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Why do I have high Cyanuric acid in Bromine Spa?


spanewb

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I have an indoor spa that I treat with Bromine.  My Cyanuric acid levels are reading as very high (~300 ppm).  While I'm aware that to lower those levels, the only solution is to add water (or drain and restart), however my questions are more about how it got there. 

From my research, i've seen that CYA accumulates because it is a stabilizer for Chlorine, but since I'm using Bromine, I'm wondering where the CYA is coming from?

Additionally, are these high CYA levels an issue with a Bromine spa? Ie does it reduce the effectiveness of Bromine, and also is it a health hazard?

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  • 2 weeks later...

CYA is a component of your oxidizer that you are probably using to generate bromine.  Regular use of granular dichlor, for example, (or the chlorine variant that is found in bromine tablets) produces bromine from the bromide salts already in the water

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By itself, CYA is a relative "don't care" as regards bromine.  that is, CYA does not moderate the strength of bromine.  however, with CYA levels 10 times the recommended normal for Spas, I would start to wonder if you are using extraordinary amounts of chlorine just to generate the bromine.  so you would have a catch-22:  your chlorine is what generates bromine from bromide, but your chlorine is so heavily moderated by CYA that it isn't a very effective oxidizer.  So you end up using even more chlorine just to obtain bromine!  ergo, an ever-increasing level of CYA.  and since you are "shocking" with bromine you are also contributing to the CYA level -- because  bromine is generated by oxidizing bromide salts. and Chlorine is a good oxidizer!  

I think I would advocate for starting over, in this case.  Im a big fan of SIMPLE -- there is no need to use a floater for bromine (unless you want to) and you can maintain a bromine spa exactly as you would a chlorine spa -- with granula chlorine.  in your situation I think I would purge with ahh-some and restart.  

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Thank you all.  I think that Dlleno is right that the high CYA levels may have been inhibiting the bromine.

I'm a bit confused about the statement "your chlorine is what generates the bromine from bromide...", as I'm not using chlorine. I take it that there is chlorine in the 2-in-1 bromine sanitizer?  The bottle says 14.7% sodium bromide and 82.5% sodium dichloro-s-triazinetrione.  Is the latter one a chlorine I'm guessing?

I take it that shocking with this sanitizer may be adding too much bromine, too much CYA, and not reactiving the existing bromine?

Anyways, I've drained and started from scratch.  The bad fumes I was having are gone, and I was surprised to see how little bromide it took to bring the levels to their ideal - much less than it was taking previously, which I think again supports the idea that maybe the CYA was inhibiting something.

 

What is your ideal method for bromine treatment?  Should I use this sanitizer mix, or is it better to have them separate so I can shock with a non-chlorine oxidizer and then see what the levels look like before adding additional bromine?  Should I use a float or is it better to only add as needed or after use?  I'd love to hear your process and exactly what chemicals you use!

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a few points on bromine:

just to be precise:  CYA doesn't inhibit bromine, it inhibits chlorine, so that there isn't enough active chlorine to oxidize sodium bromide into bromine sanitizer  

technically speaking, there is no such thing as "adding bromine to a spa" in the same sense that you "add" chlorine.    the various ingredients responsible for producing bromine  in the water are often packaged together and referred to as "adding bromine" but all of them rely on the same process:  sodium bromide (a salt), when exposed to an oxidizer (like chlorine or ozone) produces the bromine sanitizer, which is really hypobromous acid.  Sometimes, one of the ingredients, Sodium Bromide, is referred to as "bromine", but by itself Sodium bromide does nothing useful.

As you have noted, the packaged preparation of "bromine granules" is nothing more than a combination of sodium bromide and ordinary "dichlor".  It works and  it is useful -- I have used it before in a pinch, but it is not the best way to produce a bromine spa . its basically a "one step" solution that combines the two critical ingredients together -- just like a puck or tablet does -- only in granular form.  the problem with the one-step granular bromine, while it is simple, is that (a) upon a fresh fill you don't have a bromine spa yet because there isn't enough sodium bromide present to produce bromine.  so you end up with a combination of chlorine and bromine at first . (b) as you use the granules over time you will build up the sodium bromide bank beyond what is necessary and so the stuff becomes, basically, a weakened version of dichlor chlorine that is only 85% as strong as normal dichlor.  Really there is no problem using the stuff, but you're better off supplying your own bromide bank (sodium bromide is cheap) and using straight dichlor.  

Any time you add dichlor to a spa you are adding CYA, which is there as a stabilizer.  Its a good thing, because without it, swim suits wouldn't last as long.  However, just as in the bromine problem above, CYA continues to accumulate in the water as you add dichlor.  this is why many of us stop using dichlor after a few weeks and use straight bleach.  pure, ordinary un-adulterated bleach found at the grocery store.  once sufficient CYA has accumulated there is no need to add more CYA (in the form of dichlor) so thats why we switch to bleach.    the challenge with this approach is that bleach is net pH positive, while dichlor is net pH  neutral or slightly negative during the oxidation process.  Bleach users typically have more issues with pH drift.  

by now you may have realized that we bromine proponents have a very interesting and wonderful advantage:  because CYA is a don't care, we really don't care (well unless you get to the point where there is way too much, as in your case!) To illustrate this point, however,  I have run my bromine spa WITHOUT ONE GRANULE OF DICHLOR.  yup, straight pure  un-adulterated 6% sodium hypochlorite ( bleach) from the grocery store.  With sodium bromide already in the water, bleach is just an oxidizer and it makes bromine.  I don't recommend this for others because there are some risks -- spa stores heads explode, for one thing --- and a variety of self-proclaimed chemistry geeks start to predict certain doom because they don't fully  understand it --  so I did it to prove a point.   Now, however,  Instead of using straight bleach  I use dichlor until I have built up about 30ppm CYA and then I switch to bleach.   (the reason you have to be careful with straight bleach is because, during the bromine conversion there is a short period of time when un-moderated chlorine is present in the water)

Personally, my bromine method, from a fresh fill, is very simple:  you treat it exactly like you would a chlorine spa, using dichlor, only you add the  bromide bank "up front"

  1. balance and heat water
  2. add sodium bromide bank (either granular or liquid forms are available)
  3. use dichlor for sanitizer on a regular basis . after a few weeks you can switch to bleach (to avoid building up too much CYA) 

 

floaters:  they work, although I'm not a fan.  if there is no need for automated sanitizing in a chlorine spa there is no need for such in a bromine spa.  the problem with floaters is that you can over-sanitize and cover up, for example, a problem with biofilms.

shocking a bromine spa:  this is perhaps the only disadvantage of a bromine spa-- anything you shock with, i.e. dichlor, MPS, bleach -- even ozone-- , will produce bromine.  there is no such thing as a "non-bromine" shock because they all oxidize bromide salts into hypobromous acid ("bromine ") if there is sodium bromide in your water. so "shocking a bromine spa" is really just raising the bromine level to some high amount (this is a good thing, from time to time).   The other disadvantage is that if you shock too high it can be days before bromine subsides to the point where you can get in, because there is no way (as with chlorine) to neutralize bromine.  This can be a problem for spas that do not have biofilms present (yea its true,  hear me out...).  in too many cases, biofilms are present and actually consume sanitizer (produce a steep decay rate) and those with floaters or automatic dispensers are none the wiser -- so when it comes time to shock, they don't even notice that it doesn't take very long before its safe to enter the spa -- the bad guys have been consuming it!  I once shocked my bromine spa to the teens (15ppm bromine) and it took all week to get it back down to 4.  this is partly because I have an ozone generator. 

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Thank you for the detailed response!

Forgive my ignorance, but my understanding of the point of using bromine was to avoid using chlorine.  If we are using dichlor / bleach to oxidize the bromide, what is the difference between that and a spa that uses chlorine rather than bromine?

Another question - my understanding was that bromine binds with the organics and loses some ability to keep doing so, and that using a "shock" oxidizer sort of tears those bindings up and then leaves the bromine more able to bind again.  Is that way off?  I guess I'm wondering whether bromine actually disappears after a while (and so more bromide needs to be added to make more bromine), or whether it just loses "strength" and can be reactivated with the oxidizer thus yielding higher bromine levels after the fact without having added any more bromide.

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oh no problem -- I think its just terminology thats getting in the way. 

bromine:  a highly toxic element, in the Periodic Table with atomic number 35, that should never enter your spa and you should never touch it.  no spa or spa show room will ever have  elemental bromine anywhere near a human being 🙂

hypobromous acid:  the halogen sanitizer present in a "bromine spa", which is a relative of hypochlorous acid ("chlorine").  its what kills the bad guys 

sodium bromide:  the salt that is used in the chemical reaction to produce hypobromous acid via some oxidizer (like MPS, Chlorine, or Ozone). 

for purposes of discussion it is best to use the term, "bromine" to refer to the sanitizer that does the work, i.e. hypobromous acid. Spa showrooms are notorious for confusing terms and selling you "bromine" when that could  be either of three things:  (1) actual sodium bromide salts, (2)  brominating granules, or (3) bromine tablets.  the last two (granules and tablets) are typically a combination of chlorine and sodium bromide in expensive containers. 

when you operate a bromine spa you are indeed avoiding "chlorine" for the intended purpose of choosing "bromine" over "chlorine". its just that chlorine is an intermediate step to producing the bromine!    when the conversion from bromide salts to bromine is complete, there is no longer any chlorine in the water -- assuming a sufficient bromide bank of course, ALL of the chlorine you add to the water is consumed in the process of making bromine.  the only way you will have chlorine in the water is if there is insufficient bromide salts in the water -- in this case the chlorine oxidizer will convert what it can to bromine, and the remainder will still be chlorine.  typically, this is only an issue if you are using the 85/15 "bromine granules":  when you put your first teaspoon of this stuff in  the water, there is not enough bromide to produce a bromine spa.  ergo, you have a combination bromine and chlorine spa. after you keep dumping in teaspoons of 85/15, the "15" (sodium bromide) will build up and you'll have a bromine spa after several applications but not before.  This formulation is marketed as an easy "1-step" bromine sanitizer but makes some compromises that I pointed out earlier.  

the magic of bromine, if you will, is that when bromine sanitizer (hypobromous acid) does its work (kills the bad guys) it returns to the water as sodium bromide.  so you have this veritable circle of life going on:  Bromide-->bromine-->Bromide going on.  so if you start out with sufficient bromide salts in the water (a "bromine start-up" product, which is just sodium bromide) then when you add chlorine to your water -- ALL of the chlorine you add will be used to convert bromide to hypobromous acid (the "bromine" sanitizer).  Then,  when the bromine sanitizer gets used up, it will return to the bromide bank to be used all over again.  

the conversion from bromide to bromine is not instantaneous but for all practical purposes it is -- you can tell by the fresh bromine smell of your water. The last time I looked into this, if memory serves, the conversion process was on the order of seconds.  just keep in mind that you are not adding "bromine" to your water:  you pre-treat with a bromide bank and then add chlorine as an oxidizer that converts the bromide salts to  bromine sanitizer (hypobromous acid). 

its true that the above is not a perfect perpetual motion machine with no losses.  the bromide bank doesn't stay "the same size"    for  most part, however, this is a "don't care" because you can just add more bromide salts to the water (or add enough to begin with). The bonus of bromine sanitizer is that when it  "used" it does not produce the  chloramine byproducts as chlorine sanitizer does  --it turns back into bromide salts!  yea there are some byproducts, but they aren't as nasty as the the chloramines and are easily addressed with occasional use of MPS as the oxidizer.  my understanding is that MPS prolongs the conversion, so that MPS acts as MPS longer in the presence of bromide -- thus giving it a better chance of attacking bromine by products.  of course, "shocking" a bromine spa is much like shocking a chlorine spa -- you just end up with a high sanitizer level.  

Im afraid I'm not following you re:  bromine losing "strength".  when it  kills bad guys,  hypobromous acid returns to the combination of some byproducts of oxidation and sodium bromide salts, the latter of which is then reactivated next time you add an oxidizer (such as dichlor or MPS).  the lunch isn't entirely free, and its always a good idea to oxidize from time to time with a non-chlorine compound (like MPS) because that will go after the 'some byproducts' piece of the equation. 

so -- does bromine actually "disappear" after a while?  well ---  hypobromous acid (the bromine sanitizer) will get converted back to sodium bromide salts, with some imperfect losses.  in that sense it "disappears" until it is oxidized again, into hypobromous acid.  

does bromine "loose strength":  well just like its hypochlorous acid cousin, , hypobromous acid (the bromine sanitizer) gets consumed when it attacks bad guys, and thats why sanitizer levels go down.  Probably the expression "bromine looses strength" could refer to the fact that the sodium bromide bank can become depleted --- which is why we start with a big one 🙂.  as a matter of practicality I have never encountered this problem throughout the useful drain interval of a bromine spa.  And in fact is so easy to fix its just not a "thing" in my mind -- its just sodium bromide.  

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  • 8 months later...

Good stuff. However you still haven’t made clear what the problem is with the high CYA levels that result from:

1) starting the fresh fill with a sodium bromide reserve 

2) manually using small amounts of a 2in1 shock with 85% dichlor and 15% sodium bromide with each use of the tub

3) once a week shocking with MPS
 

ok so doing this would add more and more CYA and sodium bromide.   But what’s the downside to this?  What does it matter if I have more sodium bromide than needed or if the CYA levels get too high.  My understanding is that high CYA prevents chlorine from killing germs, NOT from making hypobrombus acid....

 

put another way, what is wrong with the 3 step approach is be defined above?  What’s the problem?

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I am no chemistry expert but as I understand it, cya "buffers" the reactivity, or oxidation reduction potential (orp), of chlorine, not just with "germs" but with everything, including bromide. Since it is oxidation that generates bromine from bromide, reducing the oxidation potential also reduces the amount of bromine produced. Bromine itself is not affected by cya.

@waterbear, @Cusser, @dlleno, am I fairly close?

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On 4/29/2020 at 2:12 PM, spanewb said:

Thank you for the detailed response!

Forgive my ignorance, but my understanding of the point of using bromine was to avoid using chlorine.  If we are using dichlor / bleach to oxidize the bromide, what is the difference between that and a spa that uses chlorine rather than bromine?

Another question - my understanding was that bromine binds with the organics and loses some ability to keep doing so, and that using a "shock" oxidizer sort of tears those bindings up and then leaves the bromine more able to bind again.  Is that way off?  I guess I'm wondering whether bromine actually disappears after a while (and so more bromide needs to be added to make more bromine), or whether it just loses "strength" and can be reactivated with the oxidizer thus yielding higher bromine levels after the fact without having added any more bromide.

@dlleno what is the rate of adding bleach?  How many Oz per gallons?

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11 hours ago, mscdman said:

ok so doing this would add more and more CYA and sodium bromide.   But what’s the downside to this?  What does it matter if I have more sodium bromide than needed or if the CYA levels get too high.  My understanding is that high CYA prevents chlorine from killing germs, NOT from making hypobrombus acid....

 

put another way, what is wrong with the 3 step approach is be defined above?  What’s the problem?

The problem with CYA is that it buffers or moderates the effectiveness of chlorine, whether that chlorine is used directly to oxidize bad guys, or that chlorine is used to oxidize sodium  bromide into hypobromous acid. We should  challenge that, however.  The advantage of the bromine spa is that CYA can climb, yes,  but it will take increasing amounts of chlorine to overcome the CYA and produce the bromine levels you want (thats what we need to validate).   As you can see, the natural remedy is just to add more dichlor because as long as you have enough hybobroumous acid (" bromine" as measured by a drop-wise test like Taylor 2106) then you  have met your sanitization objective and CYA is by itself a don't care.  

I have used the 15-85 concentration of "bromine granules" myself.  there really is no problem unless you care about:

1.  A mix of chlorine and bromine during the first few applications (not enough bromide reserve) 

2.  an over-abundance of sodium bromide near the end of the drain interval (more than enough bromide reserve)

3.  the use of ever-increasing doses of dichlor to acheive the same ppm level of bromine ,owing to the accumulating CYA (what we need to challenge)

4.  the resultant TDS rise from dumping unnecessary stuff into your water, which could reduce the drain interval

in short -- I don't see a problem other than shortened drain intervals.    I'm about to do an experiment my self re: the rising CYA levels, but if you're using the 15/85 granules that would be a good experiment too.  record the volume (like teaspoons) of the mixture that is required to achieve x PPM bromine and record that over time.  I'm interested to know of (3) above is a nothing burger or significant.  If the "CYA moderates chlorine" theory is true, then you'll have to dump more and more dichlor to acheive the same  bromine level. 

In short, the theory tells us that (1) CYA is a problem for Chorine  because the measured levels of chlorine are not commensurate with the oxidizing power and (2) CYA is not a problem for bromine spas because the measured bromine levels are in fact commensurate with the oxidizing power.  Even if it takes more dichlor to achieve said bromine level.  

or you could just switch to bleach!

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1 hour ago, mscdman said:

@dlleno what is the rate of adding bleach?  How many Oz per gallons?

you can go to the pool calculator.  there's an browser-based app there that will tell you.  it depends on the sodium hypo concentration you find on the store shelves.

 

1 hour ago, mscdman said:

Forgive my ignorance, but my understanding of the point of using bromine was to avoid using chlorine.  If we are using dichlor / bleach to oxidize the bromide, what is the difference between that and a spa that uses chlorine rather than bromine? [/quote]

the difference is that the chlorine is used to oxidize sodium bromide into "bromine" sanitizer, instead of attacking bad guys directly .  so what is left in the water is not chlorine but in fact bromine.  the chlorine is just a means to an end

1 hour ago, mscdman said:

Another question - my understanding was that bromine binds with the organics and loses some ability to keep doing so, and that using a "shock" oxidizer sort of tears those bindings up and then leaves the bromine more able to bind again.  Is that way off?  I guess I'm wondering whether bromine actually disappears after a while (and so more bromide needs to be added to make more bromine), or whether it just loses "strength" and can be reactivated with the oxidizer thus yielding higher bromine levels after the fact without having added any more bromide.

yes, periodic use of MPS instead of chlorine will also make bromine, and the MPS (because it works slower) ends up killing some bad guys on its own before going to work on the sodium bromide. you just can't  use MPS as a "non chlorine shock" in a bromine spa or you will end up with some very high bromine levels!

The bromine conversion is not a lossless perpetual motion machine, for sure, so its possible that the bromide bank would need to be replenished.  its just that the bromine tablets (and bromine granules) over time will probably end up adding way more bromide than necessary.  

I just use the smell test 🙂  if it smells like bromine I'm good .

  

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20 minutes ago, dlleno said:

The problem with CYA is that it buffers or moderates the effectiveness of chlorine, whether that chlorine is used directly to oxidize bad guys, or that chlorine is used to oxidize sodium  bromide into hypobromous acid. We should  challenge that, however.  The advantage of the bromine spa is that CYA can climb, yes,  but it will take increasing amounts of chlorine to overcome the CYA and produce the bromine levels you want (thats what we need to validate).   As you can see, the natural remedy is just to add more dichlor because as long as you have enough hybobroumous acid (" bromine" as measured by a drop-wise test like Taylor 2106) then you  have met your sanitization objective and CYA is by itself a don't care.  

I have used the 15-85 concentration of "bromine granules" myself.  there really is no problem unless you care about:

1.  A mix of chlorine and bromine during the first few applications (not enough bromide reserve) 

2.  an over-abundance of sodium bromide near the end of the drain interval (more than enough bromide reserve)

3.  the use of ever-increasing doses of dichlor to acheive the same ppm level of bromine ,owing to the accumulating CYA (what we need to challenge)

4.  the resultant TDS rise from dumping unnecessary stuff into your water, which could reduce the drain interval

in short -- I don't see a problem other than shortened drain intervals.    I'm about to do an experiment my self re: the rising CYA levels, but if you're using the 15/85 granules that would be a good experiment too.  record the volume (like teaspoons) of the mixture that is required to achieve x PPM bromine and record that over time.  I'm interested to know of (3) above is a nothing burger or significant.  If the "CYA moderates chlorine" theory is true, then you'll have to dump more and more dichlor to acheive the same  bromine level. 

In short, the theory tells us that (1) CYA is a problem for Chorine  because the measured levels of chlorine are not commensurate with the oxidizing power and (2) CYA is not a problem for bromine spas because the measured bromine levels are in fact commensurate with the oxidizing power.  Even if it takes more dichlor to achieve said bromine level.  

or you could just switch to bleach!

If you are hypothesizing that using the 85/15 concentrate regularly after use will increase CYA and therefore require more and more 85/15 mixture to reactivate bromine then would I be better with a daily/regular shock of MPS and then a weekly 85/15 all in one?

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3 minutes ago, mscdman said:

If you are hypothesizing that using the 85/15 concentrate regularly after use will increase CYA and therefore require more and more 85/15 mixture to reactivate bromine then would I be better with a daily/regular shock of MPS and then a weekly 85/15 all in one?

well not really because the 85/15 doesn't (when the water is new) provide enough  bromide for the MPS make bromine, and MPS isn't as good of an oxidizer as chlorine.  Personally I build the bromide bank once at startup, and then use bleach to make bromine. it makes heads explode in the spa stores but I gotta say it works.  yea I start with some dichlor just to make me feel better (have more than zero CYA),  but as a practical matter just use bleach and weekly MPS to make the bromine.

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7 minutes ago, mscdman said:

@dlleno where is the pool calculator?

also when you test for bromine are you testing with strips and if so are you checking FREE or TOTAL bromine?

just search google for TFP pool calculator.

Taylor 2106 measures total bromine.  the concept of free vs total isn't really valid in a bromine spa -- total bromine is the sanitizer

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3 hours ago, RDspaguy said:

I am no chemistry expert but as I understand it, cya "buffers" the reactivity, or oxidation reduction potential (orp), of chlorine, not just with "germs" but with everything, including bromide. Since it is oxidation that generates bromine from bromide, reducing the oxidation potential also reduces the amount of bromine produced. Bromine itself is not affected by cya.

@waterbear, @Cusser, @dlleno, am I fairly close?

this is it, in a nutshell.  

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just temporarily pretend you have a chlorine spa and use the pool calculator to determine the amount of free chlorine that you want to target.  the conversion to total bromine will happen naturally in your spa when you add the prescribed amount of free-chlorine in the form of bleach (if you have sufficient bromide bank).     for example, pool calculator might say 4 ounces of 6% bleach for 3ppm FC in a 500 gallon spa (no idea if those are correct numbers but play along with me here) --  that means 4 ounces of bleach will generate  3ppm of FC if you have a chlorine spa (no bromide present).  The same amount of bleach will produce 6.6 ppm total bromine if that bleach finds enough  sodium bromide to oxidize.  The magic math is that the atomic mass of elemental Br is 2.25 times that of elemental Cl.  So Voila you just use "free chlorine numbers" to achieve recommended "total bromine" levels.  its really quite wonderful.

just remember that measurement error occurs.  you'll end up figuring out pretty quickly how much bleach will produce the desired amount of total bromine.  People may even look at you funny when you read the label in the grocery store to see if they are selling you 6% bleach or something else.   and get a Taylor 2106 -- the drop-wise DPD test kit.  you will need real measurements not approximations from colored strips.  

oh one more thing -- do NOT, under any circumstances, get splash-free or scented bleach or anything fancy:  you'll have a mess on you hands in no time.  You want just pure un-adulterated "regular bleach"  that contains only  sodium hypo -- read the label.  I have to admit I spent an unusual amount of time the other day at Costco because they were selling some enhanced bleach of some sort with "CloroMax technology".  Turns out it was just 7.55% sodium hypo instead of 6%.  good stuff.  

I always leave the cover off for a minute,  but that's about it.  It's true that granular chlorine will dissolve slower than you can pour in 6% bleach, but the sky doesn't fall.   the spa stores are so allergic to bleach that they telegraph a fear that spills over into the rest of us.  I've heard all kinds of tales, from ruining the shell, to destroying "your equipment".  its just chlorine for pete's sake -- a liquid version of what the granules are.  I use a 1C measuring cup and just eyeball fractions thereoff -- like 4 ounces (1/2 cup).  just hold the jug and measuring cup out over the water (jets on) and pour it in. dunk both after you're finished.  no I don't add liquid bleach to the filter area -- that is too confined -- I would rather measure bleach out over the water where a little spill isn't problematic.  

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yea you just treat it like you would a chlorine spa .  you add chlorine after each use, measure frequently to dial things in.  a bromine spa is exactly the same as a chlorine spa except that it has sodium bromide salts in the water.  I'm astonished at how difficult the industry has made bromine spas out to be!  

I just edited my previous post and added a tip there on the use of regular bleach. make ABSOLUTE SURE you get regular bleach and nothing fancy

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