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Bromine, Chlorine, And Carcinogens


ncspa

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So, we all know that carcinogens are all around us, and it's certainly easy to get carried away with concern about potential cancer-causing foods, airborn particles, etc. However, we'd all agree that if we can avoid them it makes sense to do so. Far better to focus on the things that we can really control, and not to get neurotic about those we can't. So, what about the issues with sanitizing chemicals, particularly chlorine vs. bromine - where do these fit in?

As a research scientist, I'm interested in actual data (rather than suppositions) and what they might tell us about relative risks. Problem is, there doesn't seem to be much out there. However, we do have good, resourceful folks on this forum, so I'm asking you all to share your own knowledge, and contribute whatever you can. Here's my contribution:

1. Bromine may well be converted to bromate with the use of an ozonator. Bromate is listed as a carcinogen when ingested, but also apparently has mutagenic properties when absorbed through the skin.

2. Inhalation of chloramines is considered carcinogenic.

I use bromine with an ozonator and I'm having a hard time weighing the risks. In reality, how much bromate is actually produced? Is it stable enough to pose a problem?

If I knew for sure that it was an issue, I'd simply disconnect the ozonator. However, ozonators allow you to use less bromine, which may be a benefit in itself. Both are concerns, because we use the tub everyday, and my children (7 and 4) use it frequently. Switching to chlorine is also an option, but doesn't necessarily seem safer. Besides, right now bromine is working well for us, and this doesn't seem like a sufficient argument for making the switch - unless there is a real, quantifiable decrease in risk.

So, tell me what you know. Does anyone have good data related to bromate production and risk in pools and hot tubs? What about chlorine? If not, maybe we could find a good public health chemist to weigh in. Many thanks for your contributions.

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This link gives a nice discussion on trihalomethanes (THMs) including chloroform with some additional references. This link is one study on one particular haloacetic acid (HAA5). This link gives quite a lot of info on haloacetic acids. There was this link with interesting tidbits about bromate and the EPA.

More seriously, the EPA has a large database of information and references on a variety of disinfection by-products and related substances as follows:

Bromate data from the EPA is in this link.

This link is about dichloroacetic acid (the link on "TOXILOGICAL REVIEW" gives much detailed information).

You can read more about bromodichloromethane here

bromoform here

chloroform here

dibromochloromethane here

bromochloromethane here

bromomethane here

dichloromethane here

trichloroacetic acid here

Though not a THM or HAA5, you can read about monochloramine here and chlorine here.

Understand that the haloacetic acids can only be formed when one starts with acetic acids, including those found in protein. Trihalomethanes generally form from the haloform reaction which starts with a methyl ketone (which could come from oxidation of an alcohol). These reactions tend to occur faster at higher pH. Formation of higher level chloramines (which comes from ammonia/urea plus chlorine), such as dichloramine and nitrogen trichloride, tend to occur faster at lower pH.

Most of the focus has been on drinking water so unless there is information on absorption of these chemicals through the skin or on their volatility and absorption through breathing, then it is hard to determine exposure limits. I don't think you will find what you are looking for regarding ozonators and bromates -- I couldn't find a rate constant for its production even if I had the concentration of ozone (which I don't).

Regarding inhalation of chloramines, I've actually never seen anything tying these to being carcinogenic. Irritating to lungs and eyes and inducing asthma, yes (especially for nitrogen trichloride, but high levels of monochloramine appear to also be irritating), but not carcinogenic. Obviously, these are still substances to be avoided and as you know my pet peeve is how most indoor pools with no CYA I believe are producing over 10 times as much nitrogen trichloride as they would if they used a small amount (10-20 ppm) of CYA.

The worst carcinogens by far [EDIT] (I need to correct this to say the worst chemicals with health effects as their carcinogenic problems may be less than non-cancer problems) [END-EDIT] are the polychlorinated dibenzodioxins (PCDD) and the polychlorinated dibenzofurans (PCDF) and these are chemicals that bio-accumulate (more info here. Polybrominated versions of these are discussed in this link from WHO. The source of these comes from humus-like organic matter (leaves and soil with decomposed material) combining with chlorine. Fortunately, these do not form quickly unless the chlorine concentrations are higher. They have been most commonly been associated with the bleaching of paper by chlorinating wood pulp (where chlorine concentrations are exceptionally high) and to a far lesser extent in drinking water chlorination where waters with high organic content are now generally pre-treated to remove most of it before exposure to chlorine. When using CYA, the level of chlorine in pools and spas is far lower than that used in treating drinking water (upstream) and far, far lower than used in the wood pulp bleaching process.

Realistically, I think the risk of bromates from an ozonator are low. From what I've seen of the ozonators reported on this forum, many either are not functioning or are weak (low in output). They are probably fine as a supplemental system, but they can't do the primary job of oxidizing all the ammonia/urea from sweat and so still need an oxidizer for that purpose. In a bromine system, this means you'll probably still need to use an oxidizer shock to reactivate some of the bromine and to oxidize ammonia/urea and other organics.

Richard

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Richard - thanks, this is great. I'll have to take some time and sort through these references before I respond.

I have a good friend who works at the EPA and is also a pool owner....I've put some feelers in there and I'll see if they have any additional resources.

Others with experience or opinions?

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Richard - thanks, this is great. I'll have to take some time and sort through these references before I respond.

I have a good friend who works at the EPA and is also a pool owner....I've put some feelers in there and I'll see if they have any additional resources.

Others with experience or opinions?

I have worked in the industry of making ozone generating and contacting equipment for pools, municipal water treatment, and waste treatment for a number of years. The declaration of bromate as a possible human carcinogen by the EPA has doomed many large ozone companies. Wedco recently succumbed to big setbacks in the US. This leaves the Japanese and France, and a few dozen American manufacturers of pool-size equipment. (Some Chinese clones too, of course.)

Potassium bromate caused a certain rodent species to develop renal cell tumors. Potassium carbonate did the same thing in the same critter. But US-EPA cannot call carbonate a possible human carcinogen. US-NIH tested sodium bromate in mice up to 800 mg/L for a year, and no carcinogenesis was noted. EPA makes their dispensations based on assuming that one-in-a-million individuals has the kidneys of one particular rat. Two different doctors (and myself) tried arguing sense with them, but no effect obtained other than shuffle and double-speak. Apparently no way to reverse a fiat once it is made.

Bromate has a loss of 10% in concentration over a week when stored in labware in a refrigerator, according to support documents of one particular study. Raise the temperature, and add some organics or ammonia to oxidize, and there will be no bromate within seconds / minutes.

When adding ozone to pool water, it is best to use ORP, and catch the bromide as hypobromous acid... rather that super-ozonating it to bromate. Easier on the glazing if there is no ozone actually in the water. Although I have heard apocryphal stories of people in Tucson AZ USA that ran ozone as their primary disinfectant in their home outdoor pool.

When using ozone, chlorine becomes a waste of money. Bromine has a much lower vapor pressure, so it tends to last much longer.

I hope that answers the rest of your questions?

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When using ozone, chlorine becomes a waste of money. Bromine has a much lower vapor pressure, so it tends to last much longer.

Great info. When I read the EPA info on potassium bromate, I thought the same thing "maybe it's the potassium".

With your statement above, are you saying that the aeration from the ozonator will tend to outgas the hypochlorous acid? Henry's Law Constant (M/atm) for chlorine is around 660 at 25C and 250 at 104F while for hypobromous acid the literature varies a lot from 93 to 6100 at 25C. For molecular chlorine, Henry's Law Constant is around 0.095 while for molecular bromine it is around 0.76, but these are in very low concentration in water and for chlorine is rate limited in its formation (unless chloride levels are very high).

So are you saying that the aeration of the ozonator will tend to drive out chlorine (specifically, hypochlorous acid) from the water and does so more rapidly than bromine (specifically, hypobromous acid)? If so, then such strong aeration should also drive out carbon dioxide and tend to make the pH rise faster.

Richard

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chemgeek perhaps this article http://www.encyclopedia.com/doc/1G1-107277341.html will help you understand the different chemicals used to sanitize pool and spa water as well as ozone. I thought it might help you to read an article that is from a trusted pool and spa publication. Pool and spa professionals have relied on Pool & Spa news for almost 50 years. You will see that the clearly state the sodium hypochlorite causes a ph rise in your water. It also states that sodium hypochlorite becomes an inert substance rapidly in high temperatures. This is why people are having to add large doses of mps to their water and dose atleast twice a day with bleach when they apply your advice. It has information about stabilized chlorine that you are so concerned with, stating that you have to drain and refill pools more often when it's used. Of course with spas you are draining and refilling them every 3 to 4 months anyways. There is information in the ozone section about the chance of chlorine and ozone destroying each other if they are allowed to come into contact with one another. I expect you will continue with your agenda of urging people to use bleach in their spas despite unbiased information from industry experts.

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chemgeek perhaps this article http://www.encyclopedia.com/doc/1G1-107277341.html will help you understand the different chemicals used to sanitize pool and spa water as well as ozone. I thought it might help you to read an article that is from a trusted pool and spa publication. Pool and spa professionals have relied on Pool & Spa news for almost 50 years. You will see that the clearly state the sodium hypochlorite causes a ph rise in your water. It also states that sodium hypochlorite becomes an inert substance rapidly in high temperatures. This is why people are having to add large doses of mps to their water and dose atleast twice a day with bleach when they apply your advice. It has information about stabilized chlorine that you are so concerned with, stating that you have to drain and refill pools more often when it's used. Of course with spas you are draining and refilling them every 3 to 4 months anyways. There is information in the ozone section about the chance of chlorine and ozone destroying each other if they are allowed to come into contact with one another. I expect you will continue with your agenda of urging people to use bleach in their spas despite unbiased information from industry experts.

I interperate something totally different regarding sodium hypochlorite and it being an inert substance. The following is from the referenced article:

Most pool owners choose one of four compounds:

1. Sodium hypochlorite: chlorine gas mated with sodium hydroxide. You could substitute Clorox brand bleach from the grocery store in a pinch, says Osinski, but the bleach concentration would be between 5 and 6 percent available chlorine vs. the 12 to 15 percent from sodium hypochlorite sold for sanitizing and oxidizing pool water. It's safe to handle and nonflammable, which makes it a less hazardous product to store.

2. Calcium hypochlorite: chlorine gas passed over sodium hydroxide, or lye. Its available chlorine ranges between 65 and 75 percent, with a lower pH than sodium hypochlorite. Several methods can be used to introduce it into pool water: It can be added using an erosion feeder or erosion soaker, or it can be made into a liquid and pumped in with a peristaltic piston or diaphragm pump. Another method is for the pool owner or technician to broadcast the chemical over the water surface.

3. Lithium hypochlorite: chlorine gas bubbled through lithium, sodium and potassium sulfates, then dried. Because it's alkaline, like all hypochlorites, users need to adjust the pH downward. It is totally soluble, nonflammable and noncombustible, with a long shelf life. It's also one of the more expensive forms of chlorine.

4. Isocyanurates: chlorine products sold pre-mixed with the stabilizer cyanuric acid: Trichloro-s-triazinetrione (trichlor) and sodium dichloro-s-triazinetrione (dichlor). Dichlor began as trichlor, with sodium bicarbonate and cyanuric acid added. It's sold in 56- and 62 percent available chlorine dosages, with a neutral pH of 6.9. Trichlor is 90 percent chlorine, produced by cyanuric acid and the presence of gas chlorine, with a pH of 2.9. Both are stabilized and instantly soluble, so they create no residue or cloudiness.

Facts to Remember:

* Chlorine should not be sprinkled directly on the water surface, as is often done by homeowners, because it is too concentrated. The high concentration can harm bathers and equipment, Osinski warns. The best case would be to introduce it by using a feeder attached to the return line after the filter. Or pre-mix the chemical with water and put it in as far back in the system as possible.

* Sodium hypochlorite becomes an inert substance rapidly in heat and sunlight so it should be stored in a clean, well-ventilated, dark, dry place. It should never be placed near paint, fuel, solvents or paper, or other types of chemicals. Owners should not buy more than they can use in a two-week period.

* Due to sodium hypochlorite's high pH, pool owners may need a lot of pH adjustment chemicals to bring it into range.

It is well known that sodium hypochlorite looses strength over time and should not be stored in sunlight (chlorine's enemy), but there is nothing here that states this is an issue after application. These are just storage issues. Chlorine actually becomes more effective at higher temps up to about 120 degrees where it will start to fall off. The higher concentration liquid chlorine will lose some of its power faster than the lower concentration bleach on the shelf. This is all boiler plate stuff.

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watersentinal,

You are missing the point that once ANY chlorine source is dissolved and mixed in the water, then given the same CYA level the chemical components in the water are IDENTICAL (ignoring extra calcium from Cal-Hypo, etc.). When you add bleach to water that contains CYA, the hypochlorite ion mostly combines with the CYA in the water to form chlorinated cyanurates (in a matter of seconds to minutes with mixing) with a small amount of the chlorine remaining hypochlorite ion and hypochlorous acid. When you add Dichlor, then this is a single chlorinated cyanurate species and when dissolved in water it too forms other chlorinated cyanurates species with a small amount of it becoming hypochlorite ion and hypochlorous acid. The end result is an identical set of compounds regardless of source and the relative amounts of these compounds have nothing to do with the source of chlorine, but with chemical equilibrium constants.

It's one thing to say that chlorine dissipates faster regardless of source (your reference says "Bromine also remains stable at high temperatures where chlorine dissipates still more rapidly, which is why many technicians recommend bromine for spas.", NOT that bleach dissipates while Dichlor does not). It's quite another to say that the lifetime after dissolved in the water differs by source since the chemical species in the water are the same -- again, assuming you've already got CYA in the water when you add bleach. Obviously, if you add bleach to water that doesn't have any CYA in it then this won't be the same as adding Dichlor to that water since the Dichlor adds to CYA while the bleach does not.

The reference that says "Sodium hypochlorite becomes an inert substance rapidly in heat and sunlight so it should be stored in a clean, well-ventilated, dark, dry place." is referring to CONCENTRATED bleach, not sodium hypochlorite once diluted in water with CYA because as I said above, the chemical substances in the water after dilution are IDENTICAL regardless of whether the source is bleach or Dichlor (when comparing the same CYA level in both cases). The table at the bottom of this link shows the half-life of CONCENTRATED chlorine (sodium hypochlorite) as a function of concentration and temperature. You will notice that the half-life increases by roughly a factor of 4 with a halving of concentration. 6% Bleach is roughly 60,000 ppm. That is a heck of a lot higher than even 10 ppm diluted in a spa. The breakdown is no longer an issue once the chlorine is diluted in the spa (again, regardless of source of chlorine), though outgassing from the volatility of hypochlorous acid is (again, regardless of source of chlorine).

I have 12.5% chlorinating liquid that I buy from my local pool store where they have good turnover and keep the bottles out of the sun and found it to be about as stable as the table indicates -- it loses only a rather small amount of its strength to around 11.5% - 12.0% after about a month, but I don't live in a hot climate (average July day 81F, night 54F) and I keep the bottle out of the sun.

I wasn't disputing dizc -- I just wanted to know if he felt that ozonators made the dissipation of chlorine (vs. bromine) even worse and if this was due to the greater aeration.

Finally, if you read my posts you will find that I am not suggesting that everyone use bleach. I say over and over again that most people have not had any problems with Dichlor-only, and I've seen why this is the recommended approach from spa manufacturers due to its simplicity including pH management. But if you use Dichlor-only then you WILL build up CYA and you WILL get a proportionate reduction in disinfection and oxidation rate (at the same FC level). Whether this matters is the only question. My only agenda is the truth. As I've said in earlier posts, I totally get why Dichlor-only is easier for most.

And for the umpteenth time, when you add bleach the pH will rise, but when chlorine gets used up through oxidation of organics (or breakdown from sunlight, as with outdoor pools), then the pH will fall back down. But if the chlorine is outgassed through aeration or if carbon dioxide outgasses through aeration, then the pH will rise overall. Not everyone using bleach sees this rise -- some have minimized it through low (but not that low -- around 80 in one case) TA and minimizing aeration. As I've said before, in my own pool (and in hundreds of pools of pool forum users who use only chlorinating liquid or bleach) my pH is rock solid even though technically according to you the pH should be rising because all I add to it is chlorinating liquid (at the equivalent rate of around 1 ppm per day during the summer -- I have an opaque electric safety cover on it when not in use -- the cover is open about 1-2 hours every day in the summer, longer on the weekends). Nevertheless, I fully understand that many hot tub users have and want to keep lots of aeration (either from jets or from ozonators) and therefore would have to add acid before they add their bleach and for many this is too much trouble.

Richard

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chemgeek perhaps this article http://www.encyclopedia.com/doc/1G1-107277341.html will help you understand the different chemicals used to sanitize pool and spa water as well as ozone. I thought it might help you to read an article that is from a trusted pool and spa publication. Pool and spa professionals have relied on Pool & Spa news for almost 50 years.

And pool and spa professionals are still "slugging" acid to lower TA even though it has been documented in the now defunct JSPSI that it does not work! This article in you cite above is actually a decent primer for those who are just starting to learn water chemistry but it by no means is anything indepth!

I have to say that chemgeek probably has a better understanding of the different chemical used to sanitize pool and spa water than most professionals do (and I happen to work in the industry and basically agree with about 99+% of what he says!)

Sorry, just could't keep quiet on this one!

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watersentinal,

You are missing the point that once ANY chlorine source is dissolved and mixed in the water, then given the same CYA level the chemical components in the water are IDENTICAL (ignoring extra calcium from Cal-Hypo, etc.). When you add bleach to water that contains CYA, the hypochlorite ion mostly combines with the CYA in the water to form chlorinated cyanurates (in a matter of seconds to minutes with mixing) with a small amount of the chlorine remaining hypochlorite ion and hypochlorous acid. When you add Dichlor, then this is a single chlorinated cyanurate species and when dissolved in water it too forms other chlorinated cyanurates species with a small amount of it becoming hypochlorite ion and hypochlorous acid. The end result is an identical set of compounds regardless of source and the relative amounts of these compounds have nothing to do with the source of chlorine, but with chemical equilibrium constants.

It's one thing to say that chlorine dissipates faster regardless of source (your reference says "Bromine also remains stable at high temperatures where chlorine dissipates still more rapidly, which is why many technicians recommend bromine for spas.", NOT that bleach dissipates while Dichlor does not). It's quite another to say that the lifetime after dissolved in the water differs by source since the chemical species in the water are the same -- again, assuming you've already got CYA in the water when you add bleach. Obviously, if you add bleach to water that doesn't have any CYA in it then this won't be the same as adding Dichlor to that water since the Dichlor adds to CYA while the bleach does not.

The reference that says "Sodium hypochlorite becomes an inert substance rapidly in heat and sunlight so it should be stored in a clean, well-ventilated, dark, dry place." is referring to CONCENTRATED bleach, not sodium hypochlorite once diluted in water with CYA because as I said above, the chemical substances in the water after dilution are IDENTICAL regardless of whether the source is bleach or Dichlor (when comparing the same CYA level in both cases). The table at the bottom of this link shows the half-life of CONCENTRATED chlorine (sodium hypochlorite) as a function of concentration and temperature. You will notice that the half-life increases by roughly a factor of 4 with a halving of concentration. 6% Bleach is roughly 60,000 ppm. That is a heck of a lot higher than even 10 ppm diluted in a spa. The breakdown is no longer an issue once the chlorine is diluted in the spa (again, regardless of source of chlorine), though outgassing from the volatility of hypochlorous acid is (again, regardless of source of chlorine).

I have 12.5% chlorinating liquid that I buy from my local pool store where they have good turnover and keep the bottles out of the sun and found it to be about as stable as the table indicates -- it loses only a rather small amount of its strength to around 11.5% - 12.0% after about a month, but I don't live in a hot climate (average July day 81F, night 54F) and I keep the bottle out of the sun.

I wasn't disputing dizc -- I just wanted to know if he felt that ozonators made the dissipation of chlorine (vs. bromine) even worse and if this was due to the greater aeration.

Finally, if you read my posts you will find that I am not suggesting that everyone use bleach. I say over and over again that most people have not had any problems with Dichlor-only, and I've seen why this is the recommended approach from spa manufacturers due to its simplicity including pH management. But if you use Dichlor-only then you WILL build up CYA and you WILL get a proportionate reduction in disinfection and oxidation rate (at the same FC level). Whether this matters is the only question. My only agenda is the truth. As I've said in earlier posts, I totally get why Dichlor-only is easier for most.

And for the umpteenth time, when you add bleach the pH will rise, but when chlorine gets used up through oxidation of organics (or breakdown from sunlight, as with outdoor pools), then the pH will fall back down. But if the chlorine is outgassed through aeration or if carbon dioxide outgasses through aeration, then the pH will rise overall. Not everyone using bleach sees this rise -- some have minimized it through low (but not that low -- around 80 in one case) TA and minimizing aeration. As I've said before, in my own pool (and in hundreds of pools of pool forum users who use only chlorinating liquid or bleach) my pH is rock solid even though technically according to you the pH should be rising because all I add to it is chlorinating liquid (at the equivalent rate of around 1 ppm per day during the summer -- I have an opaque electric safety cover on it when not in use -- the cover is open about 1-2 hours every day in the summer, longer on the weekends). Nevertheless, I fully understand that many hot tub users have and want to keep lots of aeration (either from jets or from ozonators) and therefore would have to add acid before they add their bleach and for many this is too much trouble.

Richard

I was warned by many people through emails that you won't listen to facts. The term google king was used and I understand their frustration. Anyone can claim to be anything online these days and google any term they want. That explains someone who doesn't own a spa or work with them hanging out on a spa forum telling people how to care for them. It's a shame that you are misleading and hurting so many people. I've been helping them privately since they are afraid to speak out against you in the forum. Remember that I was brought here by a customer who followed your bleach advice. You don't listen to facts and you aren't interested in the truth. You do not have one shred of evidence to prove that dichlor is a problem in spas, period. And even if it were, bleach would not be the solution. If you need to believe the sky is red despite the truth that it's blue then keep on believing. I have over 20 years experience in the business and you don't even own a spa. It's absurd. If you don't have an agenda why don't you lead people towards bromine or other alternatives to dichlor? I helped my customer that was harmed by your advice and hopefully a few others here. One email stated that you think you own this forum. You clearly don't like your territory invaded by someone who has more knowledge than you which is understandable. Since I don't have any shortcomings in my life that send me to the internet looking for adoration, I will leave you to your little corner of the world.

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chemgeek perhaps this article http://www.encyclopedia.com/doc/1G1-107277341.html will help you understand the different chemicals used to sanitize pool and spa water as well as ozone. I thought it might help you to read an article that is from a trusted pool and spa publication. Pool and spa professionals have relied on Pool & Spa news for almost 50 years.

And pool and spa professionals are still "slugging" acid to lower TA even though it has been documented in the now defunct JSPSI that it does not work! This article in you cite above is actually a decent primer for those who are just starting to learn water chemistry but it by no means is anything indepth!

I have to say that chemgeek probably has a better understanding of the different chemical used to sanitize pool and spa water than most professionals do (and I happen to work in the industry and basically agree with about 99+% of what he says!)

Sorry, just could't keep quiet on this one!

I don't think you should keep quiet. You clearly work in the industry and have experience to back up your opinions. There is more than one way to skin a cat, but using bleach in a spa isn't a good one. That's my only arguement. I care so much about each and every customer I have that I hate to see them endangering their own health or potentially damaging their spa. Not to mention that using a spa is relaxing and you shouldn't have to add chemicals several times a day to maintain your water. There is also no way you should run a spa without fc. The people on this forum using bleach are doing that for the most part. It is a really great article and one we give to customers. I have to add that I can lower the alkanity by plugging with acid. Of course, I've been around the block a few times. But alas my time here is done. Goodbye and goodluck to everyone with their water.

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I was warned by many people through emails that you won't listen to facts. The term google king was used and I understand their frustration. Anyone can claim to be anything online these days and google any term they want. That explains someone who doesn't own a spa or work with them hanging out on a spa forum telling people how to care for them. It's a shame that you are misleading and hurting so many people. I've been helping them privately since they are afraid to speak out against you in the forum. Remember that I was brought here by a customer who followed your bleach advice. You don't listen to facts and you aren't interested in the truth. You do not have one shred of evidence to prove that dichlor is a problem in spas, period. And even if it were, bleach would not be the solution. If you need to believe the sky is red despite the truth that it's blue then keep on believing. I have over 20 years experience in the business and you don't even own a spa. It's absurd. If you don't have an agenda why don't you lead people towards bromine or other alternatives to dichlor? I helped my customer that was harmed by your advice and hopefully a few others here. One email stated that you think you own this forum. You clearly don't like your territory invaded by someone who has more knowledge than you which is understandable. Since I don't have any shortcomings in my life that send me to the internet looking for adoration, I will leave you to your little corner of the world.

I didn't realize that many people felt that way and wish they would have said so or PMd or E-mailed to me. I noticed that TinyBubbles stopped responding so figured something was wrong there and said so. Many links that I post are to scientific studies and not just hearsay, but if people believe I'm just making stuff up and that the chemistry isn't sound, then that's not true, but unless they look at the chemistry themselves or have a chemist review it with them, then there's no way to prove it to themselves.

I told you before about the initial 4 hot tub itch/lung reports on this forum and the 3 subsequent ones, all but one of which occurred after 1.5 (most were 2) months of Dichlor-only use (one incident was with MPS use where chlorine levels were zero). I told you before that doesn't prove the problem is Dichlor, but is what got me looking into it. I have mentioned bromine and biguanide/PHMB as alternative sanitizers and with bromine have said that it smells different and some people have some sensitivity to it, but it works for many people and has floating feeders for dispensing so is convenient. Chlorine doesn't have that automated convenience (for spas) except for some SWG-equivalent for spas some have talked about.

I'll stop posting on this forum. For those who are still interested in the water chemistry, I can be found in the Advanced Chemistry section in this link and there is a spa/hot tub care section here. I'm sorry I offended anyone.

Richard

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chemgeek perhaps this article http://www.encyclopedia.com/doc/1G1-107277341.html will help you understand the different chemicals used to sanitize pool and spa water as well as ozone. I thought it might help you to read an article that is from a trusted pool and spa publication. Pool and spa professionals have relied on Pool & Spa news for almost 50 years.

And pool and spa professionals are still "slugging" acid to lower TA even though it has been documented in the now defunct JSPSI that it does not work! This article in you cite above is actually a decent primer for those who are just starting to learn water chemistry but it by no means is anything indepth!

I have to say that chemgeek probably has a better understanding of the different chemical used to sanitize pool and spa water than most professionals do (and I happen to work in the industry and basically agree with about 99+% of what he says!)

Sorry, just could't keep quiet on this one!

I don't think you should keep quiet. You clearly work in the industry and have experience to back up your opinions. There is more than one way to skin a cat, but using bleach in a spa isn't a good one. That's my only arguement. I care so much about each and every customer I have that I hate to see them endangering their own health or potentially damaging their spa. Not to mention that using a spa is relaxing and you shouldn't have to add chemicals several times a day to maintain your water. There is also no way you should run a spa without fc. The people on this forum using bleach are doing that for the most part. It is a really great article and one we give to customers. I have to add that I can lower the alkanity by plugging with acid. Of course, I've been around the block a few times. But alas my time here is done. Goodbye and goodluck to everyone with their water.

You have come in and now you are going? That's sort of cheap! Why not stick around and give you expertise to this board like I and some others in the industry do? You have also driven off chemgeek. That is a real loss! As far as bleach in a spa, I recommend it also and I am not the only one. I know of a spa dealer in S. FL that recommeded using bleach for chlorination and for 'shocking' bromine systems. (His main business is actually sellling spas and NOT chemicals!) Also at least one state (PA) and possibly others by now have outlawed the use of dichlor in commercial spas for precisely the reasons that chemgeek states (overstabilization)! Consider also that one of the largest pool/spa chemical companies (Arch Chemical) does NOT make a spa dichlor but only offes unstabilzed cal hypo for spa use and shocking! Your 'dichlor is the only way to go' argument is losing steam! I have successfully used bleach in my own spas. It does take daily water testing and shocking on a regular basis. Unfortunately many spa owners just don't want to put the work into it. As far as balancing pH and TA, well once again, testing and balancing is the answer. No one ever said that maintaining a spa was work free. IF someone is not going to test their water and balance it as needed then maybe a spa is not for them. Look at all the spas on chlorine and with ozone which goes directly against the info in the article you posted (and is something I have stated on here many times--that ozone and chlorine don't 'play well together).

As far as running a spa without FC I agree with you but I have seem many poster who use dichlor that state that if you add the dichlor after you soak there is NO CHLORINE PRESENT the next time you use the tub and they think this is a good thing!

I don't know who got you here to get rid of chemgeek but I suspect I will be next for 'bashing' biguanide :rolleyes: since I don't recommend it except for people who actually are allergic to chlorine or bromine because of the problems associated with it's use (and which were also listed in the article you referenced!) not to mention my support of using bleach or other unstabilzied chlorine in a spa. I am wondering if you feel the same way about lithium hypochlorite? If you sell it I am sure you recommend it. It is a high ticket item. Bleach is not and, unless you also sell pool supplies it is doubtful that you carry liquid chlorine! Hmmm, maybe THIS is why bleach is not recommened. Dealers can't make a profit off of it!

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To dlcz - many thanks for that information! That's exactly the kind of response I was looking for. So, in a nutshell would it be correct to say that 1) at temps in a spa, bromate would not be stable enough to hang around very long, and 2) there's no strong evidence that bromate is, in-and-of itself a carcinogen? Ignoring the chlorine issue, it sounds like you wouldn't recommend against an ozonator in a bromine spa? Please confirm, and thanks very much again.

To chemgeek - I'd think twice about letting the abrasive comments of one user drive you away. I've read through many, many links (including my own) where you've been a tremendous help to people. I've never considered your advice biased or overbearing, and I can tell that you have no agenda other than providing good information. I suspect others will write in to agree, and I'm hopeful that you'll hang around - I'm looking forward to more good advice!

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To chemgeek - I'd think twice about letting the abrasive comments of one user drive you away. I've read through many, many links (including my own) where you've been a tremendous help to people. I've never considered your advice biased or overbearing, and I can tell that you have no agenda other than providing good information. I suspect others will write in to agree, and I'm hopeful that you'll hang around - I'm looking forward to more good advice!

I agree. If you decide not to post at this forum there will be tremendous disappointment. You are a wonderful source of information and make this forum interesting to visit. This hasn't always been the case here as it has sometimes been quite confrontational. You have spent an awful lot of time and energy helping people with their water problems which is much appreciated. I, for one, certainly hope you reconsider.

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Chem Geek and watersentinel -- I realize this disagreement does not involve me, and perhaps I should leave well enough alone, but Chem Geek has helped me quite a few times and I sincerely appreciate his time and expertise.

Granted, I don't read every thread that is posted, especially if it is not something that is going to help my situation, but I have never read anything from Chem Geek that would make someone feel "afraid to speak out against (Chem Geek) in the forum". I have found him to be very helpful, humble and even apologetic at times. Nothing that would make me fear speaking out against him.

Perhaps this next observation is out of line, but watersentinel has been a member of this forum for only 1 week...what has he/she done in that time to develop such a "following"?

Plus, there have been topics raised where Chem Geek is the ONLY one willing to step in and offer advice, without him around, many of us would be stranded. If waterbear, with his knowledge and background, agrees with most of what Chem Geek says, there must be some validity and accuracy to it.

Richard, don't let the comments of one person influence you that way. Stick around; you have helped many people with problems that they perceived to be quite severe and distressing. I realize we can find you at another site, but what is there to stop this same individual from attacking you at that site as well. Just keep doing what you believe to be true and accurate…and realize you will NEVER please to everyone. Come back!!!

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I agree. I feel bad that someone as helpful and polite as Chem Geek would be attacked like that. But as they say, "no good deed goes unpunished". My favorite part of the forum is the Hot Tub Water Chemistry and all of Chem Geek's posts are interesting and thought-provoking. The information I gathered here gave me the confidence to get a good hot tub and learn how to test water and sanitize it. I hope he will reconsider and return to the forum. I am very grateful for everything I have learned from him and would like to thank him for giving so freely of his time and knowledge.

Rebecca

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I realize we can find you at another site, but what is there to stop this same individual from attacking you at that site as well.

I can answer that question. I happen to be one of the Moderators at the site in question and and Richard is held in very high regard at that site. I would not allow it to happen nor would the other mods or the site owner! I can say that for a fact!

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Sorry to see this topic trashed, it seems like there are other much more appropriate threads that all this drama over conventional spa wisdom versus real scientific analysis. I am a firm believer that halogens are by far the easiest way to maintain a pool or a spa and would like to see furhter discussion of the topic of cancer concerns.

Chris W

P.S. for the last 10 days, I have used nothing but Chlorinating liquid and a little acid in my spa and my water quality and control of combined chlorines is better than ever before. I do use my spa every day, and I believe that testing the water every day (real testing, not BS strips) and adjusting sanitizer and pH levels are all part of spa ownership. It is never necessary to adjust chemistry twice a day and with proper preparations, I can leave for several days at a time without dramatic water quality problems. Just my experience. I will continue to seek out the best advice from the smartest people I can find who do not sell pool and spa supplies for a living. If that will be on a different forum , so be it. I was on other forums before I came here and came here becasue of the higher level of activity in the spa area and the relatively high ratio of owners to dealers on this forum. If that changes, I will move on.

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P.S. for the last 10 days, I have used nothing but Chlorinating liquid and a little acid in my spa and my water quality and control of combined chlorines is better than ever before. I do use my spa every day, and I believe that testing the water every day (real testing, not BS strips) and adjusting sanitizer and pH levels are all part of spa ownership. It is never necessary to adjust chemistry twice a day and with proper preparations, I can leave for several days at a time without dramatic water quality problems. Just my experience.

And it's exactly what I've been saying also!!!!! If you manage the water PROPERLY it's easy to do. If you are having problems you are doing something wrong! Figure out what you are doing wrong and solve the problem! The big three mistakes I have seen are improper testing (or just not testing or using strips and deluding yourself into thinking you have accurate test results), improper or infrequent chemical dosing (lazy doesn't work when you have a spa!), or just dumping in a teaspoon of this and a tablespoon of that because it's what it said on the package and then wondering why there are problems!

I will continue to seek out the best advice from the smartest people I can find who do not sell pool and spa supplies for a living.

Whoops! Guess that leaves me out! :lol:

If that will be on a different forum , so be it. I was on other forums before I came here and came here becasue of the higher level of activity in the spa area and the relatively high ratio of owners to dealers on this forum. If that changes, I will move on.

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When using ozone, chlorine becomes a waste of money. Bromine has a much lower vapor pressure, so it tends to last much longer.

Great info. When I read the EPA info on potassium bromate, I thought the same thing "maybe it's the potassium".

With your statement above, are you saying that the aeration from the ozonator will tend to outgas the hypochlorous acid? Henry's Law Constant (M/atm) for chlorine is around 660 at 25C and 250 at 104F while for hypobromous acid the literature varies a lot from 93 to 6100 at 25C. For molecular chlorine, Henry's Law Constant is around 0.095 while for molecular bromine it is around 0.76, but these are in very low concentration in water and for chlorine is rate limited in its formation (unless chloride levels are very high).

So are you saying that the aeration of the ozonator will tend to drive out chlorine (specifically, hypochlorous acid) from the water and does so more rapidly than bromine (specifically, hypobromous acid)? If so, then such strong aeration should also drive out carbon dioxide and tend to make the pH rise faster.

Richard

It seems to me it is the (forgive the caps)

POTASSIUM bromATE

POTASSIUM carbonATE

... combination of potassium (a vital ion, that happens to be radioactive) and excess oxygen. Sodium bromate can be made in certain tests to generate carcinogenic behavior... and the same test shows table salt and ethanol are carcinogens. The sodium potassium pump is non-trivial when dosing individual cells.

Chlorine and bromine stripping will occur where ozone is applied. But it is usual to have it strip from the pool surface, and bather entery/exit. And I won't get into the specific ions involved, but bromine-based compounds tends to stay in water more. Even found concentrated in sea spray!

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To dlcz - many thanks for that information! That's exactly the kind of response I was looking for. So, in a nutshell would it be correct to say that 1) at temps in a spa, bromate would not be stable enough to hang around very long, and 2) there's no strong evidence that bromate is, in-and-of itself a carcinogen? Ignoring the chlorine issue, it sounds like you wouldn't recommend against an ozonator in a bromine spa? Please confirm, and thanks very much again.

The answer to 1) is "Yes" if and only if ozone is applied "in moderation". Meaning ORP / redox is used to control the ozone dose to what is necessary to maintain kill (>500 mV) but not infinite kill (>700 mV).

As to 2) I would recommend ozone in water with high bromides, even with high bromate formation. Bromate compounds in high concentrations are used to dye hair. If a lot of "oral ***" is performed underwater, might be an issue...

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To dlcz - many thanks for that information! That's exactly the kind of response I was looking for. So, in a nutshell would it be correct to say that 1) at temps in a spa, bromate would not be stable enough to hang around very long, and 2) there's no strong evidence that bromate is, in-and-of itself a carcinogen? Ignoring the chlorine issue, it sounds like you wouldn't recommend against an ozonator in a bromine spa? Please confirm, and thanks very much again.

The answer to 1) is "Yes" if and only if ozone is applied "in moderation". Meaning ORP / redox is used to control the ozone dose to what is necessary to maintain kill (>500 mV) but not infinite kill (>700 mV).

As to 2) I would recommend ozone in water with high bromides, even with high bromate formation. Bromate compounds in high concentrations are used to dye hair. If a lot of "oral ***" is performed underwater, might be an issue...

Hmm - so (in response to 1): how would one tell if the ozone is being applied in moderation? My ozonator is inline. It is not driven by a 25/7 pump as in other system, but instead comes on only during filter cycles (2 hours, 2 X day).

In response to 2: Why would you recommend it even with high bromate formation? And, more importantly, how can I go about encouraging lots of oral *** in the tub :lol:

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... combination of potassium (a vital ion, that happens to be radioactive)

Not all isotopes of potassium are radioactive. Both the K39 and K41 isotopes are not. K40 is but it makes up only .0118% of the naturally occuring potassium. It is also not the only common substace with radioactive isotopes. A large number of common elements have naturally occuring radioactive isotopes. This is not anything unusual at all.

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[ Bromate compounds in high concentrations are used to dye hair.

This is a new one on me and I was a hair colorist for many years. Bromates have been used as a permenant wave oxidizer (neutralizer) but I know of no use for them in the coloring of hair. (and I am even more familiar with the chemistry involved in that than I am in the chemistry of pool or spa water!!!!!!!)

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