Hydrogen peroxyde as a sanitizer

[ducru]

I am thinking of switching from Lithium to Hydrogen peroxyde.  I have seen little written on this sanitizer in this forum, but it is just now coming onto the market in Canada (Quebec), but has been used for a few years in Europe.  Can anyone tell me anything about it ?  There are 2 products to be used in combination, once a week : 1/2 tsp of Crystal-O (pure micronized silica mineral) and about 10 oz of Oxypur (an oxygenation and oxydizing agent containing, I believe, 29% hydrogen peroxyde). The products are sold by Oxygenia, specifically for the hot tub, as an ecological way of treating the water and work best with a PH level of 7.0.  Although expensive ($250.00 of products, should last me 8 months), I have no problem spending this money if it will do everything it claims :  Soft on the skin, on the spa components and on the environment.  Also, it leaves virtually no TDS, since hydrogen peroxyde dissolves into water and oxygen, meaning that you can go for longer periods before dumping your water. Any thoughts ? Can it be that good ?  Is anyone presently using it (or a similar product) ?   

[chem geek]

If you have been using ONLY lithium hypochlorite without adding any Cyanuric Acid first either as pure CYA or by using Dichlor initially, then your active chlorine level has been WAY too high which will oxidize your swimsuits, skin, and hair much faster, will outgas and smell and get used up much faster, will create disinfection by-products faster, be harsher on spa components including the hot tub cover, etc.

Why don't you first try using chlorine properly before switching.  Use the Dichlor-then-bleach method or at least Dichlor-only.  It's also a lot less expensive than lithium hypochlorite.  If you don't want to use bleach, you can use lithium hypochlorite instead, but you must start off with some CYA in the water and that's most easily done by using Dichlor until you've cumulatively added about 33-44 ppm FC which is about a week or two depending on usage.

Hydrogen peroxide is not as effective a disinfectant as chlorine.  The issue isn't whether it disinfects at all or oxidizes at all, but whether it does so quickly enough to a large range of pathogens in order to meet the criteria as a swimming pool disinfectant.  This paper  indicates that silver ions combined with hydrogen peroxide in the Nanosil product at 20 mg/L (ppm) prevented uncontrolled bacterial growth but killed Staphylococcus aureus slowly requiring 20,000 ppm for 30 minutes (a bacterial species that chlorine kills in seconds). As noted in this paper, some bacteria are resistant to hydrogen peroxide because they produce the enzyme catalase (this is why silver ions are also needed since they interfere with catalase). This paper indicates that hydrogen peroxide vapor was effective at inactivating viruses.  Also, this link shows hydrogen peroxide to be ineffective against bacteria at swimming pool concentrations. In fact, it showed log reductions lower than 0.301 (a 50% kill rate) in 30 minutes against Pseudomonas aeruginosa (0.16-log reduction) and Escherichia coli (0.13-log reduction) and just 0.33-log reduction after 30 minutes for Staphylococcus aureus and just 0.41-log reduction for Legionella pneumophila. This isn't even enough to prevent uncontrolled bacterial growth under ideal conditions for such growth.  However, something smells fishy about this study because they found no improvements when using silver ions in the water. Other studies have shown silver ions to have at least a slow kill against fecal bacteria. This paper in Figure 2(a) shows 1.5 hours for a 3-log reduction of Staphylococcus aureus with silver ion at 0.05 ppm (50 ppb) while Figure 2(b) shows around 20 minutes for a 3-log reduction of Escherichia coli at 0.05 ppm (50 ppb). The Borgmann-Strahsen study used 23.6 ppb silver so perhaps this difference is a minimal inhibitory concentration effect (23.6 ppb vs. 50 ppb for silver).

to be continued...

[chem geek]

...continued from above

Hydrogen peroxide is not approved by Health Canada nor by the EPA in the U.S. nor by the DIN 19643 standard used by some countries in Europe, but it is approved on its own only for spas by Australia (there is one product approved for pools Poppit Sanosil Pool & Spa Sanitiser that also has silver ions, but the label requires it to be used in combination with Polyhexamethylene Biguanidehydochloride while Poppit Sanitiser which is hydrogen peroxide alone says "The level required for spas is lOOppm of hydrogen peroxide (see chart) and for swimming pools is lOOppm" and cannot go below 40 ppm, according to label instructions.  There is no product listed under APVMA called "Sanosil Super" -- search PUBCRIS yourself and see what you can find, so perhaps that name is covered under the Poppit Sanitiser registration.  There are a bunch of hydrogen peroxide registrations, but only three where two are for use in spas ("POOL SANITISER" is the category for disinfectants able to be used in pools and spas, two of which I mentioned already with their limitations -- SPA FRESH SPA SANITISER, CONDITIONER, CLARIFIER & BACTERIACIDE appears to be for spas only).

For the EPA, one of four approved disinfectant chemical systems is Baquacil/biguanide/PHMB and it uses hydrogen peroxide as an oxidizer, but the disinfection is from the biguanide.  Hydrogen peroxide alone is apparently not able to pass the stringent laboratory efficacy portion of the test that requires 6-log kill of some fecal bacteria in 30 seconds -- basically what 0.4 to 0.6 ppm FC of chlorine is able to do (with no CYA).

As for Health Canada specifically, the Pesticide Database shows the hydrogen peroxide registered pesticides (which includes disinfectants) in this link (note that chlorine products are found under "A" for "Available Chlorine" if you look at "Applications by active" in this link) and there are only two products listed as "swimming pool bactericide" both of which have been withdrawn.

As for longer periods of time before dumping water, for people using Dichlor-only it is the buildup of CYA that is usually the problem.  With Dichlor-then-bleach (or Dichlor-then-lithium hypochlorite) you should be able to go twice as long between water changes.  It is true that salt will build up when using chlorine, but usually the water is going to need changing before the salt level gets too high anyway and that's also true for hydrogen peroxide (i.e. you still need to change the water with it)

Because hydrogen peroxide is not as strong an oxidizer as chlorine, if you were to use hydrogen peroxide I suggest you do so in a spa with a strong ozonator.

[Quickbeam]

I can't give anywhere near the chemical knowledge Chem Geek can provide, but I can give you some real world experience. We bought our first tub about 1 1/2 years ago and have used nothing but hydrogen peroxide. My wife has some pretty serious chemical sensitivities, so chlorine or bromine were just not an option for us. We were over at a friends house who had originally used either chlorine or bromine (sorry I don't remember which) and then switched over to hydrogen peroxide. We went for a soak in her tub and were hooked. Our skin actually felt moisturized after we got out. No chemical smell and soft feeling skin. It really doesn't get much better.

There are reports that hydrogen peroxide will shorten the life of some of the spa components, but I really don't know. So far no problem with our spa, but again it's only been 1 1/2 years. There are also a couple of pretty good websites on how to get started. If you are interested let me know and I'll PM them to you.

As for the costs you quoted, that sounds outrageously high to me. We are using straight 29%, non food grade hydrogen peroxide. We pay $50 for 5 gallons which lasts a very long time. You don't need food grade - it is quite a bit more expensive. A lot of people also buy their hydrogen peroxide from health food stores, but if you get it from a chemical company it is much cheaper. As I said, we pay $50 for 5 gallons.

As for water changes, I change my water about every 3 months. I have a Taylor test kit and you can special order some reagents that will test for hydrogen peroxide. I would highly recommend doing this if you are going to switch over. I can keep track of how much hydrogen peroxide my tub uses. If the tub starts eating more hydrogen peroxide than normal, I will shock with either lithium or MPS, but I don't do it often and to be honest I'm not sure how effective it is. Chem Geek says hydrogen peroxide and lithium react with each other so I have stopped using that, and the MPS has not proven to work the best for me so far. I would like to find something I could use as an effective shock, but so far haven't found it.

And finally, I should point out that we have a Jacuzzi model tub which has the "ClearRay" bulb on it. I don't know if this is doing anything to help the hydrogen peroxide work or not. Our friend that I mentioned earlier does not have either ozone or ClearRay. She just uses straight hydrogen peroxide and has not had any problems.

For the most part we are extremely happy with the hydrogen peroxide. I really think that even if my wife did not have her health problems we would still be using hydrogen peroxide. It is easy to use, and your skin feels almost moisturized after a soak.

If you have any further questions please let me know.

[Hottubguy]

What level do you keep the peroxide at quickbeam?  I have a customer that does something similar to you. When he adds too much peroxide he says he has a hard time breathing

[chem geek]

Hydrogen peroxide reacts with chlorine, so not just lithium hypochlorite but any source of chlorine.  It's an effective chlorine neutralizer.  But that means you can't use chlorine as a shock and unfortunately MPS isn't as broad an oxidizer as chlorine.

Quickbeam, instead of looking for a shock product, have you thought about using enzymes such as Orenda CV-600?  The issue is that there are some organics that hydrogen peroxide isn't oxidizing so there might be some good enzymes that would handle that.  This is why I said it would be best if one had an ozonator since ozone will take care of oxidizing a wide variety of chemicals in bather load.

Usually it's recommended that hydrogen peroxide levels be at least 50 ppm and some recommend 100 ppm.  Quickbeam, what is the level you are running at?  It's true that some people find it to be irritating at higher levels, but not everyone.

[Quickbeam]

Chem Geek and Hottubguy,

It is really difficult for me to give you a level we keep our H2O2 at, because it is not all that consistent. Our tub is at a vacation home. We are generally only away for one or two weeks at a time, but when we are leaving, I dose pretty heavily to make sure there is still H2O2 present for the time we are away. I will quite often adjust levels to be in the 350 ppm to 400 ppm range when we are leaving (sometimes even a bit higher than 400 ppm). I know both my wife and I have been in the tub when the level is over 250 ppm. Probably even higher than that, as I'm going from memory. Neither my wife or I have ever had a problem being in the tub with higher levels of H2O2.

What I do monitor very closely is how much H2O2 the tub is using and it does vary. I've learned that in the summer (hot weather) the tub uses more H2O2 than in the winter (colder weather).

The only problem I've ever had using H2O2 is that at times the tub will start using more H2O2 than it should. I know there has to be a reason for this so I am assuming it is working to kill something in the tub. The problem is, I haven't found anything I can shock with to take care of this.

I will look into your suggestion Chem Geek of the "Orenda CV-600". This may be the answer I'm looking for. If I was to try something like this, would I use it as a shock, or is this something I would add on a regular basis? I looked on the "Orenda CV-600" website and they have a dosing calculator. It looks to me like for a 340 gallon spa I would use 1.09 ounces to "purge" (I am assuming this would be like a one time shock???) and then 0.17 ounces for maintenance. Does this sound correct to you? And for a maintenance dose would you know how often I should add it? I suppose that would depend on bather load. Given that we are not always in the same location where the tub is located, our bather load is not that high.

Or do you think it would work if I just used the "Orenda CV-600"  as a shock whenever I noticed my tub using more H2O2 than it should? In other words, if I notice the tub starting to use more H2O2 than it should, then I would just add 1.09 ounces of the "Orenda CV-600". That would probably be the easiest way for me to use the product, if it would be effective??? (I'm just thinking that a maintenance dose would be difficult because our bather load fluctuates so much).

And finally, do you know of anything that would be in this product that would be harmful to someone who has chemical sensitivities (my wife)?

Thanks so much for any help you might be able to provide.

[Vinny]

Quickbeam,

What you're experiencing with more peroxide consumption happens with chlorine as well which is why it's important to know what's going on in your tub - you obviously have a handle on it. I can't speak of bromine but I remember reading that bromines are fairly good at disinfecting where chloramines are not.

I can't go into the details the way chem geek does but knowing what's going on is the key IMO. Observing a greater demand and acting to combat it is important. I have no advice for what you're using other than if you don't have a ozone generator in your tub, maybe it's good to try one. My tub gets "chlorine lock" every so often where a dose of chlorine will stay the same for many days ... I find it weird but my tub is chlorine efficient!

[Quickbeam]

Thanks Vinny,

I also thought I should post at least a couple of answers to my own questions, in case anyone else ever wants to go this route. I just contacted the manufacturers of "Orenda CV-600". He said one thing to be careful of is that if you use too much of this product it will cause foaming. He originally suggested I use the product to clean the tub when doing a drain and refill. I told him I use Ahh-Some when doing a drain and refill and then told him what I was really looking for was a product I could use when I noticed my tub was starting to use more H2O2 than it should. He thought their product might work in that situation but cautioned me not to use the "purge" value on their dosing calculator, but rather to use the "maintenance" value. He said for pools they normally recommend a dose of 5 ounces per 10,000 gallons. On their dosing calculator, for a tub my size their purge value shows at 1.09 ounces and their maintenance dose shows at 0.17 ounces. The maintenance dose of 0.17 ounces fits right in with what he told me they recommend for pools, that being 5 ounces per 10,000 gallons. I also asked if there was anything in the product that I should be concerned about given my wife's chemical sensitivities and he didn't think there would be. I think I'll will order a bottle of this and give it a try. Thanks Chem Geek for the suggestion!

[chem geek]

Yes, I was thinking of you using it for maintenance only.  It's like having a supplemental oxidizer like having an ozonator.  It doesn't oxidize directly -- it's enzymes that accelerate oxidation from other oxidizers, particularly oxygen.  So it can help to keep the water clear by oxidizing some of your bather load -- hopefully that which hydrogen peroxide doesn't do well on its own.

Because enzymes are not consumed by bather load, you don't dose them proportionately.  Instead, they get slowly oxidized by other oxidizers such as chlorine or hydrogen peroxide.  So they need to be replenished at a constant rate independent of bather load.

[Quickbeam]

Yes, I was thinking of you using it for maintenance only.  It's like having a supplemental oxidizer like having an ozonator.  It doesn't oxidize directly -- it's enzymes that accelerate oxidation from other oxidizers, particularly oxygen.  So it can help to keep the water clear by oxidizing some of your bather load -- hopefully that which hydrogen peroxide doesn't do well on its own.

Because enzymes are not consumed by bather load, you don't dose them proportionately.  Instead, they get slowly oxidized by other oxidizers such as chlorine or hydrogen peroxide.  So they need to be replenished at a constant rate independent of bather load.

Thanks so much for this idea ChemGeek. I’ve got some on order.

The only problem I’ve ever had with hydrogen peroxide is that every so often the tub will start eating more than it should and I just have not found a solution to this. It seems to plateau out - in other words the demand doesn’t keep building, but I know the tub is using more hydrogen peroxide than it should. Doesn’t happen all that often, but when it does the only solution I’ve found is to do a water change. And even when the tub is using more H2O2 than it should, it doesn’t seem to affect water clarity. My water is almost always crystal clear.

So ChemGeek, given the problem I’ve had, do you think it would be O.K. to use this enzyme like a shock? In other words, once I notice the tub starting to use more hydrogen peroxide than it should, I would add some of the enzyme at that time? Or would I be better off adding a little bit say once per week as a kind of maintenance dose?

I was hoping to be able to use it like a shock and just add it when the tub is using more H2O2 than it should, but if it would be better to add it on a more regular basis I’ll certainly try that.

[chem geek]

If you add a lot of enzyme at once, you can get foaming.  You can certainly try it both ways to see what works best for you.  If you see the hydrogen peroxide demand rise you can add the enzymes and see if they help.  Or you can do a regular maintenance dose and see if the hydrogen peroxide demand doesn't jump up.

If the reason the hydrogen peroxide demand jumps up is due to a buildup of slower-to-oxidize organics (most likely from accumulated bather load) then if the enzymes are able to help oxidize (preferably with dissolved oxygen) those organics, that should cut down the hydrogen peroxide demand.

[ducru]

Hello all,
I just spoke with the producers of these products (Oxygenia Process) and here is what I've been able to gather.  Not being too chemical-savvy, I can only try and explain or repeat what was told to me.  I guess the philosophy behind the treatment is that you maintain the water and avoid it from becoming contaminated, by using  Crystal-O (a pure micronized silica mineral, or basically, powdered quartz).  The quartz charges the water in a way that does not allow the pathogens to grow in the first place.  Then, the hydrogen peroxyde product (29.4% stabilized hydrogen peroxyde) is actually used for shocking the water on a weekly basis, in an amount that maintains H2O2 levels at a minimum of 30 ppm.  Their products have been in use in Europe since the early 2000s. Does any of this make sense ?   

[Quickbeam]

If you add a lot of enzyme at once, you can get foaming.  You can certainly try it both ways to see what works best for you.  If you see the hydrogen peroxide demand rise you can add the enzymes and see if they help.  Or you can do a regular maintenance dose and see if the hydrogen peroxide demand doesn't jump up.

If the reason the hydrogen peroxide demand jumps up is due to a buildup of slower-to-oxidize organics (most likely from accumulated bather load) then if the enzymes are able to help oxidize (preferably with dissolved oxygen) those organics, that should cut down the hydrogen peroxide demand.

Thanks ChemGeek,
I'm really hoping this is the answer I've been looking for. It won't be for a while, but I will report back when I find out if this has worked for me.

[chem geek]

Hello all,
I just spoke with the producers of these products (Oxygenia Process) and here is what I've been able to gather.  Not being too chemical-savvy, I can only try and explain or repeat what was told to me.  I guess the philosophy behind the treatment is that you maintain the water and avoid it from becoming contaminated, by using  Crystal-O (a pure micronized silica mineral, or basically, powdered quartz).  The quartz charges the water in a way that does not allow the pathogens to grow in the first place.  Then, the hydrogen peroxyde product (29.4% stabilized hydrogen peroxyde) is actually used for shocking the water on a weekly basis, in an amount that maintains H2O2 levels at a minimum of 30 ppm.  Their products have been in use in Europe since the early 2000s. Does any of this make sense ?

No it doesn't make any sense because it's just a line of B.S. from the manufacturer.  Is the manufacturer the link Oxygenia Process?  That site doesn't describe any products for spas in their English site, but their French language site does though it doesn't say much -- just that it maintains an aerobic process not favorable to pathogens (note that there are both aerobic and anaerobic bacteria so having oxygen in the water does not disinfect it).  The reason the English language site doesn't mention this product and specifically making disinfection claims is that it is against the law (FIFRA regulations) for any product to make disinfection claims without registering as a pesticide and passing specific criteria which for pools and spas is EPA DIS/TSS-12.  There's no way this product would pass such criteria -- even hydrogen peroxide is not able to pass this criteria which requires 6-log reductions in specific bacteria in 30 seconds (for one species) and 2 minutes (for another species).

As for silica or quartz material changing the water to prevent pathogen growth, see Water Cluster Quackery.  As for inhibiting pathogen growth, you could use copper and silver ions for that, but the issue is that keeping a spa disinfected isn't just about preventing pathogen growth (which silica/quartz will not do) but about killing pathogens shed from one person so that they disease is not transmitted to another person in the spa.  The only peer-reviewed scientific paper in a respected journal I could find on silica or quartz regarding disinfection was Water disinfection using photosensitizers supported on silica where it stated:

The disinfection efficiency against Escherichia coli in water of new silica-based materials containing aromatic photosensitizers (APS) was compared to that of TiO2 under UV irradiation.
:
While no bacterial inactivation took place in the presence of silica in the dark and in the absence of silica under UVA, a slow bactericidal effect was observed in the presence of pure silica under UVA.

In other words, silica alone does nothing.  Silica with specific light-sensitive chemicals under UV radiation showed a slow bactericidal effect but that's not what goes on in a spa.

It's one thing to consider using hydrogen peroxide AT ALL TIMES as a possible disinfectant, but quite another to only use it on occasion and depend on silica/quartz to keep your spa safe.  If you use their system and run into any problems such as hot tub itch/rash/lung or worse, be sure and report back so I can add it to the 20 or so reports I accumulated on another forum due at least in part to such "alternative" disinfection systems.