Interesting Zeolite/nutrient thread in SPS forum

[tatuvaaj]

Randy,

Your message didn't post...

I think this is the thread: http://www.reefcentral.com/vbulletin...hreadid=133406

[simonh]

Tatu/Randy,

I'll throw in this from a German website:

Analysis

also a search around this German BB may shed a little light on it:

German BB


Now I'll throw around a few personal thoughts as there doesn't seem too much out there on the mechanics of the method. I did buy some out of intrigue into exactly what it was... I like to subject things to my chemisty tests... how does it smell what does it look like

I suspect that the zeolite has a large internal surface area ideal for colonization by anaerobic bacteria. If so, then this may reduce the nitrate levels? Also, it seemed that Iron was slightly depleted from the zeolite in the tests and in my translation possibly it is possibly present the Zeofood? Zeofood itself smells acetic acid like too. It is also said that after using the bacteria and food the skimmer will produce darker skimmate. Could the iron be binding phosphates (possibly increased bacteria too from the acetic acid binding phosphate?) and then removed by the skimmer similar to how the liquid phosphate removers work?

I am not sure what many of the German tanks have in the way of nitrate reduction other than a classical berlin type setup. I know many use phosphate removers and some are using them incombination with this product. I'm sure the product works... but I'm sure that other methods acheive the same goals (assuming nitrate and phosphate reduction are the goals/effect of the method).

[Mike_Noren]

Originally posted by tatuvaaj
Randy,

Your message didn't post...

I think this is the thread: http://www.reefcentral.com/vbulletin...hreadid=133406

Hmm... Zeolite is a group of minerals with clay-like properties, it does do ion exchange, and depending on what zeolite it is, it may adsorb nitrate, as well as provide huge area for bacteria.
The bacteria sold with the stuff, however, is snake-oil - noone to date knows what bacteria do denitrification in reef tanks. The bacterial food is interesting, it is said to smell like acetic acid, and acetate is a substance I've seen suggested to improve the efficiency of denitrification (by acting as a carbon source for the denitrifying bacteria).

But really, isn't it time to drop this fixation with nitrate? Nitrate buildup is rarely a problem in a modern reef tank.

[G.Alexander]

Dear Simon,

indeed the zeolite has a large internal surface area. But the execution of the material is in a PVC pipe with a water flow of about 2000 liters. With this flow ratio it is not possible to reduce nutrients by bacteria colonies.

In the first 10 month using this method I placed the material directly to my sump. The effect to the looking of the SPS was good.

Since 4 weeks I run the material in a PVC pipe with the flow ration named above. Some days later I could notice that the SPS show better coloration than using the material directly in the sump.

Generally the SPS placed not directly under the bulbs show this effect.

Alexander

[Randy Holmes-Farley]

That's strange. I don't know how the thread could show up without the post.

Yes, that is the thread that I was pointing out.

FWIW, I don't know how many of the pores inside of a zeolite are large enough for bacteria. I thought most we more on the size scale of molecules, and that is why they bind molecules like phosphate so well.

[simonh]

I never considered the pore size in the zeolite I just jumped to that conclusion due to adding the Zeobac and Zeofood when the Zeolite media was changed.

[Boomer]

Zeolites have been used in this hobby in the USA for over a decade. It is what Nitrate Sponges are made of, e.g. X-Nitrate. As some one has mentioned "kitty litter", which is correct and the same for "water softeners" and "floor dry", all which are made of the same Zeolite_Clinoptilolite_, which is the end mineral of the Heulandite Series, where there has been a replacement of K for NA.. These minerals are often confused with clays, which they are not even related to, other than the fact they are both Al silicates often with water. They belong to or are some times put in the Feldspar Group and are in the same silicate Subclass as Quartz_Tektosilicates_. They are not structured like clay at all. Heulandite/Clinoptilolite is (Na, Ca)2-3 Al3 (Al, Si)2 Si13 O36 : 12H20. Clay mienrals are Phyllosilcates, which form sheets of tetrahedra, each sharing 3O. Tektosilicares are 3-dimensioanl frameworks of tetrahedra, each sharing all 4 O. All clays are also hydoxides and Zeolites are not

The thing about Zeolites is that they can loose all their water without changing their crystallographic structure, where other ions/compounds can replace the water. The general formula is Wm'Zr'O2r'_sH20. Where W is chiefly Na and Ca (K, Ba and Sr lesser). Z is Si + Al, where Si:Al is 1 or greater and s is variable. The ratio Al2O3:(CaO + Na2O) is always 1:1 and the (Al + Si):O is always 1:2. There are different composition ranges in different Zeolite minerals but it is narrow. They all have a very open wide meshed structure, where the cavities in the framework contain cations that balance the anions. However, the easy of the exchange is what makes them unique.

Beside the many Natural Zeolites there are 100's of artificial Zeolites. O2 Generators are a good example where 3 different Zeolites are used to remove ambient air gases, while leaving behind O2. A DIY unit can take ambient air and give you a return of 50 % O2 and high-tech units as high as 95 % O2. The word Zeolite is Greek, which means to boil, which is what "appears" to happen when you heat a Zeolite to drive off the water.

Zeolites have almost nil application in seawater due to it's ionic strength. The amount of Nitrate Zeolites can actually adsorb is also nil, if at all. The use of them in this hobby is that they end up acting like LR and bring about Facultative Anaerobic Denitrification, which can be accomplished with any pores media that meets the requirement, like certain GAC's

As far as does the product do what is claimed, that's hard to answer and would like to see some real serious tests. I would also like to see them EXPLAIN how the product really works and just what are the _3 Zeolites_

[Habib]

Boomer,

O2 Generators are a good example where 3 different Zeolites are used to remove ambient air gases, while leaving behind O2.

Are they good enough to reduce elevated CO2 as encoutered in some houses to what is it 0.03%?

And if so are they still effective at the required flow rates for skimmer operation?

Might become the Boomer (CO2) stripper.

[Boomer]

Oop's, now I'm in trouble I forgot about Randy .

I don't know how many of the pores inside of a zeolite are large enough for bacteria

The pore structure and its internal free dimensional cavities its dependent on "building blocks"

Primary-Tetrahedron (TO4)

Tetrahedron of 4O ions with a central ion (T) of Si +4 or Al+3


Secondary

Rings: S-4, S-5, S-6, S-8, S-10, S-12

Doulbe Rings: D-4, D-6, D-8



Large Symmetrical Polyhedra

Truncated Octahedraon or Sodalite Units

11-Hedron or Cancrinite Units
14-Hedron or Gmelinite Units

These structures and their arrangment give them the internal pore free dimensions/ main cavities, which can be as high as 15.1 x 6.3 A ( in one I looked at). The norm is more on the order of 4-7 A, biggest dimension.

[Habib]

Simon,

Could the iron be binding phosphates (possibly increased bacteria too from the acetic acid binding phosphate?) and then removed by the skimmer similar to how the liquid phosphate removers work?


I have not seen or tried the product but the iron is very likely the cause of PO4 decrease.

The analyses by Lars were also done after usage and no PO4 was detected on the used Zeovit. One would, IMO, expect it to be detected given the decrease in PO4 concentration and method used.

The bacteria food also seems to contain iron which, if present in a high enough concentration, could also decrease phosphate concentration.

Like Boomer already noted, natural zeolites have limited use in adsorbing ions. Even in freshwater it is limited. Problems arise, and many don't know, when it has been used in freshwater adsorbing things like ammonia and some salt is added. This results in release of the ammonia and many other nasty substances.

Perhaps the most useful zeolite adsorbing a lot in an aquarium would be the 3 or 5 Angstrom molecular sieves

[Randy Holmes-Farley]

These structures and their arrangment give them the internal pore free dimensions/ main cavities, which can be as high as 15.1 x 6.3 A ( in one I looked at). The norm is more on the order of 4-7 A, biggest dimension.

Pretty darn tight for anything bigger then a glucose molecule.

[Boomer]

Are they good enough to reduce elevated CO2 as encoutered in some houses to what is it 0.03%


Yes, some have a high affintiy for CO2 and it is one of their uses in industry.

I will review my Zeolite text books (4) on the CO2 issue. I thought I did this years ago when I tried to introduce O2 generator into the hobby and I'm a little rusty but it seems to me the CO2 is partly moved by a prefilter then the old common Clinoptilolite. Moderite also has the abilities for CO2 adsorption. The key here Habib is the right Zeolites to remove X and leave the other stuff behind. It is most common now to use artificial Zeolites, as the Natural ones can vary from mine to mine even if the same Zeolite mineral. Some Zeolites are used as N Generators just as they are for O2 Generators. The worlds leading company is AirSep, whom I contacted years ago. Modern units work by Pressure Swing Adsorption (PSA) . We played with a couple of their O2 units. I will give them a buzz later, as I must get to Christmas shopping.

[Boomer]

Ok Randy, let me get this staight. The average bacterium is 1,000 nanometers long and there are 10 A in 1 nm, so 10 x 1,000 = 10,000 A for the bactiera and the some pore openigs are 10 A. Are you trying to saying I would find it easier to stuff a water melon up my butt end

Ok, now I'm leaving

[Mike_Noren]

Originally posted by Boomer
Ok Randy, let me get this staight. The average bacterium is 1,000 nanometers long and there are 10 A in 1 nm, so 10 x 1,000 = 10,000 A for the bactiera and the some pore openigs are 10 A. Are you trying to saying I would find it easier to stuff a water melon up my butt end

The smallest 'real' bacteria are about 200 nm, the as yet rather uncertain nanobacteria may be as small as 20 nm, if they at all exist, so even they would have serious problems squeezing in to those pores.
However, the surface area available to bacteria in clay-like materials is huge anyway, even if the pores are too small for the bacteria to enter.

[G.Alexander]

@ Habib

I know that the analysis from Lars only contains one zeolite of the mixture. I do not know how the analysis looks to the other two zeolite.

What do you think about the adoption that the zeolite, the bacteria and the food changes nutrients to a form that can be targeted by the skimmer ?

Without strong skimming this method do not work with this result.

Thank you.

Alexander

[Randy Holmes-Farley]

I think the watermelon analogy is a good one.

I do agree that they may have substantial surface area that isn't part of the normal pore structure. I just don't know what it is, nor do I know how one would easily measure the surface area accessible to bacteria.



What do you think about the adoption that the zeolite, the bacteria and the food changes nutrients to a form that can be targeted by the skimmer ?

I had figured that the zeolite was just used for absorption of nutrients, and then tossed. If it remains at a steady state as a bacterial colony support, then I'm not sure where the nutrients end up. Skimming is a possibility.

[Boomer]

Mike

However, the surface area available to bacteria in clay-like materials is huge anyway, even if the pores are too small for the bacteria to enter.

I know that Mike, that's why I said this:

Zeolites have been used in this hobby in the USA for over a decade. It is what Nitrate Sponges are made of, e.g. X-Nitrate.


The use of them in this hobby is that they end up acting like LR and bring about Facultative Anaerobic Denitrification, which can be accomplished with any pores media that meets the requirement, like certain GAC's

They do work like LR, I'm one of the people that help bring them into the hobby and is the reason I have 4 Zeolite testbooks. X- Nitrate comes from my source not Thiels, where his orginally came from Hungary through Pete Escobal at Aquatronics/Filtronics, "Pro-Ore". When they parted Albert ask me to find a new soruce, which was East West Minerals, now under a different name. Yes the surface area is hudge. Void fractions are on the order of .50f in some, which = 50 %. It is not a question does it (Clinoptiloite) bring about Facultative Anaerobic Denitrification, it is fact. You can do the same thing with "sinter stone" or even lava rock. I think what we are trying to figure out is do Zeolites have some special properties which makes it a better choice.

I might add I enjoyed your commnet "snake oil". Right to the point

[Boomer]

Randy

I do agree that they may have substantial surface area that isn't part of the normal pore structure. I just don't know what it is, nor do I know how one would easily measure the surface area accessible to bacteria.

I don't either

What do you think about the adoption that the zeolite, the bacteria and the food changes nutrients to a form that can be targeted by the skimmer ?

Well, let me go out on a limb. As soon as water begins to flow through it there IS going to be ionic exchange, so it is now for all practical purposes inert. Once it is colonized could there be some kind of ionic exchange or adsorption of some of the ions by the bacteria or maybe even the food. There is also the iron issue. Some Clino's also contain varying amounts of Iron. I am not a chemist, so I leave this in the hands of my mentors Randy and Habib


I had figured that the zeolite was just used for absorption of nutrients, and then tossed.,

I thought the same, so I am also puzzled

I can't see at all If it remains at a steady state as a bacterial colony support,, it makes no sense, how could it remain steady state as far as nutrients go

[Yellotang]

Boy Boomer, this brings up memories of years ago when I asked you about kitty litter.

[simonh]

Originally posted by Boomer
I thought the same, so I am also puzzled

I thought the same too originally. Then after seeing the analysis and manufacturers comments awhile ago this seemed to be not the case. I then switched to the idea it grew the anarobic bacteria given that the bac/food was only used when changing the media for 14 days and then usage of those stopped. Now I am told that the pore size is too small for the bacteria... So, I am left puzzled too Hence my change to could the media release something that binds to the nutrients and makes them preferable for export by skimming.

[Boomer]

Habib

I still working on the CO2 scrubbers. I have some CO2 absorption curves and am suppose to be getting some info from Airsep and a return phone call from the chief engineer. My question was, yes, they will scrub CO2, but how much. Tests in the past have shown that preferential absorption is in the following sequence; C02>CO>N2>O2>Ar>H2. My main concern is there a way to regenerate the zeolite or find a way to exhaust the CO2 from the zeolite. Also, how well a scrubber would work without PSA and how often would the media (zeolite) need to be changed. Of course there would be a number or variables here, grain size, column size , flow rate, etc.. So far I have found nothing on the application and use of zeolites as CO2 scrubbers for ambient air.

[Frisco]

I figured that this worked through the diffusion of atoms and/or small molecules into the pores and that it did nothing more than act as a molecular sieve.

[Randy Holmes-Farley]

To some extent that is true, but also, some things fit right into the structure, giving it some selectivity even with long periods of time for things to equilibrate.

[Habib]

Originally posted by G.Alexander
@ Habib

I know that the analysis from Lars only contains one zeolite of the mixture. I do not know how the analysis looks to the other two zeolite.


Neither do I know what the property of the other two is.

What do you think about the adoption that the zeolite, the bacteria and the food changes nutrients to a form that can be targeted by the skimmer ?

I personally don't think that a zeolite has any advantages over any anaerobic parts in an aquarium. But it could be that they have discovered something new with zeolites.

But I doubt that because the zeolite after use shows only depletion and an increase in sodium and chloride content which is exactly what one would expect using a zeolite in marine water.

There seems no sign of increased phosphate (bacteria!) on the zeolite so I doubt if there has been any significant bacteria growth in the zeolite's pores. This also in line with the expected pore size and the size required by bactreia to grow , multiply and still have enough diffusion around it (about 0.05 mm or so).


Without strong skimming this method do not work with this result.

It could be that the iron dissolving from the zeolite binds some phosphate on it's surface after being oxidized. This can then be removed by skimming.

If it is true that the method does not work when not skimming then it seems IMO very unlikely that some essential and otherwise absent substances are produced biologically.
If that were true then one would also probably notice a difference when not skimming.



Thank you.

Alexander

Thank you Alexander. Aufwiederhören!

[Habib]

I'm going to revive this thread.

There was a quite lengthy discussion in the Advanced forum and at that time I looked into it and found that certain zeolites have still enough affinity for ammonia in seawater.

One can easily imagine what advantages that would offer if on that same zeolite's surface also bacteria are present.

The combination of a high enough affinity and the bacteria which use ammonia can result in a much faster uptake of ammonia.

Ammonia is a nutrient which can increse the number of zooxanthellae and change the color of corals more towards brown.

Another way to reduce nutrients such as phosphate and nitrate can be creating a sort of bacteria bloom but not to such an extent that it is noticeable to the eye. That is just increasing the bacteria count in the water column to acceptable values.

This can be accomplished by many substances like ethanol (alcohol) or glycerol to name a few.

Growth and multiplication of bacteria will also require nitrogen and phosphor and can be acquired by the uptake of nitrogen and phosphate from the water column.

Using a good quality and powerful skimmer should allow to skim out most of the waterborn bacteria. Some additional tricks could even enhance it.

IMO that could be a good method to further reduce the nutrients in a reef tank and transform it to a state not easily uptakeable by zooxanthellae.

This could aid in reducing the brown color of some corals and enhance the more vibrant colors.