbs lead if the home is served by a lead service line.
As you can see the issue is complex. The challenge would be to add just the right amount of calcium carbonate sufficient to line lead containing plumbing without creating a scaling problem.
The side issue is whether water which is chlorinated but not fluoridated could be neutralized to the point where there was little or no lead leaching.
Roman aqueducts, water mains, and smaller water lines were all made of lead, but they were completely coated inside with calcium carbonate. Roman water passed through limestone and thus contained natural calcium carbonate. The water was what we call “hard”. It contained a lot of minerals. If the Romans could line their lead pipes with calcium carbonate accidentally, it might be possible for us to accomplish the same thing intentionally. Our advantage would be that we would be able to set a level of calcium carbonate in the water that would deposit the right amount of calcium carbonate without causing excessive scaling.
The Romans suffered from lead poisoning. They made their plumbing of lead, and so some say that it was the lead plumbing which caused the problem. This is not true. Their plumbing was lined with calcium carbonate. The problem was that the Romans cooked with lead pots and pans. They cooked sweet, acidic grapes in lead pots to produce their primary sweetener, and this high-lead sweeter is what poisoned them.
Seventh, the pH of drinking water should be kept as alkaline as possible. In Southern CA, one of the most prized sources of pristine water is Carlsbad Alkaline Water. It comes from an underground aquifer that drains from the Cleveland National Forest. It is free of fluoride, arsenic, lead, uranium, and other contaminants, and has a natural alkaline pH of about 8.3 from the dissolved nutrient minerals calcium and magnesium.
Eighth, until chlorination, chlorimination, and fluoridation end, make distilled or reverse osmosis drinking water available at public fountains everywhere. Pregnant women most of all need a source of water which is free of chlorine, chloramine, and lead.
In conclusion, I would emphasize the following:
Adding fluoride to drinking water can only increase lead leaching. Silicic acid is a patient and potent lead solvent.
Fluoridated drinking water will always have more lead in it than non-fluoridated water.
Non-fluoridated water will always have less lead in it that fluoridated water.
Do not fluoridate drinking water.
To follow links go to: www.Fluoride-Class-Action.com/Flint
For more information read:
James Robert Deal, J.D.
University of Washington Law School
Rihchard Sauerheber, PH.D.
B.A. Biology, Ph.D. Chemistry, University of California, San Diego
Palomar College, STAR Center, San Marcos, CA 92078