Jump to content

Chem Geek Back In A Limited Way


chem geek

Recommended Posts

I have been struggling with my desire to provide information that may be helpful to people, but not wanting to be personally attacked so I left this forum for a time to sort that out. I thank everyone who has been supportive (including the "thank you" thread I read) and I believe I can contribute again to this forum, but I will only provide information and not give advice.

Hot Tub Itch/Rash

One thing that needs to be figured out by y'all is why there appears to be a significant number of reports of itching, rashes, and even hot tub lung (one case) and why these cases mostly seem to occur under conditions of either no chlorine over periods of at least a few days (including during the first month) or with chlorine after 1 month or more of frequent Dichlor use (i.e. the Vermont/Northman method) or with use of bromine. The following is a chart linking to every reported case I could find on this forum (and one that may be a duplicated one on TroubleFreePool). DO NOT BE SCARED BY THIS CHART! Most people do not have any problems with their spas and many of the following issues are most likely not related to Pseudomonas bacteria. I've only been looking for trends to figure out what is going on.

Type ..... Sanitizer . Time after Refill . Link and status

Rash/Itch ... ? ......... ? ........ EcoOne treatment works

Rash/Itch . Dichlor & N2 . 2 months ..... not resolved (switched to bromine)

Itch ....... None ..... Immediately ..... OK now

Lung ..... Enzyme .... 2 months ..... AquaFinesse was used; Since Dichlor/Bleach, better, but not cured

Itch ..... Bromine ........ ? .......... Unknown resolution

Itch ..... Dichlor ...... >1 month? ... Unknown resolution

Rash ... Low Chlorine & N2 . ? ......... Unknown resolution

Itch ..... Bromine .... Immediately . Unknown resolution

Rash .. No Chlorine ...... 1 week .... Unknown resolution

Rash .. MPS with FC? .... 3 weeks .. Thinks it's the heat

Rash .. Bromine/MPS ..... 1 month .. Unknown resolution

Cough .... Bromine ....... 2 months . Unknown resolution

Ear ..... Chlorine (zero?) . 2 weeks . Better now

Rash/Itch . Bromine .... 1 month? ... Unknown resolution (Chloe)

Rash ... Dichlor ........ 1 month ... Unknown resolution (Delpha)

Rash .... Bromine ......... ? ....... Unknown resolution

Rash .. Low Dichlor ... 1 month .... ozonator wasn't working

Rash ... Dichlor ....... 1 week .... Unknown resolution; possibly MPS sensitivity

Itch/Rash . Bromine ...... ? ....... Unknown resolution

Rash . Dichlor / Bromine . 2 months / 2 weeks .. Unknown resolution

Rash ....... ? ............. ? ...... Unknown resolution (dilauro)

Rash .... Dichlor ....... 3 months .... Unknown resolution (also dilauro)

Rash .... Bromine ..... 1.5 months ... Unknown resolution (not MPS)

Rash/Itch . Dichlor ... few months ... Dichlor then switch to bleach worked

Itch ... Low/No Bromine ... ? ....... Confirmed hot tub itch; Unknown resolution

Itch .... Dichlor ...... 3 weeks .... Unknown resolution; also used MPS weekly

Itch .. Low/No Bromine .. Days ...... Unknown resolution

Itch .... Chlorine ........ ? ....... Unknown resolution

Cough . Dichlor/Nature2 . 1 month ... Unknown resolution

Lung ... No Chlorine ...... ? ....... Used The Natural; hot tub is possible source

Rash . Copper/MPS/Dichlor . 2 months . Clearwater Blue for copper; MPS after each soak; Dichlor weekly

Itch/Rash . Low Chlorine . 1 month .. Confirmed Pseudomonas; Unknown resolution

Rash ..... Copper ........ ? ........ Cleanwater Blue system

Rash .. Frog/Bromine .... 10 days ... Unknown resolution

Spots .... Bromine ...... 1 week .... Unknown resolution

Itchy Bumps . Bromine ... Months? ... Unknown resolution

There were also several posts regarding how poor jet design or setup (such as not rotating and hitting in one place) can lead to itching (I did not include those above). So the thing to focus on is not whether there is an itch or rash that is caused by physical irritation and goes away quickly, but on whether the rash takes days to subside after stopping use of the hot tub. The table in this link can help distinguish between a chemical vs. bacterial cause for the rash. It should also be remembered that the number of incidents is very small compared to the total number of tub/spa users.

pH Rise and Chlorine Usage with Bleach

In separate E-mail discussions with a user who did some very careful measurements, it is very clear that a functioning ozonator will aerate chlorine (as well as carbon dioxide) which will cause the pH to rise and will lead to faster chlorine loss. [EDIT] We now know that ozone oxidizes chlorine to chloride and chlorate (as described in this paper referring to this paper) and that the chlorine loss isn't just from increased outgassing. [END-EDIT] The rate for this user was a half-life of 9-12 hours for chlorine so over 24 hours the chlorine would drop to 16-25% of its starting FC level plus additional loss due to usage of the tub (i.e. oxidizing urea/ammonia from sweat). However, this extra loss due to usage was quite a bit less than seen in tubs not using an ozonator so perhaps the ozonator is oxidizing some of the urea/ammonia (since FC was low at the start of soaking). There was no difference in chlorine loss when using Dichlor vs. bleach vs. Lithium hypochlorite (other users also reported no difference in Dichlor vs. bleach chlorine loss), but the Lithium hypochlorite did show a greater pH rise than the bleach. Therefore, the brand probably matters a lot since standard Lithium hypochlorite contains only a small amount of extra lye as does normal (e.g. Clorox Regular) bleach and we've seen one user where bleach (of unknown brand) wouldn't last as long as Dichlor.

Users who have had the best experiences with bleach (after initial Dichlor for a week or so) are those with minimal aeration in their tubs -- no ozonator and most jets having aeration turned off -- and using known good brands of bleach. One user experiences a drop in pH when using Dichlor and a small rise (acid added only every other week) when using bleach. This latter result is consistent with the chemistry, but clearly requires a combination of using the right brand that does not contain contaminants or excessive lye and a tub where aeration has been minimized (otherwise, acid will need to be added prior to addition of bleach). It is also important to use enough chlorine, of any source, as we found that there is a LOT of urea/ammonia introduced from sweat and this may be as much as 7 ppm FC in 350 gallons per person-hour of soaking. THIS IS NOT A RECOMMENDATION TO USE BLEACH. Depending on your situation, it can take more work. [EDIT] We now know that the pH rise from aeration can be significantly reduced by lowering the TA level a lot, to around 40-50 ppm, and by adding 50 ppm Borates as an additional pH buffer. [END-EDIT]

Nature2 EPA Silver+MPS Submission

[EDIT] I finally found some scientific literature that backs up the Nature2 "low chlorine recipe" that uses Nature2 silver ions with MPS here. The following was written before I found such scientific literature. [END-EDIT]

I have not found any scientific studies showing the significant killing power of silver+MPS as was shown in the Nature2 submission posted on this forum so I have contacted those who should know (including the main manufacture of MPS) about this. There are clear studies showing cobalt as a powerful catalyst to MPS (creating short-lived hydroxyl radicals) and copper is known to break down MPS faster and silver is known to break down the irritating persulfate aka peroxydisulfate (S2O82- -- this is not monopersulfate aka peroxymonosulfate which is HSO5-) that is found in small (3%) quantities in MPS products, but nothing on silver+MPS being pretty much as powerful as chlorine against bacteria. I'll let you know what I find out.

I do think the EPA laboratory portion of the test is way, way too strict (6-log reduction in 30 seconds or less) and is far stricter than the field test. In fact, stabilized chlorine (i.e. Dichlor and Trichlor) would not pass the lab test if the CYA level in the water were even 3 ppm or higher -- such tests are done by adding product to water without CYA already being present which is why they pass the test. The field tests clearly build up CYA over time, but are much less stringent (I think they are much more realistic, though up to 15% of the samples can fail the bacterial indices criteria and Pseudomonas are not explicitly tested -- the focus is more on fecal bacteria though there is a standard plate count test). This link is to a scientific paper giving the kill times for the bacteria Streptococcus faecalis which is one of the two bacteria used in the EPA lab test. Figure 4 shows the increase in the time it takes to kill this bacteria when CYA is present. The implied CT value for a 2-log reduction is around 0.06 (4*0.5/25=0.08, 6*0.5/50=0.06, 12*0.5/100=0.06) so a 6-log reduction would have a CT of around 0.18. If 1 ppm FC of Dichlor is added to water not containing CYA, then this is equivalent to 0.65 ppm FC with no CYA (that is, the CYA from Dichlor reduces the effective FC from 1 ppm to 0.65 ppm). The 6-log kill time is then 0.18/0.65 = 0.28 minutes or about 17 seconds which is clearly faster than the 30 second criteria. However, if there is 100 ppm CYA in the water, then the 6-log (99.9999%) kill time is about 24 minutes. Though this sounds bad, this is a huge reduction in bacteria. A 2-log (99%) reduction would be around 8 minutes. This may not be ideal for preventing person-to-person transmission, but it's certainly more than fast enough to kill this bacteria faster than it can reproduce (bacteria generation or doubling time is 15 minutes to an hour or so under ideal conditions -- see this link).

A good summary of pathogens in pool and spa water may be found in this WHO document in Chapter 3 (starting at page 26, PDF page 49) and Pseudomonas are described on page 43 (PDF page 66).

Richard

Link to comment
Share on other sites

So glad to see you are back. There has been a dearth of good information in the chemistry section, except for some posts by Water Bear.

I have had my 150 gallon tub for almost 2 months now. I am using clorox twice a day, more if needed, and adding acid every other day or so. I am really impressed how the water stays so clear in spite of us using it about 2 to 2.5 bather hours a day.

I gave up on testing for combined chloramines and just go by sense of smell. So my question is, if I keep my FC between 4 and 10 and everything smells okay, do I still need to shock? I have used MPS on occasion, but it seems to make me itch, so I would rather avoid it if possible.

I usually add a quarter to half a cup of clorox, depending on how soon we are planning to tub, and it gets the FC above 10 easily. I've already had to buy a third bottle of 871 testing solution so I don't usually keep testing once I see that the FC is over 10.

If I should shock, how much clorox should I add? Would too high a level cause problems with the plumbing or the pump?

Anyway, so glad you are back. Don't let yourself be discouraged by argumentative people.

Thanks, Rebecca

Link to comment
Share on other sites

Rebecca,

Unfortunately, as I posted, I do not want to give specific advice telling you what to do as that may just bring out those with differing opinions who will bash me for my not being in the industry, not owning a hot tub, not listenting, etc. Combined Chlorine (of at least 0.5 ppm) is a problem when it persists because it usually means you aren't using enough chlorine to have enough Free Chlorine. When you soak in a tub, you sweat and that releases urea and ammonia into the water. Either during your soak or afterwards (depending on the level of chlorine you soak with and whether you add chlorine afterwards), the urea/ammonia will combine with the Free Chlorine and produce Combined Chlorine, specifically monochloramine. This happens very quickly -- pretty much complete in under a minute even at higher CYA levels.

What happens next is much slower where the Combined Chlorine further reacts with additional Free Chlorine to get broken down ultimately to nitrogen gas, hydrochloric acid and water. This process could take about an hour, but the best breakpoint model I have (Jafvert & Valentine) does not have temperature dependence so I'm estimating as to how long it really takes. So if you measure Combined Chlorine after you have soaked, then that is not really a problem. The time to measure Combined Chlorine is before you get in for your soak because if you measure some at that time (or you measure near zero Free Chlorine), then that may mean you aren't using enough chlorine. Also, if you don't find an annoying smell, then you probably don't have a lot of monochloramine so it's probably not a problem.

Some people find MPS irritating. One can shock with chlorine instead of MPS, though maintaining an FC residual would normally preclude any need for shocking at all. There's the adage, if it ain't broke, don't fix it. Shocking is to fix a problem such as Combined Chlorine or cloudy water or an alage bloom (for pools). However, several instructions on products say to shock regularly; in my own pool I hardly ever shock (only once last year with MPS) and instead keep the chlorine level consistent at all times and this is also true of a very large number of pool users on The Pool Forum and Trouble Free Pool.

If the FC level is brought up to 10 in order to have a residual, then a CYA level higher than 20 (say, 40) would prevent getting the chlorine level too high. It's not at all at dangerous levels since even 10 ppm FC with 20 ppm CYA is technically equivalent to 0.9 ppm FC with no CYA. If you have an FC level of 10 ppm over a reasonable period of time, then shocking should not be necessary. I'm just saying that it is the FC/CYA ratio that determines chlorine's "power" so 4 ppm FC at 20 ppm CYA is equivalent to 10 ppm FC at 50 ppm CYA. The main concern with higher chlorine levels (at the levels we are talking about) isn't so much with plumbing, but with hot tub covers. The main reason to use a somewhat higher CYA level would be to moderate the chlorine to reduce the rate of cover degradation and it would help lower oxidation rates of swimsuits, skin and hair as well (by a factor of 2 if you raised the CYA from 20 to 40).

1/4 cup of 6% Clorox Regular (unscented) bleach in 150 gallons increases the FC by about 6.4 ppm so 1/2 cup increases it by about 12.9 ppm. With the 7 ppm FC in 350 gallons per person-hour rule, 2 bather hours per day would be 14 ppm FC in 350 gallons or about 33 ppm FC in 150 gallons so this explains why you are adding 13-26 ppm FC per day. So long as you measure a residual and never get to zero chlorine, then it sounds like you're in balance. The 7 ppm rule may be conservative (it certainly seems to be in your case) or your bathers sweat less (possibly the temperature is below 104F).

The Water Replacement Interval (WRI) for spas is typically given as (1/3) * (spa volume in U.S. gallons) / (number of bathers per day). Of course, it should really be based more on bather-hours, but the rule was made to be simple, not accurate. Even if we just use 2 bathers per day (and I think the WRI rule assumes something closer to 30 minutes soaks rather than 1 hour soaks), then this would say the WRI for your spa would be (1/3) * (150) / 2 = 25 days so have you not changed the water for the entire 2 months? If you haven't, then the fact that your water is remaining so clear and without problems and that your spa experience is still good is, well, I'll let you draw your own conclusions. If you are adding, say, 20 ppm FC per day, then you are increasing the salt level by as much as around 1000 ppm per month (though outgassed chlorine will make this number less). So, after 3 months you might be at 3000 ppm salt which is the level of saltwater chlorine generator (SWG) pools. If you have metal parts exposed to the water that aren't stainless steel, then the higher salt level could be somewhat corrosive combined with the chlorine, but usually it's low pH that is most corrosive to metal. If you want to check your salt level to be sure, you can get a salt test -- the Aquacheck White - Salt strips are actually one of the few test strips that are as good as drop tests or you can get the Taylor K-1766 drop-based test.

The chemistry of your routine sounds correct to me, but as to other side effects or problems or issues or reasons why anything you are doing should be changed, others can give their opinion.

Richard

Link to comment
Share on other sites

I have been struggling with my desire to provide information that may be helpful to people, but not wanting to be personally attacked so I left this forum for a time to sort that out. I thank everyone who has been supportive (including the "thank you" thread I read) and I believe I can contribute again to this forum, but I will only provide information and not give advice.

Welcome back, Richard!!

Link to comment
Share on other sites

So glad to see you are back. There has been a dearth of good information in the chemistry section, except for some posts by Water Bear.

I have had my 150 gallon tub for almost 2 months now. I am using clorox twice a day, more if needed, and adding acid every other day or so. I am really impressed how the water stays so clear in spite of us using it about 2 to 2.5 bather hours a day.

I gave up on testing for combined chloramines and just go by sense of smell. So my question is, if I keep my FC between 4 and 10 and everything smells okay, do I still need to shock? I have used MPS on occasion, but it seems to make me itch, so I would rather avoid it if possible.

I usually add a quarter to half a cup of clorox, depending on how soon we are planning to tub, and it gets the FC above 10 easily. I've already had to buy a third bottle of 871 testing solution so I don't usually keep testing once I see that the FC is over 10.

If I should shock, how much clorox should I add? Would too high a level cause problems with the plumbing or the pump?

Anyway, so glad you are back. Don't let yourself be discouraged by argumentative people.

Thanks, Rebecca

I find it rude that you think only a couple of people give good knowledge in this forum. Because you use bleach and not another type of sanitizer does not mean the information others are giving about those sanitizers are not good. All that give info in this forum may have good information depending on the information they seek. Don't shoot them in the back. This kind of stuff is how part of the arguments start, when you are rude to other people.

Chem Geek, I am also glad to see you back. As I stated before, we can all learn from each other. It takes all of us to give information to come to conclusions, as you have shown.

Link to comment
Share on other sites

I have been struggling with my desire to provide information that may be helpful to people, but not wanting to be personally attacked so I left this forum for a time to sort that out. I thank everyone who has been supportive (including the "thank you" thread I read) and I believe I can contribute again to this forum, but I will only provide information and not give advice.

Welcome back - glad to have you. I've been doing too much soaking to do much posting, but I look forward to more interesting discussions.

Link to comment
Share on other sites

  • 1 month later...

I noticed that TinyBubbles found a routine that worked (see this thread) using the newer N2 approach of daily MPS and weekly Dichlor. This isn't the actual recommended N2 approach (see the "low chlorine recipe" in this PDF file on page 6) since they say to have an MPS residual before soaking, but MPS can be irritating to some (though apparently the silver in N2 can catalyze the breakdown the potentially irritating persulfate ion, S2O82-) . TinyBubbles never had rash/itch so was just worried about sanitation, but it got me thinking about correlating N2 against the rash/itch reports since I would expect the N2 to prevent uncontrolled bacterial growth so possibly preventing hot tub itch. I updated the table at the start of this thread and only found two of the reports using N2 (these had low chlorine or high CYA). Still too few reports to draw conclusions.

There is likely to be a spectrum of risk roughly ordered as follows from greatest sanitation (lowest risk) to lowest sanitation (highest risk) with some guessing on my part based on predicted sanitation plus the rash/itch reports:

Bleach Only >> Dichlor then Bleach > N2 with daily Dichlor > Dichlor Only >? N2 with daily MPS >>? N2 alone >> nothing

The "Bleach Only" is too strong with associated side effects of faster deterioration of hot tub covers, bleaching of swimsuits, rougher on skin, hair, etc. and is not necessary since it doesn't take that much disinfectant to kill most pathogens. The ">?" and ">>?" is due to not knowing if the N2 with MPS combination is truly effective and a fast sanitizer. If it is, then it could be better than Dichlor Only; if not, then could be worse as shown above. Remember, that even having nothing in the water doesn't mean one absolutely positively gets hot tub itch. It just significantly increases the risk.

The above is NOT a recommendation to use Dichlor then Bleach. As noted elsewhere, the pH will tend to rise with this method and may do so at a fast rate if there is aeration, such as from an ozonator or significant use of aerated jets. It takes more work to manage the water in this situation since regular acid addition is required. It has worked well for some people and was way too much effort for others.

Richard

Link to comment
Share on other sites

Richard, I've had a very good experience with the dichlor then bleach after soaking sanitizing routine. My water has stayed crystal clear and fresh to the end with what to me seems to be very little TDS accumulation. I've just changed my water after five months, but really don't think I needed to.

Link to comment
Share on other sites

  • 1 year later...

Hello I'm new here. Our hot tub is new to us/but used.

There is an extreme wealth of information and I have been reading for a bout 2 hours now.

Both my husband and I have the red spots.(not ichy thank goodness) We have had the tub up less than a week. Silly time of year up here to put in a tub(outdoors) but it's done.

Upon install of the tub we found leakes to fix. Parts were replaced and we were left with a minor leak. We used a Stop Leak and that worked. I first thought I was reacting to one of the chemicals (Stop Leak or Bromine)as I have a tendance to react to stuff, but my husband has the spots too. I think we have filled and emptied the tub 4-5 times now. Each time scrubbing walls and washing down the tub and removing all water.

Questions:

What I have not been able to find here is does bromine by itself cause the itch?

How do you test for pseudmonas? Can you test water or is it the red blotches on the body that get tested?

How long does that particular bacteia take to grow in the tub?

Can you get rid of it without draining the tub (oh lord yet again it's going to minus 18 tonight???)

Can you switch from a bromine tub to a chlorine tub by letting the levels drop first and then switching without having to empty again?

Any answers/advice to my querys is really appreciated. There is just waaaaaaay too much info/reading here and the more I read the more confused I get. Please use the kiss method and my brain is full.

Thanks !!!!!!!!!!

Link to comment
Share on other sites

Wow...this post is kind of old!

Hope "The Man" does not still have you feeling down Chem Geek.

I hopped on this forum way after this post was started, So I didn't know you were a punching bag for a while.

Just a heads up, your expertise and advice has made my tubbing experience much, much better.

I am down to about 5-10 minutes per week of attention that my tub needs for maintenance.

On another note, I understand how you can feel about getting beat up on a forum, as you have probably noticed about my posts, some are a bit on the edge...I get a little carried away. This leaves me open to a whole bunch of sucker punches.

never sweat the petty....but make sure pet the.....well I think you know the rest!

Thanks again!

Link to comment
Share on other sites

First my intention is not to dig up old crap with posting to this thread!

This is just a thread that had the most info in it for what I am looking for.

I skip over garbage posts to find the real information shared out of the goodness of someones heart!!!

Just incase you were thinking/asking.

Link to comment
Share on other sites

I'm sorry you've been having problems with red spots (and a leak, but at least that appears to have been fixed). You should look at the table in this link and see if you think you have a chemical reaction vs. a bacterial infection.

Some people are sensitive to bromine and some (though fewer) to chlorine, so it's possible that it is the bromine.

You can't easily test for bacteria. You can see a competent doctor who can tell you if your spots are from a bacterial infection, but he/she would need to take a swab and have it tested to be sure. The bacteria that causes hot tub itch (Pseudomonas aeruginosa) is rather ubiquitous so can be on your skin already -- it's when it grows uncontrolled in hot tub water and overwhelms your natural defenses that it becomes a problem, usually in areas with cuts or abrasions or weakened skin.

Bacteria can double in population every 15 to 60 minutes. So one bacteria can become over 4 billion in just 8 hours, though realistically their growth is more limited. Nevertheless, you can certainly have enough bacteria to cause a problem if the sanitizer is near zero for just half a day (I wouldn't want it zero for more than a few hours). The hot tub itch bacteria tends to form biofilms quite readily after which it will be far more resistant to getting killed from a sanitizer. So the key is to kill the bacteria before it can form any substantial biofilms and that means maintaining a sufficient sanitizer level at all times.

The normal decontamination procedure does require draining the tub, doing a super chlorination and/or using Spa System Flush, and then dumping again and refilling with fresh water. That is the surefire way of killing everything in the tub. A link on the decontamination procedure as well as other useful links (mostly for the Dichlor-then-bleach method) is here.

As for switching to chlorine, this unfortunately does require a drain/refill unless you only just started using bromine and didn't add a large bromide bank (i.e. didn't add a lot of sodium bromide) or use tablets for too long.

Link to comment
Share on other sites

First my intention is not to dig up old crap with posting to this thread!

This is just a thread that had the most info in it for what I am looking for.

I skip over garbage posts to find the real information shared out of the goodness of someones heart!!!

Just incase you were thinking/asking.

Easy turbo....no one was slinging mud.

Link to comment
Share on other sites

THANK YOU ! chem geek!!! That article was bang on. I'm guessing chemical rash for sure. Not so much itchy but dang sore welts that came on so fast (10 min or less)

Our tub has had 4 complete Spa System Flushes & wash downs in a week, so I was really thinking nothing bacterial could have survived that.

So I'm now thinking my husband can play guinea pig with himself and when (or if) he gets this chem balance under control, I'll try it one more time. I may very well be over sensitive to Bromine. I have never had a problem with chlorine in our pool, so I'll keep my fingers crossed.

A better test kit is in order for sure. I don't think running back and forth with water to a dealer is watching closely enough.

So thank you again from my spotty self.... wish us luck!!!

Link to comment
Share on other sites

Join the conversation

You can post now and register later. If you have an account, sign in now to post with your account.
Note: Your post will require moderator approval before it will be visible.

Guest
Unfortunately, your content contains terms that we do not allow. Please edit your content to remove the highlighted words below.
Reply to this topic...

×   Pasted as rich text.   Paste as plain text instead

  Only 75 emoji are allowed.

×   Your link has been automatically embedded.   Display as a link instead

×   Your previous content has been restored.   Clear editor

×   You cannot paste images directly. Upload or insert images from URL.

Loading...


×
×
  • Create New...