Sensitive To Bromine?

[Brookdog]

We have a hot tub sanitized with bromine and MSP using the 3 step method. After adding Borax a few weeks ago, I am able to keep the pH around 7.5 to 7.8, the TA is at 50 and the Br fluctuates from 1 to 5 with the CA at 150 with not much work.

My problem and question is that my wife experienced a burning sensation in her woman areas after having a soak this weekend. She hadn't been in for a couple weeks because we were away for a while, but noticed it shortly after getting out. Neither my daughter or myself have had any discomfort from the spa and we use it 3-4 time a week.

Is it possible that she could be sensitive to bromine? Could it be the temp of the spa (102)? How could we test to see if it the bromine or maybe some other issue with the hot tub? I did a Spa Purge and decon a month ago and the spa seems to look and smell fine.

Maybe we could ask to use someone elses spa, both bromine and clorine, and see if they are irritating to her. Could I add some bromine salts to the bath tub and see if that bothers her? I hate to experiment using my wife, but I don't know where to go from here. Thanks for any advice you might have.

[quantumchromodynamics]

It could be the MPS (Potassium monopersulfate or Potassium peroxymonosulfate) or the sulfates.

Is this a new issue? Have you made any changes to the chemistry that could explain it? I mean, if she wasn't having problems before, then what are you doing differently now that you didn't do before?

It is most likely chemical as opposed to bacterial due to the immediacy of the reaction.

Are you adding the MPS or other oxidizer before or after tub use?

Try draining, refilling and not using any sulfate products such as dry acid or MPS. You can use regular, unscented Clorox bleach to shock instead of MPS.

If you are using bromine tabs, you might want to switch over to DBDMH (1,3-Dibromo-5,5-dimethylhydantoin) type tabs, like Brilliance. They seem to work better for some people.

Brilliance MSDS

2KHSO₅ + KHSO₄ + K₂SO₄ + H⁺ + 4e^- --> 5K⁺ + 4SO₄^2- + 2H₂O

(2KHSO₅)(KHSO₄)(K₂SO₄) + 2Br^- --> 5K⁺ + 4SO₄^2- + 2HOBr + H⁺

[rckymtntim]

My issue (I think) was with MPS. I got a rash on my legs. I stopped using MPS and go with Nitro's bleach method without using any MPS just the clorox bleach. Things seem to be going well for me now.

Tim

[Brookdog]

Thank you both for your replies.

To answer QCD's questions, we got the tub in December. I neglected to flush the tub first, and just washed it and filled it up. During the first week, wifey complained of sensitivity and went on treatment for a UTI.

I thought (knew) it was contaminated, so I drained, flushed and deconed the tub. She stayed out because we were going on vacation. When we got back last week she went in again and felt the discomfort again.

I am using Leisure Time products, Brom Tabs, that are 1-bromo 3-chloro5, 5 dimeth--- 60%, 1,3 dichloro-5, 5-dimeth--- 27.4%, 1,3 dichloro-5, 5ethyl-5-methylhdantoin 10.6%. Are these the BCDMH tabs? I use the Leisure TIme OZ shock tabs for ozone spas, Potassium Peroxymonosulfate 32.25%. I throw in 4 tabs after about 1 man hour of soak time. Always after, not before a soak.

I can try draining and refilling but it is not the best time of the year. When I do, you suggest not to use dry acid. Would that mean using muratic acid to lower the pH? I would prefer not to use the liquid acid if possible. I have powdered sodium bisulfate and liquid sodium bisulfate at 27%. I use alk increase that is sodium hydrogen carbonate at 100%.

Can I still use the Borax on the new refill? I didn't have any in the first fill, so I don't think that is a problem.

Is it proper to put 1-2 brom tabs in the floater each week to keep a reserve and to shock after use to oxidize? Does the shock revive the bromine level? I haven't looked to see, but will the bromine level go up just by adding the OZ tabs or do I have to increase the brom tabs in the floater.

Thanks for all your help. It's coming slowly, but I think I'm getting this balance thing....

[quantumchromodynamics]

You have BCDMH + DCDMH + DCEMH.

BCDMH + DCDMH + DCEMH (1-bromo-3-chloro-5,5-dimethylhydantoin + 1,3-dichloro-5,5-dimethylhydantoin + 1,3-dichloro-5-ethyl-5-methylhydantoin) is a newer formulation (Sometimes referred to as Dantobrom).

Brilliance is DBDMH (1,3-dibromo-5,5-dimethylhydantoin). It has a higher pH than the other formulations and is more pH neutral.

I suspect that the sulfates from the dry acid and the MPS are the most likely cause. You can use muriatic acid instead of dry acid (sodium bisulfate) to lower pH or alkalinity.

I think that this is going to come down to a process of elimination. You are probably going to have to try different methods and see what works.

Method 1: Eliminate sulfates to see if that is the issue.

Method 2: Switch to DBDMH to see if that works.

Method 3: Eliminate DMH (dimethylhydantoin) by not using bromine tabs. Just shock with regular, unscented Clorox bleach.

Method 4: Switch over to chlorine instead of bromine.

You should be adding about 30 to 50 ppm of sodium bromide after every refill for a bromine tub. Are you adding the sodium bromide?

You can add borates from Borax or boric acid on a new fill.

It is important to maintain consistent sanitizer levels at all times to prevent bacterial growth and to help eliminate bacteria as a contributing factor to the problem.

If the problem is bacteriological or fungal, then the heat might be making an underlying infection suddenly become noticeable. You should consult a doctor if you think that this might be a medical issue.

Is it proper to put 1-2 brom tabs in the floater each week to keep a reserve and to shock after use to oxidize?

Yes, that's fine.

Does the shock revive the bromine level?

Only if there is enough bromide in the water.

I haven't looked to see, but will the bromine level go up just by adding the OZ tabs or do I have to increase the brom tabs in the floater.

The bromine will go up from adding MPS only if there is enough bromide in the water.

I use alk increase that is sodium hydrogen carbonate at 100%.

Sodium hydrogen carbonate is sodium bicarbonate. It is the exact same thing as regular Arm & Hammer baking soda.

[quantumchromodynamics]

I think that this might be a sanitizer related issue, especially if you didn't add 30 to 50 ppm of bromide to the water on startup. (38.635 grams of sodium bromide per 1,000 liters)(0.51582 ounces weight per 100 gallons).

When you add MPS to the water, and the water has enough bromide, then the MPS will oxidize the bromide to bromine, which is a good sanitizer.

However, if there is not enough bromide in the water, then the MPS will stay as MPS, which is a good oxidizer, but it not as good of a sanitizer as bromine.

MPS will show up as bromine on a bromine test and you could think that you have enough bromine when it is really MPS.

For bromine, it is important to add 30 to 50 ppm bromide to the water on startup. You should also use a chlorine shock on a regular basis to ensure good sanitation.

You can use sodium hypochlorite, lithium hypochlorite or dichlor to shock (dichlor should be limited to a cumulative total of 2 ounces per 100 gallons of spa water on any single fill of the tub).

See this reference for bromine related sensitivity.

Reference 2

It is my personal hypothesis that DMH might be responsible for some of the issues normally attributed to bromine use, such as smell and sensitivity.

[Brookdog]

Yes, I did add 2 oz of sodium bromide after the last refill, so I'm thinkinig that the sanitizer levels are in order.

I can try using Clorox to shock instead of the MPS. I think Chem Geek recomends 5oz of 6% per person hour. Will this reactivate the bromine, or am I turning towards a clorine spa?

Any idea how long it takes for the MPS to be out of the water?

Can I still measure the sanitizer with my Taylor 2106 kit?

What about CYA?

Should I just drain and refill as a clorine spa?

I will get some muratic acid and use that for the pH decrease adjustment.

Thanks again for all your help.

[quantumchromodynamics]

I think that your best option would be to drain, refill and switch over to the dichlor/bleach method. Don't use MPS or dry acid. Also, don't use the "liquid sodium bisulfate at 27%"; It is sulfuric acid.

You can get the FAS-DPD chlorine test as a stand-alone kit # K-1515-A

Or, you can get the entire kit # K-2006.

Decontamination

Clean filters 1

Clean filters 2

Nitro's approach to water maintenance

Chlorine demand

Dichlor/bleach Method In A Nutshell

[chem geek]

My answers to your questions in your quote below.

Yes, I did add 2 oz of sodium bromide after the last refill, so I'm thinkinig that the sanitizer levels are in order.

I can try using Clorox to shock instead of the MPS. I think Chem Geek recomends 5oz of 6% per person hour. Will this reactivate the bromine, or am I turning towards a clorine spa?

If you keep the bromine, but use Clorox to shock instead of MPS, it is still a bromine spa. The chlorine just reactivates bromide to bromine.

Any idea how long it takes for the MPS to be out of the water?

MPS will stick around if there is nothing to oxidize, but with a bromide bank it should not stay around for very long (minutes).

Can I still measure the sanitizer with my Taylor 2106 kit?

The FAS-DPD in the K-2106 only measures Total Bromine, so though it could measure Total Chlorine by dividing by 2.25 (i.e. count as 0.2 ppm per drop with 25 ml sample or 0.5 ppm per drop with 10 ml sample), you really need to distinguish between FC and CC so should get the K-1515-A kit QCD referred to and can get it at a good price here which has 36% more volume of reagents than Taylor version (it's still Taylor reagents, just repackaged).

What about CYA?

If you stick with bromine, then CYA doesn't matter. If you drain and refill and switch to chlorine, then use the Dichlor-then-bleach method as described in this post.

Should I just drain and refill as a clorine spa?

Up to you, but if you want to switch to chlorine, then you do need to drain and refill (and probably decontaminate to be on the safe side)

I will get some muratic acid and use that for the pH decrease adjustment.

Thanks again for all your help.

[Brookdog]

Thanks QCD and chem geek. Talking to my wife, it seems she has other reactions to sulfates; like headaches after drinking wine. So, I guess I need to get away from the sulfates.

I just was starting to get a grip on the whole bromine thing... Now I will need to read up on the clorine way to sanitize. I like simple, like everyone else.

Should I look at the BBB method or is there any other?

Is the BBB method sulfate free?

I need to get the new Taylor kit, so I will stay with the bromine until it comes in.

Anyone need some Brom Tabs and OZ tabs???

Thanks again.... I'll be back after the switch to clorine.

[quantumchromodynamics]

Since you have the K-2106, all you need to get are the following reagents to test for Free and Combined chlorine and cyanuric acid:

R-0013-C (Cyanuric acid test reagent)

R-0871

R-003

(The chlorine test also uses reagent # R-0870, which comes with the K-2106.)

Instructions

Cyanuric acid testing using less reagent.

If you think that the reaction is only to sulfates, then you can continue to use bromine. Sulfates come from MPS and dry acid.

Even though the active part of MPS will not last long, the sulfates that are produced do not go away. You have to drain and refill to get rid of them.

It could be the bromine or the DMH in the bromine tabs, so I think that switching to chlorine would be best.

Nitro's approach to water maintenance

[chem geek]

Just so you know, the problem your wife (and many people) have with wine is sulfites (SO₃^2-), not sulfates (SO₄^2-) and though related, they are not the same. Also, you would need to drink the water to get the headache issues. Nevertheless, moving away from non-chlorine shock (MPS) in general is certainly something to try.

Yes, the Dichlor-then-bleach (or even Dichlor-only) method is sulfate free so long as you use Muritatic Acid for pH control instead of dry acid. However, as QCD noted, I suspect the reaction may have more to do with bromine (or DMH).