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/showthread.php?s=&threadid=133406

[simonh]

Tatu/Randy,

I'll throw in this from a German website:

Analysis (http://216.239.39.120/translate_c?hl=en&ie=UTF-8&oe=UTF-8&langpair=de%7Cen&u=http://www%252elars%252dsebralla%252ede/ma_zeovit.html&prev=/language_tools)

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

German BB (http://www.meeresaquaristik.de/forum/main.php/)


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 :D

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/showthread.php?s=&threadid=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 :eek: 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:D .

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 :D

[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.:D

[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 :D

Ok, now I'm leaving:smokin:

[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 :D

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.:D

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 :D

[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 :D


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. :D

[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 :D 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.

[Randy Holmes-Farley]

In the data that you posted suggesting that at least one type of zeolite can bind ammonia in seawater:

http://reefcentral.com/forums/showthread.php?s=&postid=3328693#post3328693

Did you see the actual paper to see what was bound at what concentration of ammonia?

Is it really clear that it did bind ammonia, and that it wasn't some other mechanism?

[Habib]

No, I don't have the full paper.

Let me post it here too and in the next post extract a few sentences from it:


Mar Pollut Bull. 2003 May;46(5):607-18.


Removal of ammonia toxicity in marine sediment TIEs: a comparison of Ulva lactuca, zeolite and aeration methods.

Burgess RM, Pelletier MC, Ho KT, Serbst JR, Ryba SA, Kuhn A, Perron MM, Raczelowski P, Cantwell MG.

U.S. Environmental Protection Agency, ORD/NHEERL Atlantic Ecology Division, 27 Tarzwell Drive, Narragansett, RI 02882, USA.

Toxicity Identification Evaluations (TIEs) can be used to determine the specific toxicant(s), including ammonia, causing toxicity observed in marine sediments. Two primary TIE manipulations are available for characterizing and identifying ammonia in marine sediments: Ulva lactuca addition and zeolite addition. In this study, we compared the efficacy of these methods to (1) remove NH(x) and NH(3) from overlying and interstitial waters and (2) reduce toxicity to the amphipod Ampelisca abdita and mysid Americamysis bahia using both spiked and environmentally contaminated sediments. The utility of aeration for removing NH(x) and NH(3) during a marine sediment TIE was also evaluated preliminarily. In general, the U. lactuca and zeolite addition methods performed similarly well at removing spiked NH(x) and NH(3) from overlying and interstitial waters compared to an unmanipulated sediment. Toxicity to the amphipod was reduced approximately the same by both methods. However, toxicity to the mysid was most effectively reduced by the U. lactuca addition indicating this method functions best with epibenthic species exposed to ammonia in the water column. Aeration removed NH(x) and NH(3) from seawater when the pH was adjusted to 10; however, very little ammonia was removed at ambient pHs ( approximately 8.0). This comparison demonstrates both U. lactuca and zeolite addition methods are effective TIE tools for reducing the concentrations and toxicity of ammonia in whole sediment toxicity tests.

[Habib]

I'll be back later. Accidentally erased a reply and have to rush to home. :)

[invincible569]

We were getting some answers in the Vodka thread and since Jorge cant answer them anymore because Pohl asked him to stop speaking about his products, I wanted to bring my questions over here:

Can clinoptilolites be regenerated by boiling them or any other method? Also, why does Zeo translate from Greek "to bubble". Is this where the regenaration takes place?

Also, we use Zeostart to drop levels. Supposedly Acetic Acid/Vinegar. It is said that Zeostart has more than just this, but how can any other element be in conjuction with such a strong liquid?

[Habib]

The bolding given in the other thread from the above abstract was:
This comparison demonstrates both U. lactuca and zeolite addition methods are effective TIE tools for reducing the concentrations and toxicity of ammonia in whole sediment toxicity tests.


One might argue that the reduced toxicity was due to something else but they also use the word "concentration"

also from the same abstract:

In general, the U. lactuca and zeolite addition methods performed similarly well at removing spiked NH(x) and NH(3) from overlying and interstitial waters compared to an unmanipulated sediment

For what they are saying they must have measured the ammonia concentrations. Still bacteria might have caused it.

[Habib]

In the following abstract they are talking about an artificially made zeolite or modified zeolite:

Water Sci Technol. 2003;48(3):105-12. Related Articles, Links


Influence of porosity and composition of porous carriers on the uptake of nutrients.

Khelifi O, Kozuki Y, Murakami H, Kurata K, Kono Y.

Department of Ecosystem Engineering, The University of Tokushima 2-1 Minamijosanjima, Tokushima 770-8506, Japan. olfa@eco.tokushima-u.ac.jp

The current paper assesses the potential of industrial solid wastes utilization such as blast furnace slag (BFS) and zeolite synthesized from fly ash (ZFA), which are effective as well as economically attractive for the uptake of phosphate and ammonium from polluted seawater. The solidification of BFS and ZFA has been developed in different proportions of BFS/ZFA (30/70, 50/50 and 70/30 (w/w)) with different porosities (25%, 40% and 52%, respectively) to cylindrical porous carriers using a Hydrothermal Hot-Pressing (HHP) method. The concentrations of heavy metals in ZFA and BFS were too low to affect the aquatic environment. The main finding is that the high rate of BFS (70%) in porous carriers enhanced phosphate uptake explained by the higher percentage of calcium (35.7%) in porous carriers and high pH conditions. The efficient ammonium uptake was observed with high rate of ZFA (70%) in porous carriers. Results found through this experimental work imply that porous carriers with BFS/ZFA proportion of 70/30 are suitable for potential practical application in the aquatic environment due to their efficient uptake of phosphate and ammonium. The choice was made upon their porosity (40%) and their compressive strength (56 kgf/cm2) which are relatively higher than those with BFS/ZFA proportion of 30/70 and 50/50.

[Mike_Noren]

I wonder if the reason this doesn't add up is because the company behind the zeolite/zeostart product is using not one complex but THREE simple methods to reduce nitrate?

There's the zeolite, which may (or may not) bind ammonia, and it will do so regardless of whether there are bacteria or acetate present.

There's the acetate, which will increase denitrification by acting as a carbon source for bacteria, whether there is zeolite present or not.

There's the addition of bacteria, which probably does nothing at all, but which MAY also add to the denitrification, and may utilize some of the acetate in doing so.

Basically.... I'm wondering if this isn't a glorified version of AZ-NO3 with added whistles and bells.

Just my spontaneous thoughts.

[OUinLA]

Originally posted by 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.

I'm not a scientist, nor to I pretend to be one but I am positive that the zeoliths do more than provide surface area for bacteria. I have been using the ZEOvit system for some time and I am about to switch to a larger tank, so I decided to replace my zeolith with bio balls just as a test. In previous theories, this would be a similar action as replacing the zeovit media as we do every 6-8 weeks. It only took 2 days before I noticed my corals darkening (usually they lighten after replacing zeovit media) and I had a small spike in P04 that appeared about 4 days later. Thanks for sharing that info Habib.

[invincible569]

Another note about Zeolith rocks...

when used in a reef aquarium, Zeovit recommends pumping a reactor such as a Grotech up and down to release the bacteria living in these microcavities (microscopic pores). This could be true, but i feel the main reason is to clean the rocks from detritus. If algae grew on these rocks or if they got clogged, the purpose of these rocks would decrease in efficiency from ion exchange and absorption.

Another thing to think about is that only high flow is recommended to pass through these rocks. I feel the reason for this is to also have less of a chance for algae to grow on or detritus to get stuck. Other than that, this detritus, called duff, is suppose to feed corals. Whats the difference in cleaning your tank walls causing this type of feed?

[javajaws]

Just thought I would cross post some other stuff on Zeolite I've read since it seems relevant:

From http://reefcentral.com/forums/showthread.php?s=&postid=2373042#post2373042:

"This note reports the results of experiments aimed at confirming the luxury uptake of phosphorus (P) by sediment
bacteria as polyphosphate (Poly-P). Aerobic suspensions of sediments from two different sites were spiked with 1mg P/L
as orthophosphate and augmented with acetate (a fermentation product) or glucose. The orthophosphate was rapidly
taken up over a period of a few hours. When these aerobic uptake experiments were made anaerobic and additional
organic carbon added, only the acetate-amended sediment released a significant amount of the added phosphorus. It was
hypothesised that during the aerobic stage, and with the addition of acetate, some of the phosphorus was accumulated
as Poly-P by sediment microorganisms, which was released during the subsequent anaerobic stage (provided acetate was
still present). Two lines of evidenceFtransmission electron microscope analysis of sediment bacteria and 31P-NMR
analysis of sediment extractsFare presented to support the hypothesis that a portion of the phosphorus taken up
during the aerobic experiments was stored as Poly-P. r 2002 Elsevier Science Ltd. All rights reserved."


And from http://www.abrisousroche.com/Images/Zeolith/zeolithe_ASR.htm , the contents of "ULTRABAK", a ZeoFood-like solution (roughly translated from French):

Water, chloride of clacium, magnesium sulfate, éthylène acetate , sodium acetate, Ethanol, Pepton, Trypton, L. Histidinhydrochlorid , d-phenylalanin, l-threonin, dl-tryptophan,
Dl-valin, Thiaminchlorid, Nicotinamid, Riboflavin, Pridoxinhydrochlorid, Cyanococobalamin , Natriummethyl4hydroxybenzoat and many amino acids and oligo-éléments.

And the contents of their "ULTRABio" product (like ZeoBak):

Nitrification bacteria
- Nitrosomonas europea
- Nitrobacter winogradskyi

Bacteria hétérotrophes
- Paracoccus dénitrificans
- Pseudomonas stuzeril

[Boomer]

Hab

On one of those posts I gave al link on the ability of Clinoptilolite to remove ammonia from seawater. It did have a small affinity but was greater in FW. This was the H. Emadi, J.E. Nezhad and H. Pourbagher paper.


http://reefcentral.com/forums/showthread.php?s=&threadid=183193&highlight=bower

http://www.worldfishcenter.org/Naga/Naga24-1&2/pdf/aquabyte%204.pdf

Removal of ammonia toxicity in marine sediment TIEs: a comparison of Ulva lactuca, zeolite and aeration methods.

It would be nice to know what zeolite, there are 100's of them. More than likely it is Clinoptilolite.

For what they are saying they must have measured the ammonia concentrations. Still bacteria might have caused it

Who knows, looks like still no real answer :D

Invincible

Can clinoptilolites be regenerated by boiling them or any other method? Also, why does Zeo translate from Greek "to bubble". Is this where the regenaration takes place?

No, it is regenerated with salt water :D Clino was/is often used in water softeners, where it is regenerated with rock salt.

Bubble, kinda actually means to boil. If you heat up a zeolite it will "boil/bubble" off its water content, which is weakly held. Thus, they can go through hydration/dehydration reactions, giving them some useful properties and applications.

the bacteria living in these microcavities (microscopic pores0

They won't fit they are to big, it is like sticking a watermelon up your butt ;) However, some can have open cavities produced during formation, which really aren't pores, that can/could house some

OUinLA& Java

and I had a small spike in P04 that appeared about 4 days later

In regards to phosphates. Zeolites can remove some phosphate although the are rather poor at it compared to other phosphate media. At the same time they can release iron and manganese which can combined with phosphate removing it from solution.

Hab

See what you can find on this, I have a very short version, the full one is in German :D

Kokott, J. and M. Murtzek ( 2003), in Heft 2/2003.Der Meerwasswer-aquarianer 07 (3) 56-59

Mike

Nice piece and thoughts :D

[Jörg Kokott]

Hi,

zeolites have individually different pore sizes, on the one hand the molecular sieve which is in the range 1 - 10 Angströms (0,1 - 1 nm), and bigger sized pores or channels between the crystals > 50 nm. The latter are big enough for bacteria, however, only small inorganic nutrients will reach the small sized pores, where ion exchange potentially occurs.

The thing with polyphosphate accumulating bacteria I have discussed in Michael Mrutzek's and my Vodka article in January 2004 in a German magazine. One can shift the border between anoxic and oxic zones within a biofilm by up- and downregulating the flow rate, thus PAB could potentially occur in aquaria btw filters which show regular changes in the water flow rate. Paracoccus denitrificans is thought to accumulate phosphate, however, it has been demonstrated in scientific investigations that P. denitrificans' phosphate uptake is independetly from anoxic or oxic conditions, thus it is not a PAB.

Actually nobody has identified the true PAB yet... however, it's a beta-proteobacterium called "candidatus accumulibater phosphatis". Acinetobacter has been discussed, but it seems unlikely that this genera is "candidatus a. p.". Further candidates are Microlunatus phosphovorus, Lampropedia spp. and species of the genera rhodocyclus.

[Habib]

invincible:

If one would like to use the ability of a media which attracts ammonia towards it's surface then one would not like to have a thick biofilm. The biofilm is the layer of bacteria and perhaps some sort of "glue" the bacteria excrete.

The thickness of a biofilm is reduced if the flow rate is higher.


Originally posted by invincible569
Another note about Zeolith rocks...

when used in a reef aquarium, Zeovit recommends pumping a reactor such as a Grotech up and down to release the bacteria living in these microcavities (microscopic pores). This could be true, but i feel the main reason is to clean the rocks from detritus. If algae grew on these rocks or if they got clogged, the purpose of these rocks would decrease in efficiency from ion exchange and absorption.

Another thing to think about is that only high flow is recommended to pass through these rocks. I feel the reason for this is to also have less of a chance for algae to grow on or detritus to get stuck. Other than that, this detritus, called duff, is suppose to feed corals. Whats the difference in cleaning your tank walls causing this type of feed?

[Habib]

Boomer:

See what you can find on this, I have a very short version, the full one is in German

Kokott, J. and M. Murtzek ( 2003), in Heft 2/2003.Der Meerwasswer-aquarianer 07 (3) 56-59


That guy who has posted between your and mine post is the author of that article. ;) :D


I know that pdf but I was missing some important information in there.

Do you or anyone else have the values for the affinities (relative selectivity coefficients) for the cations on clinoptilolite?

If the relative selectivity coefficient for ammonia is significantly higher than that for the other cations that material might increase the rate of ammonia removal.

[Jörg Kokott]

check this source:

http://www.zeolith.org/Datenblatt-Dateien/image001.gif

it's a relatively pure clinotilolithe (84%), sorry, it's in German and relative selectivity is given for this material. Ion-exchange total capacities for potassium is 0.22 - 0.45 mol/kg and for sodium 0.01 - 0.19 mol/kg.

However, I don't understand what's refering to 0.64 - 0.98 mol/kg, and 0.06 - 0.19 mol/kg?

[Jörg Kokott]

OK, this one should be the same clinoptilolithe, but much more detailed:



clinoptilolithe (http://www.naturelemente.de/zeodaten.html)

but no data available for ammonia.

[Jörg Kokott]

Originally posted by Habib
If one would like to use the ability of a media which attracts ammonia towards it's surface then one would not like to have a thick biofilm. The biofilm is the layer of bacteria and perhaps some sort of "glue" the bacteria excrete.
The thickness of a biofilm is reduced if the flow rate is higher. [/B]

That's right. when the biofilm breaks off new settling surface is available. The released bacteria are effectively skimmed. However, I had applied a zeolithe to an Eheim pot filter equipped with a 1000 L pump, and I wrapped the filter with Al-foild to rule out alga growth. I regularily took off the foil for checking the zeolite and always observed gas bubbles coming up the zeolite column. As photosynthestic oxygen release can be ruled out, it might be dinitrogen gas I reckon. However, sometimes motor pumps generate a vacuum and dissolved air is outgassing, thus the gas bubbles might be of that origin.

But I think that bacteria settle on zeolite, with the thickness of the biofilms is depending on the flow rate.

[Habib]

Jörg,

Thanks for the links. :)

The following is what I'm looking for but then with numbers. :

Cs+ > NH4+ > Pb2+ > K+ > Na+ > Ca2+ > Mg2+ > Ba2+ > Cu2+ > Zn2+

For some others following this thread the ">" sign means more here.

So ammonia (NH4+) is adsorbed more than lead (Pb2+) which is adsorbed more than potassium which is adsorbed more than sodium (Na+) etc.


I would like to see figures of what ammonia would be if the selectivity of say sodium is 1.

If the numerical value is say twice as large for ammonia compared to sodium then the ammonia/sodium ratio would be larger on the zeolites surface compared to the water column.

From what I have seen so far clinoptilolite has the largest affinity for ammonia over other cations when looking at zeolites only.

This makes me believe that if one would design a filter which transforms ammonia faster using bacteria and would only want to use zeolites that clinoptilolite is probably the best candidate.

It is readily available and it is very cheap.

[Habib]

Here is an abstract of an article which IMO , if I understood it correctly, supports our views but is not in saltwater:

Bioresource Technology
Volume 82, Issue 2 , April 2002, Pages 183-189

The evaluation of enhanced nitrification by immobilized biofilm on a clinoptilolite carrier

Se Jin Park, , a, Hyung Sool Leeb and Tae Il Yoona

a Division of Environmental and Geosystem Engineering, Inha University, 253 Yong Hyun Dong, Nam Gu, Inchon 402-751, Republic of Korea
b Regional Research Center for Coastal Environments of Yellow Sea, Inha University, 253 Yong Hyun Dong, Nam Gu, Inchon 402-751, Republic of Korea

Received 9 May 2001; revised 27 August 2001; accepted 3 September 2001.



Abstract
This study was conducted to evaluate the effect of clinoptilolite on nitrification in activated sludge (AS), and was focused on a relationship between ammonium exchange capacity of this mineral and improvement of nitrification. In batch experiments, the adsorption property of biofilm-attached clinoptilolite did not show substantial difference from that of natural clinoptilolite, indicating that bioregeneration became completely achieved without any regenerant in the AS. The AS with added clinoptilolite (ZR) was compared to the control AS (CR) when the ratio of chemical oxygen demand (COD) to total kjeldahl nitrogen (TKN) of influent, i.e. C/N ratio, was varied from 3.25 to 7.5 at a hydraulic retention time (HRT) of 3 h. Enhanced nitrification was comparatively observed for the ZR as C/N ratio gradually increased. The results indicated that the clinoptilolite provided a relatively low C/N ratio for nitrifiers, due to ammonium adsorption of this mineral, and consequently nitrification was accelerated

[Habib]

From: http://www.pubmedcentral.nih.gov/articlerender.fcgi?artid=34179

Phillipsite from the Neapolitan Yellow Tuff was used to remove NH4+ from the effluent from saline water in shrimp-culture tanks (86). Although zeolites are not as successful with saline-water as they are with freshwater effluents, these results suggest limited applications in seawater systems.

[Habib]

from:
http://dx.doi.org/10.1016/S0032-9592(03)00062-1

AS = activated sludge , Z=zeolite

....Enhanced nitrification efficiency in AS+Z was accomplished by the attached growth of nitrifier on-the-surface of carriers because zeolite has a superior ammonium adsorption capacity.

[Habib]

http://dx.doi.org/10.1016/S0040-6031(97)00316-X

.......Homoionic K-clinoptilolite was evaluated as both sink for NH+4 and as a source of nutrient such as K+ through a thermodynamic model.............
.........The maximum selectivity coefficient () values of clinoptilolite (20–50 and 50–75 m) to NH+4 from aqueous solution were found to be 2.4 and 1.9, respectively at lower concentration of 0.01 M.

[Randy Holmes-Farley]

I'm a little confused about the theory of how absorbing ammonia onto a nearby surface will help bacteria take it up.

Accepting that some surface has a high enough affinity for ammonia that it has a higher local bound concentration than in seawater, that does not make the near surface areas, where a bacterium will collect ammonia, any higher in ammonia. In reality, it may make the near surface ammonium concentration lower, if the system hasn't reached equilibrium yet, between bulk water, the near surface, and the actual bound surface areas.

The only possibility of how thismight help bacteria gather ammonia is to imagine the bacterium actually moving on top of and physically contacting the bound ammonia with an active transporter. That sounds unlikely to be important to me. :D

[Habib]

I'm a little confused about the theory of how absorbing ammonia onto a nearby surface will help bacteria take it up.


Locally higher ammonia concentration.

[Habib]

Diffusion rate increases if the solute is removed from the solvent.

Removal by e.g. adsorption, reaction, uptake etc

[Randy Holmes-Farley]

It still isn't making sense to me. I do not believe that the local concentration "near" the surface will be higher. I believe that it will be lower (before equilibrium) or the same (at equilibrium).

If we were talking about a simple electrical double layer, then I agree that the cations may be higher in the near surface region (near being maybe 3 nM). But that isn't, I presume, what we are talking about. Instead, I'm figuring it is a clear surface bound situation, and that the concentration of ammonia 5 nm from the surface will not be above the bulk water.

[Habib]

Randy:

If I would use other terms such as the mass transfer rate will increase does it then make more sense to you? :)

[Randy Holmes-Farley]

Sorry, no.

Do you believe that the phosphate concentration 1 um away from your Phosphate Killer is higher, lower, or the same as the bulk water?

[Boomer]

Jörg

Thanks for popping in :D

is in the range 1 - 10 Angströms (0,1 - 1 nm), and bigger sized pores or channels between the crystals > 50 nm.

Yes, but not all zeolites are the same or lets say have channels or voids. It depends on their geologic origin. Clino from formation x may not respond the same as clino from formation y. So the affinity will be less with some and more for others.


Hab

From what I have seen so far clinoptilolite has the largest affinity for ammonia over other cations when looking at zeolites only

Yes, most others aren't this high or those that are not common zeolites. Clino by far is much more common that other natural zeolites.

Do you or anyone else have the values for the affinities (relative selectivity coefficients) for the cations on clinoptilolite?


I see you found some coefficients, when I get home I will go through my 4 zeolite text books and see what I can find for you on Clino :D

This makes me believe that if one would design a filter which transforms ammonia faster using bacteria and would only want to use zeolites that clinoptilolite is probably the best candidate.

If one would like to use the ability of a media which attracts ammonia towards it's surface then one would not like to have a thick biofilm. The biofilm is the layer of bacteria and perhaps some sort of "glue" the bacteria excrete.
The thickness of a biofilm is reduced if the flow rate is higher.

Good thoughts, I guess I never thought of Clino in seawater and its ability to remove some Ammonia would mean much of anything. Now it does :lol:

[Randy Holmes-Farley]

FWIW, I think we have to be clear that no binding agent in seawater "attracts something toward its surface" (IMO).

What it may do is hold something right on the surface that randomly diffuses onto it, hits it, and sticks to it. It only holds it when exactly down onto the surface.

There is no "attractive force" for any ion that is more than a molecule diameter away from the surface, except for the electrical double layer effect, which can't be specific for ammonia or a zeolite.

[Jörg Kokott]

Originally posted by Boomer
Jörg

Thanks for popping in :D

no worries!

is in the range 1 - 10 Angströms (0,1 - 1 nm), and bigger sized pores or channels between the crystals > 50 nm.

Yes, but not all zeolites are the same or lets say have channels or voids. It depends on their geologic origin. Clino from formation x may not respond the same as clino from formation y. So the affinity will be less with some and more for others.

that's why I said "individually different pore size". ;)

[invincible569]

I got this response from Aquareearch:

Edward,

Zeolite is used to absorb ammonia. This works in fresh water.
Saltwater, however, is used to recharge the zeolite by making it release the ammonia. If you use a good biofilter and have an adequate supply of calcareous material such as oyster shell, coral or coraline algae you should not have a problem. Bacta-Pur® N3000 is even used in lobster holding tanks at 4°C (40°F).

Best wishes,
IET-Aquareearch Ltd
Karl
Karl F. Ehrlich, Ph.D.

[Boomer]

Jorg

that's why I said "individually different pore size".

I wasn't sure what you meant by that so thanks for clearing it up ;)

invincible

Go up a few posts, I answered that for you :D

[javajaws]

Originally posted by Randy Holmes-Farley
FWIW, I think we have to be clear that no binding agent in seawater "attracts something toward its surface" (IMO).

What it may do is hold something right on the surface that randomly diffuses onto it, hits it, and sticks to it. It only holds it when exactly down onto the surface.

There is no "attractive force" for any ion that is more than a molecule diameter away from the surface, except for the electrical double layer effect, which can't be specific for ammonia or a zeolite.

That makes perfect sense and doesn't contradict why they recommend high flow through the ZEOvit reactor. If you can't "attract" the ammonia to the zeolite, then just push it into it instead. Could be another reason why it's also important to "cleanse" the zeolite and replace it every few monthes - all to ensure that the zeolite has a clear shot.

So can denitrifying bacteria use this ammonia that is presumably "stuck" to the zeolite? Will the presence of bacteria prevent additional ammonia from "sticking"?

[Randy Holmes-Farley]

So can denitrifying bacteria use this ammonia that is presumably "stuck" to the zeolite? Will the presence of bacteria prevent additional ammonia from "sticking"?

Since the zeolite does not hold ammonia very strongly, it is in rapid on/off equilibrium between surface bound and free in solution. The bacteria can certainly use that portion that is free in solution for the time that it is free in solution. Sort of like bears catching salmon as they jump the falls going upstream. :D.

Can they use ammonia that is actually bound to a zeolite, while it is still bound? Or in other words, can they take advantage of a local plethora of bound ammonia? Only if they triggered it to release in some fashion, IMO, and then caught it before it left for greener pastures in the bulk water column (by diffuson to an area that would suddenly have a lower concentration).

Certain organisms might be able to take up phosphate this way when it is bound to a substrate, like CaCO3, by releasing some acid, so it is at least theoretically possible to do something similar for ammonia, although it sounds unlikely to me.

A lot of marine organisms, likely including bacteria, already have active uptake of ammonium ion. So they are already "magnets' for ammonia in the sense that they take up what ammonium drifts near them and into the clutches of active uptake proteins. Whether some nearby bound ammonia would be of interest to them is unknown to me. In the absence of having such ammonia/substrate systems naturally present in the ocean, developing such methods to release bound ammonia from zeolites seems a bit unlikely.

[Habib]

Originally posted by Randy Holmes-Farley
Sorry, no.

Do you believe that the phosphate concentration 1 um away from your Phosphate Killer is higher, lower, or the same as the bulk water?

Same as the bulk water.

But that is IMO not relevant.

The mass transfer rate is what is IMO relevant.

For example assume that the calcium concentration in the water is constant. The uptake rate (mass transfer rate) will increase if teh coral can remove the calcium ions faster from the various compartments. This happens if the coral grows faster.
The mass transfer rate increases

Another example.

Algae have a charge on their cell wall which attracts cations including ammonia. Now assume that the alga could increase the charge density then the concentration of cations around the cell wall will increase and the uptake rate will also increase (depending on the type of uptake mechanism).
The mass transfer rate increases.

If there is a substrate which does not bind ammonia too strongly on it's surface and if bacteria can grow on that surface then the number of ammonia molecules around the bacteria (neglecting membrane surface charges) will be what is in the bulk water + adsorbed on the zeolite surface (moles/ area).

This equates to a higher number of ammonia molecules per volume at a submicroscopical level.

Higher number of molecules per volume equates to a higher amount of ammonia transformed per unit time.

[Randy Holmes-Farley]

That assumes that the bacteria can consume an ammonia molecule that is actually bound.

[Habib]

Originally posted by Randy Holmes-Farley
That assumes that the bacteria can consume an ammonia molecule that is actually bound.

I expect it to be a dynamic process and don't see any reason why the ammonia would not be released from the zeolite surface at a high frequency especially at conditions in which there are so many other cations and the low capacity for ammonia in saline waters.

[Randy Holmes-Farley]

Yes, I agree that there will be a fast equilibrium. But I still contend that away from the actual surface (where I don't believe bacteria can utilize the ammonia), the ammonia in those parts of the system accessible to bacteria will be no higher, so no more bioavailable.

[Ger]

Boomer, Randy and Habib. You guys have come quite some ways since Boomer and I had a discussion not to long ago if and how zeolites have any application in saltwater ;)

Is it to much to ask to have one of you summarize in laymens terms what you have come up with so far? To be honest, some of this information is above my head.

Thanks, Gary

[Randy Holmes-Farley]

From my standpoint, I do not know what, if anything, it does in a marine aquarium other than provide support for biofilms.

[Habib]

Originally posted by Randy Holmes-Farley
Yes, I agree that there will be a fast equilibrium. But I still contend that away from the actual surface (where I don't believe bacteria can utilize the ammonia), the ammonia in those parts of the system accessible to bacteria will be no higher, so no more bioavailable.

I think that is the point we disagree on and I think that a substance allowing to settle nitrifiers on a substrate which also binds ammonia loosly should be an heaven for those nitrifiers.

Like kids in a toyshop. :D

Perhaps we both will agree soon on what I think happens, or a modification of it or on what you think happens. :)

Allow me to add a few sentences from various publications in the following post(s)

[Habib]

from: http://www.pnas.org/cgi/content/full/96/7/3463

Nitrification of sludge is accelerated by the use of clinoptilolite, which selectively exchanges NH4+ from wastewater and provides an ideal growth medium for nitrifying bacteria, which then oxidize NH4+ to nitrate (17-19).


Only a title:
Environ Lett. 1973;4(1):27-34.


Enhanced nitrification by addition of clinoptilolite to tertiary activated sludge units.

Sims RC, Little LW.



From: http://dx.doi.org/10.1016/S0032-9592(03)00062-1

Enhanced nitrification efficiency in AS+Z was accomplished by the attached growth of nitrifier on-the-surface of carriers because zeolite has a superior ammonium adsorption capacity.
P.S. AS = activated sludge and Z= zeolite

[Habib]

Just a title:

Preston, K.T. and Alleman, J.E. (1993) "Co-Immobilization of Nitrifying
Bacteria and Clinoptilolite for Enhanced Control of Nitrification,"
Proceedings of the 48th Purdue Industrial Waste Conference, West
Lafayette, Indiana, pgs. 407-412.



From: http://dx.doi.org/10.1016/S0960-8524(01)00160-2

The results indicated that the clinoptilolite provided a relatively low C/N ratio for nitrifiers, due to ammonium adsorption of this mineral, and consequently nitrification was accelerated.

[Jörg Kokott]

Hi,

had some work to do and was unable to quickly react on this interesting discussion.

As a mineral ion-exchanger (clinoptilolithe as a cation exchanger) the zeolite simply binds cations on its surface. However, every particle is surrounded by a dead layer where particles approach the surface via diffusion. The thickness of this dead layer is largely determined by the current/water flow. That means, the zeolite doesn't catch cations, but the latter approach the adsorptive surface and are bound to the surface after contact. Thereby, the charged environment quickens this binding process.

To get back to the hobby: if one puts zeolite into a pot filter, the surface might get saturated with ammonia, which is kept in an equilibrium as sodium and potassium compete with ammonia. Although ammonia is preferentially adsorbed, the high sodium and potassium concentration might fully displace ammonia. That may happen. But this is hypothetically, as we do not know the binding constants for ammonia, sodium and potassium. It even occured that the calcium concentration in seawater was significantly lower after zeolite was applied to the system. That means, although calcium is not preferentially adsorbed, the high concentration of the salt solution has great impact on the adsorption characteristics of the zeolite.

Assuming that the fresh zeolite is saturated with ammonia, AOB can settle on the surface and utilize the ammonia to produce nitrite. But as the establishement of NOB populations characteristically show a lag phase (because they're ammonia-sensitive and toxified by high ammonia concentrations), these NOB would settle on the zeolite after AOB have already developed. Thus, they would potentially occur when almost all adsorbed ammonium is already oxidized to nitrite. This nitrite would then be released to the water and washed off the zeolite filter without being further oxidized to nitrate within the zeolite filter. But this would mean that the zeolite filter would as work as good as a wet/dry filter filled with bioballs and would strongly increase the nitrate concentration in the water.

So, I would suppose something else is happening.

When bacteria settle on a given surface they release strong organic glues to the surface to attach themselves. As these biofilms may break off the substrate, the glue would still stick to the surface and would clog the pores. Consequently, the ion-exchange capacities of the zeolite would strongly decrease with time or even would approach zero. However, if the zeolite grains scratch against each other due to the strong current in the filter, and rub off the surface which is thereby regularily removed to a degree, that ammonia could newly be adsorbed, and new AOB settle on the surface.

I know, some of you are really bored by all these theoretical approaches to the truth, while we're simply speculating about things which might happen or might not happen. This is off course non-scientific, however, as there's great knowledge within this forum, we might rule out specific issues and might have the chance to proof certain hypotheses by experiments in the future.

[Jörg Kokott]

Originally posted by Habib
Just a title:

Preston, K.T. and Alleman, J.E. (1993) "Co-Immobilization of Nitrifying
Bacteria and Clinoptilolite for Enhanced Control of Nitrification,"
Proceedings of the 48th Purdue Industrial Waste Conference, West
Lafayette, Indiana, pgs. 407-412.



From: http://dx.doi.org/10.1016/S0960-8524(01)00160-2

The results indicated that the clinoptilolite provided a relatively low C/N ratio for nitrifiers, due to ammonium adsorption of this mineral, and consequently nitrification was accelerated.

Dear Habib,

all these papers are interesting, but they all use industrial wastewaters, and not seawater for their experiments!

[Habib]

Originally posted by Ger
Boomer, Randy and Habib. You guys have come quite some ways since Boomer and I had a discussion not to long ago if and how zeolites have any application in saltwater ;)

Is it to much to ask to have one of you summarize in laymens terms what you have come up with so far? To be honest, some of this information is above my head.

Thanks, Gary

My current opinion (but can change) is that some zeolites have the potential to enhance nitrification rates thus reducing the nutrient ammonia at a faster rate.

Experiments would have to show if some zeolites are really much better than some other substrates in a seawater environment.

[Habib]

Originally posted by Jörg Kokott
Dear Habib,

all these papers are interesting, but they all use industrial wastewaters, and not seawater for their experiments!

Yes, they are and I also expect these effects to be (far) less pronounced in seawater but still they might be significant enough. :)

I also wanted to show that that using an ammonia adsorbing substrate can enhance nitrification rates.

[Habib]

Jörg:

A high flow rate would IMO, and we talked about it before, would allow to keep the biofilm thin so that the surface of the zeolite can still act as a binder of ammonia.


Ammonia is positively charfed whereas nitrite and nitrate are negatively charged and would be taken up by corals and zooxanthellae throug differnt channels.

Furthermore, IMO, ammonia is a better nutrient if at the same concentration as combined nitrte + nitrate.


Removal of ammonia should IMO be the first priority.

Nitrite will be transformed in the tank to nitrate and nitrate can be removed by many methods. E.g by creating biomass (water borne bacteria) and removing them by skimming. Would also lower phosphate.

[Randy Holmes-Farley]

I still don't buy the argument that bacteria can utilize ammonia that is bound in a way that makes it more available than the same solution and solid surface in the absence of such binding properties.

The folks in one of Habib's articles assert that " Enhanced nitrification efficiency in AS+Z was accomplished by the attached growth of nitrifier on-the-surface of carriers because zeolite has a superior ammonium adsorption capacity. "

But there can be many explanations of why one substrate is better for biofilm formation and subsequent nitrification than another. It is the "because" part that I question. :)

[Habib]

But there can be many explanations of why one substrate is better for biofilm formation and subsequent nitrification than another. It is the "because" part that I question

I agree. :)

[Jens Kallmeyer]

HI

Regarding the ammonium removal, has anyone ever given a thought to anaerobic ammonium oxidation, the "anamox" Process) I know that it is well known from Sewage plants and has been shown to occurr in Nature only once (Black Sea, along the Chemocline), but I can at least imagine that inside the Zeolite Grains something like this is occurring. The proof would be close to impossible, you would need to identify these ladderanes (already a nightmare in open water).
In all cases where this process has been identified, it was connected with ammonia enrichments, compared to the surrounding environment, and thats what we see in Zeolites

Best wishes

Jens

PS: this is the literature about its occurrence in Nature

Kuypers, M. M. M., A. O. Sliekers, G. Lavik, M. Schmidt, B. B. Jørgensen, J. G. Kuenen, J. S. Sinninghe Damste, M. Strous, and M. S. M. Jetten. 2003. Anaerobic ammonium oxidation by anammox bacteria in the Black Sea. Nature 422:608-611.

[Boomer]

Hab

I don't mean to break your pop but :D

Cs+ > NH4+ > Pb2+ > K+ > Na+ > Ca2+ > Mg2+ > Ba2+ > Cu2+ > Zn2+

Was this just a good guess ;) or from an unreliable source :(

It is actually;

Cs > Rb > K > NH4 > Ba > Sr > Na > Ca > Fe > Al > Mg > Li

From what I have seen so far clinoptilolite has the largest affinity for ammonia over other cations when looking at zeolites only.

So it would have a greater affinity for K rather than NH4. Clino is #1 when it comes to NH4 but I haven't looked at all of them yet.


selectivity

There are none, as such numbers are based on a selected zeolite for even Clino from x formation. The e# ( selectivity coefficient) could change. There is also the issue of temp and flow on e#'s. There is a chapter in two of my books on what e is and how there are calculated. Not all Clino's have the same composition. Then there is there is the issue as to how pure is the Clino, its pore structure and channel network. Don't forget it will also be releasing things to the water other than just Na. There is a slow release of such things as, Fe, Mn, Cu, Zn and Co.

I though you guys may like this;

Ion Exchange Capacity in Meq / l

Linde A3 5.48, Natrolite 5.26, Analcime 4.54, Erionite 3.12, Clinoptilolite 2.5, Mordenite 2.29. On a table of 14 is # 12

Have to go mining so be back with more after work :D

[Habib]

Boom go back to your mine. :lol:

Hab

I don't mean to break your pop but

Cs+ > NH4+ > Pb2+ > K+ > Na+ > Ca2+ > Mg2+ > Ba2+ > Cu2+ > Zn2+

Was this just a good guess or from an unreliable source

It is actually;

Cs > Rb > K > NH4 > Ba > Sr > Na > Ca > Fe > Al > Mg > Li


I copied and pasted it IIRC from a spec sheet.

Where is your's from?
If the clino has a higher affinity for K than ammonia then I would not expect much good. :D

[Randy Holmes-Farley]

Some food for thought:

Microbial characteristics of biofilter in a closed marine system. Liu, Yan-hong; Luo, Guo-zhi; Zhu, Xue-bao. Mengzi High Teachers Training School, Yunnan, Mengzi, Peop. Rep. China. Nongye Huanjing Kexue Xuebao (2004), 23(3), 540-544.

Abstract

The microbial characters of film and its relation of the chem. characters have been reported in this paper. Changes in bacterial colonization on initially clean zeolite grains in exptl. system were studied by scanning electron, microscopy (SEM). Total bacterial nos. and growth rates in exptl. system have been studied with the method of 3H-thymidine, incorporation into DNA and technique of AODC. Stabilization of inorg. nitrogen after sequential changes of ammonia-N, nitrite-N, and nitrate-N in exptl. system takes about 75 days at (25 ± 1) °C. There was a clear relation between the change of the bacterial no. and the concns. of the chem. indexes. For the highly sp. surface area of zeolite, the highest no. of the bacteria was, 1016, much more than other related reports. All the results showed that the complete nitrification could be set up in full closed seawater system. The procedure was similar to which in freshwater system, but it needed a much longer start-up period in which nitrite accumulates. The results can be used in the sea fish aquaculture and seawater treatment.

[Randy Holmes-Farley]

Here, carbon granules work about as well as a zeolite:

Nitrification kinetics of biofilm on three types of filter media. He, Jie; Liu, Changfa; Wu, Yu. College of Life Science and Technology, Dalian Fisheries University, Dailian, Liaoning Province, Peop. Rep. China. Yingyong Yu Huanjing Shengwu Xuebao (2003), 9(5), 546-548.

Abstract

The nitrification kinetics and denitrification of biofilm on zeolites, carbon granules and sands were studied by detg. the concn. of COD, NH4+-N, NO2--N and NO3- -N. The results showed that the biodegrdn. of organism (expressed by COD) on the biofilm of three types of filter media followed the first-order dynamics and the biodegrdn. rates were: sands 0.0848 h-1, carbon granules 0.1187 h-1 and zeolites 0.1334 h-1, resp. The biodegrdn. of ammonia nitrogen followed zero-order kinetics and biodegrdn. rates were: sands -0.7743 h-1, carbon granules -0.9886 h-1, and zeolites -1.0714 h-1, resp. The biodegrdn. of nitrite nitrogen of the sands followed the zero-order kinetics and the biodegrdn. rate was -0.6057 h-1. There were denitrifying bacteria on the zeolites and the carbon granules when the concn. of nitrate nitrogen was high.

[Randy Holmes-Farley]

Introduction of some new materials for combined biological and ion-exchange wastewater treatment for ammonia removal. Weatherley, L.; Miladinovic, N.; Lopez-Ruiz, J. Department of Chemical and Process Engineering, University of Canterbury, N. Z. Progress in Water Resources (2003), 9(Water Pollution VII), 251-259.

Abstract

NH3 is a water pollutant which causes serious problems in terrestrial and saline receiving water. A classical soln. to the NH3 removal problem is biol. wastewater treatment which can be easily inhibited by toxic shock, pH change, low dissolved O2 concn., and low temp. Ion exchange materials have been used as an alternative to the biol. process; however, chem. regeneration of ion exchangers can be expensive, and if the influent NH3 concn. drops, desorption may occur resulting in increased effluent NH3 concns. When ion exchange and biol. oxidn. processes are combined, some drawbacks can be overcome. A literature review suggested only clinoptilolite (natural zeolite) has been studied in terms of biol. regeneration. In the research described, some new materials were evaluated in terms of biol. activation, including mordenite (natural zeolite); MN 500 (Macronet materials), and chem.-modified zeolite for NH3 removal from saline wastewater. Enriched cultures of nitrifying bacteria in a growth medium were established and used to obtain batch adsorption results on biol.-active materials. Uptake by biol. active, bacteria-free materials was compared. The same expts. were done for terrestrial and saline wastewater. For non-saline media, natural materials (zeolites) had overall better NH3 uptake and experienced highly biol. regeneration vs. synthetic MN 500. In saline media, synthetic material (MN 500) exhibited better NH3 removal vs. modified zeolite (ZZ).

[Habib]

Randy thanks. :)

From thes econd abstract: There were denitrifying bacteria on the zeolites and the carbon granules when the concn. of nitrate nitrogen was high.

Do you know what the conditions were (aerobic, anaerobic, anoxic) ?

[Randy Holmes-Farley]

It is in Chinese (and I don't have the full paper anyway). :D

[pi]

It is in Chinese

Shoot, you mean that is English????

[Habib]

:lol:

[Randy Holmes-Farley]

Perhaps we both will agree soon on what I think happens, or a modification of it or on what you think happens.

I'll concede that all comments that I've seen in these articles indicate that the authors think it possible that ammonia bound to the zeolite can in some fashion be used to enhance ammonia uptake by bacteria. I'm not convinced that it is true, but it is a reasonable hypothesis. :)

[wasp]

Just a laymans thought on the comparison between zeolite and carbon, unlike carbon, zeolite pores are too small to house bacteria, the bacteria can only live on the outside, where they can be knocked off and skimmed, hence the nutrient export potential. Carbon, with bacteria actually in it, could become a nutrient sink, and eventually leach.

[Randy Holmes-Farley]

Yes, that is a good point.

How are the zeolites used in the Zeovit or similar systems?

[wasp]

Quote - "How are the zeolites used in the Zeovit or similar systems?"
Don't actually have zeovit myself so cannot comment, I am just trying to gain an understanding before proceeding.
But I do know they are used with strong current, and have to be shaken every day to release bacteria.
It is after this "shake" that people claim to see huge polyp extension in their corals.

[Randy Holmes-Farley]

OK, that makes sense. :)

[GTR]

Randy,
I'm one month into the Zeo Systems. Aswasp said the zeolit is in a canister filter with water flowing into the bottom and exiting the top. Inside the chamber, at the bottom is a plate to support the media, then through that is an attached pipe which protrudes out the top. By lifting this pipe attached to the plate we are able to "lift" the media. Basically shaking it off without lifting the filter.
This is done by most once per day and it's suggested that the output from that filter be returned to the tank prior to reaching the skimmer.
EDIT: Also the recommendation is to have the feed pump cycle on and off in 3 hour time periods.
As you can imagine, when you do the mixing thing there are "things" being released from the media or just trapped duff which is then sent to the display. This duff is visable just as though you stirred up the bottom of the tank, not a 10 year old DSB but maybe like cleaning off a couple pieces of LR in your tank with a turkey baster. This duff is said to be by some, coral food.

After only one month I can not verify the huge polyp extension part though.

Steve U

[Randy Holmes-Farley]

Also the recommendation is to have the feed pump cycle on and off in 3 hour time periods.

Does that mean that it becomes anoxic inside of it?

[GTR]

I can't say if it would become anoxic in that three hour time period or not. My thoughts were that's what the method was meant to produce.

Those few that have run the system for a longer period find it not necessary once nutrient levels are reduced though.

Steve U

[wasp]

My understanding was it was supposed to be low flow three hours, high flow three hours.
Or did I get that wrong and it is high flow three hours, no flow three hours?

[GTR]

Pump on for three and pump off for three. The design of the canister should be such that the filter remain full when the pump is off.

Steve U

[wasp]

Well that's interesting. Not sure how big the cannister is but I would have thought it would have to go anoxic in that time.
Also, could there be a risk of sulpherication? ( or sulpher whatever-it's-called :) )

[eAlex]

Originally posted by Boomer
Don't forget it will also be releasing things to the water other than just Na. There is a slow release of such things as, Fe, Mn, Cu, Zn and Co.
When zeovit became popular few years ago I got the impression that this method mostly rely on controlled bleaching of corals to bring colours up, not only by lowering nutrients but mostly by controlled irritating of corals. :rolleyes: This impression stronger up year by year. ;) By this I don’t mean new products, like zeospur(2), where they use metals directly to “lighting colours up�, but also basic zeovit-system (zeolites, food and bacteria). I thing this is the reason why one do not get exactly same results with vodka or sugar method, but I also do not thing that bleaching corals like in most zeovit-tanks is desirable. ;)

Originally posted by Randy Holmes-Farley
Also the recommendation is to have the feed pump cycle on and off in 3 hour time periods.

Does that mean that it becomes anoxic inside of it?
They claim that zeovit rely on heterotrophic bacteria and best environment for them will be changing environment from oxic to anoxic. :rolleyes:

[Boomer]

Hab


Boom go back to your mine

Now why did I know you would dispute that :D. Hmm, you say IIRC, mine is in front of me ;) As I had said I have 4 zeolite text books, about a total of 1400 pages :lol: Two of them give the same sequence.

pge 169, Reviews on Mineralogy. Volume 4; Mineraology and Geology of Natural Zeolites, ed by F. A. Mumpton ( one of the zeolite Gods)

You may want to look into the works of Ames LL Jr, wh come to Clino, where most where published in the 60's, in the American Mineralogist.

If the clino has a higher affinity for K than ammonia then I would not expect much good.

I would agree on that and figured you would say that. Zeolites are a very nasty and difficult mineral to study.

So we are on the same page not all sequences are necessarily the same for x type clinoptilolite

4.1. Ion exchange and adsorption

Clinoptilolite and heulandite are low field strength zeolites for which the cation specivities.

Cs+ > Rb+ > NH4 + > K+ > Na+ > Li+ > H+, and Ba2+ > Sr2+ > Ca2+ > Mg2+ are predicted [11,
12]. Corresponding theoretical estimates yielded Ba2+ > Pb2+ > Cd2+ > Zn2+ > Cu2+ [16] butexperiments revealed Pb2+ ¡Ö Ba2+ >> Cu2+, Zn2+, Cd2+. Using clinoptilolite-Na as reference
NH4 + > Pb2+ > Na+ > Cd2+ > Cu2+ ≅ Zn2+ [14] and Pb2+ > NH4 + > Cu2+ ≅ Cd2+ > Zn2+ ≅ Co2+ >
Ni2+ > Hg2+ [15] has been determined.

From ; http://www.krist.unibe.ch/pdf/Clinoptilolite.pdf


If you want to know about zeolites think Cs and nuclear ;)


Do you know what the conditions were


I would bet FAB (Facultative Anaerobic Bacteria)



Since you guys are dropping abstracts;

Rhodes University Electronic Theses Collection
TR 00-89
Author Mwale, Monica
Title Ammonia removal from water by ion exchange using South African and Zambian zeolite samples
Degree M.Sc. (Ichthyology) - Rhodes University, 2000.

Abstract One problem of intensive fish culture systems is the progressive build-up of toxic wastes such as ammonia. The possibility of improving aquaculture water quality using two kinds of zeolite is discussed. Zeolites are alumino-silicates whose framework allows them to exchange cations. Ion exchange has been demonstrated to be competitive with other methods of ammonia removal due to the high selectivity for ammonia exhibited by zeolite materials. In this study an unknown Zambian zeolite (identified as laumontite by X-ray diffraction techniques) and Pratley clinoptilolite (a South African zeolite) were tested under laboratory conditions and in a fresh water recirculating system. Ammonia cation exchange capacities (CEC) and suitable application rates for efficient water treatment were determined using the batch and column ion exchange procedures. Estimated ammonia uptake, the most important criterion used to assess performance of zeolite filters was strongly influenced by zeolite type, particle size, pre-treatment, regeneration and ion exchange method used.

Statistical analysis showed significant differences in average ammonia CEC values between clinoptilolite (14.94 mg g-1) and laumontite (2.77 mg g-1), with the former displaying a higher Na+ -> NH4+ exchange rate especially in the early reaction stages. This difference accords with the higher purity of clinoptilolite, 47% as opposed to 4.7% for laumontite, which makes it a better zeolite for ammonium removal. CEC increased linearly as particle size of the clinoptilolite was reduced resulting in a linear regression model (y = 18.29 ¨C3.704 x; r2 = 74 %). Pre-treatment of clinoptilolite using 1N NaCl significantly improved the ammonia CEC of clinoptilolite. Overall performance of both the batch and column methods achieved after regeneration (18.3 mg g-1) was 25% higher than the estimated CEC values (13.0 mg g-1) for the unregenerated samples of clinoptilolite. Comparison of CEC estimates using Pratley clinoptilolite, showed that average batch CEC estimates were significantly lower than the column method estimates. The average ammonia CEC values estimated in a fresh water recirculating system (5.80 mg g-1 and 4.12 mg g-1 for the 0.7-1.0 and 1.0-1.4 mm particle sizes, respectively) were significantly lower than the column and batch estimates for the same particle sizes (P < 0.05). Some nitrite (NO2) and nitrate (NO3) build up was experienced probably due to the growth of autotrophs in the filters. Mass balance of nitrogen (N) for the three treatments of the fish trial (0.7-1.0 mm, 1.0-1.4 mm and the control treatment that had no zeolite in the filter) indicated that less that 10% of the N was retained for growth. It was found that 60 % of the NH4-N present associated with the soluble N was available for absorption by the zeolite filter or biological nitrification and that a total of approximately 22 % of NH4-N available was absorbed by clinoptilolite. The results indicate that the rate of nitrification can be deductively estimated by allowing a zeolite filter to become a biological filter. It is concluded that water treatment by ion exchange using natural zeolites, provides a reliable and efficient method for ammonia removal and appears to be a viable supplementary water treatment method for fresh water systems.


http://www.cape.canterbury.ac.nz/webdb/Apcche_Proceedings/APCChE/Data/974REV.pdf


Better than Clino on ammonia

http://www.zeoliteproducer.com/techpapers/Ammonia%20removal%20from%20wastewater.pdf


This one will give you and Randy a Buzz :D

http://www.minsocam.org/MSA/AmMin/TOC/Articles_Free/2001/Yang_p438-447_01.pdf

Something on a clino doing its job;

Based on the results of Chelishchev et al. (1973) noted above and others, clinoptilolite may be a useful ion-exchanger for Pb, Cu, Cd, Zn and Co in the final polished step of the tertiary treatment of industrial wastewaters. Studies of exchange between Na-Clino and various alkyl-ammonium cations have revealed interesting steric and ion-sieve properties that can be readily expalined on the bases for the Merkle-Slaughter Stucture (Barrer et al., 1976). Ions small enough to enter both channels fully replace Na+ (NH4+, CH3NH3+, C2H5NH3+, (CH3)2NH2+ and n-C3H7NH3+ ); those to large to enter the 8-ting channel but small enough tp penetrate the 10-ring channel are partially exchanged ( (CH3)3NH+ and iso-C3H7NH3+ ); and the largest ions are totally excluded ( (CH3)4N+ and tetra-C4H9NH3+ ). The n-C4H9NH3+ ion, which should penetrate both the 8- and 10-ring channels is only partially replaced. In this case ( and possibly in the case of (CH3)3NH+ and iso-C3H7NH3+ ), the free volume of the alkyl ammonium cation exceeds the total free volume of the channels and exchange is therefore limited by the stereo-chemistry for the sorbent and sorbate system


Randy

I'll concede that all comments that I've seen in these articles indicate that the authors think it possible that ammonia bound to the zeolite can in some fashion be used to enhance ammonia uptake by bacteria. I'm not convinced that it is true, but it is a reasonable hypothesis

That was the theory I also gave on the Zeovit thread to Alex and Gary. I also stated that GAC could do about the same thing as your abstract stated to include other porous media.

Your are not convinced ? Why not, some "bacteria" can do such things extracellular such as Cyanobacteria :D

Example ( Am I stretching it here ?)

Cyano's take organic phosphate, which is hydrolyzed outside the cell by extracelluar phosphatase and the phosphorus is taken up as orthophosphate.

Hi Gary :wavehand:

Where is Alex he should be here: D

I don't know where I/we are. It seems to be up and down, I have changed my view twice in the last couple of days. It is getting more confusing :lol:

[Habib]

Here is something about the anammox process. I have not read it yet.


http://www.ias.ac.in/currsci/jun252003/1507.pdf


Also here is the abstract from the Nature article Jens is referring to:

Anaerobic ammonium oxidation by anammox bacteria in the Black Sea.

Kuypers MM, Sliekers AO, Lavik G, Schmid M, Jorgensen BB, Kuenen JG, Sinninghe Damste JS, Strous M, Jetten MS.

Max Planck Institute for Marine Microbiology, Department of Biogeochemistry, Celsiusstrasse 1, 28359 Bremen, Germany. mkuypers@mpi-bremen.de

The availability of fixed inorganic nitrogen (nitrate, nitrite and ammonium) limits primary productivity in many oceanic regions. The conversion of nitrate to N2 by heterotrophic bacteria (denitrification) is believed to be the only important sink for fixed inorganic nitrogen in the ocean. Here we provide evidence for bacteria that anaerobically oxidize ammonium with nitrite to N2 in the world's largest anoxic basin, the Black Sea. Phylogenetic analysis of 16S ribosomal RNA gene sequences shows that these bacteria are related to members of the order Planctomycetales performing the anammox (anaerobic ammonium oxidation) process in ammonium-removing bioreactors. Nutrient profiles, fluorescently labelled RNA probes, 15N tracer experiments and the distribution of specific 'ladderane' membrane lipids indicate that ammonium diffusing upwards from the anoxic deep water is consumed by anammox bacteria below the oxic zone. This is the first time that anammox bacteria have been identified and directly linked to the removal of fixed inorganic nitrogen in the environment. The widespread occurrence of ammonium consumption in suboxic marine settings indicates that anammox might be important in the oceanic nitrogen cycle

Originally posted by Jens Kallmeyer
HI

Regarding the ammonium removal, has anyone ever given a thought to anaerobic ammonium oxidation, the "anamox" Process) I know that it is well known from Sewage plants and has been shown to occurr in Nature only once (Black Sea, along the Chemocline), but I can at least imagine that inside the Zeolite Grains something like this is occurring. The proof would be close to impossible, you would need to identify these ladderanes (already a nightmare in open water).
In all cases where this process has been identified, it was connected with ammonia enrichments, compared to the surrounding environment, and thats what we see in Zeolites

Best wishes

Jens

PS: this is the literature about its occurrence in Nature

Kuypers, M. M. M., A. O. Sliekers, G. Lavik, M. Schmidt, B. B. Jørgensen, J. G. Kuenen, J. S. Sinninghe Damste, M. Strous, and M. S. M. Jetten. 2003. Anaerobic ammonium oxidation by anammox bacteria in the Black Sea. Nature 422:608-611.

[Habib]

Hi Boom,

Thanks again. :)

However, I found something, skimmed only through it, looks like we would not need to worry much about potassium and perhaps also not the other cations. Atleast if we are not interested in ammonia removal solely by adsorption.

http://www.cape.canterbury.ac.nz/webdb/Apcche_Proceedings/APCChE/Data/974REV.pdf

[Boomer]

Yes, tables 1 ,2 & 3 show there is not that much of a difference to worry about ;) I was a little surprised.:(

[Randy Holmes-Farley]

Why do you suppose they did not test sodium?

[jfinch]

Wasn't the zeolite precharged with sodium?

[Habib]

Originally posted by Randy Holmes-Farley
Why do you suppose they did not test sodium?

They talk about sodium and the various placement of sodium in the affinty serie depending on the publication.

The way they did the experiment (batch process) and the initial form of the clinoptilolite (sodium form) each mol/L uptake of ammonia or other cation would displace sodium and add the same mol/L of sodium into solution thus changing the medium.

Based on the amount of ammonia concentrations used and the amount removed from solution it looks like that ammonia had a far higher affinity for the clino than sodium.

It even looks like (in a quick glance) that sodium has a lower affinity than magnesium in their experiments for the type of clino used.


I'm not sure if that was your answer? :)

[Habib]

Originally posted by jfinch
Wasn't the zeolite precharged with sodium?

Yes. :) You posted while I was reading that article and typing. :)

[Randy Holmes-Farley]

Yes, but my concern reflects the fact that sodium in seawater is so much higher in concentration than any of those other ions. :)

The experiment is easily done by putting in much more sodium than could come off.

[Habib]

Originally posted by Randy Holmes-Farley
Yes, but my concern reflects the fact that sodium in seawater is so much higher in concentration than any of those other ions. :)

The experiment is easily done by putting in much more sodium than could come off.

That's why I was initially (and still) interested in knowing how much higher the affity for ammonia is compared to the other cations. :)

I think it would be worthwile to obtain some clino and perhaps also the zeovit stuff, condition it with ammonia free seawater and then do a batch experiment by spiking with ammonia.

[Boomer]

Hab

Does this help ?

http://www.gsaresources.com/cationexchange.htm

From the same site

http://www.gsaresources.com/toc.htm


Just me reading some things;

Zeolites have a critical advantage as model cation exchangers in that their swelling is not significant and salt imbibition is usually very samell under concentrations commonly used to study their exchange properties.

----------------

This is illistrated by the observation that the presence of small concentrations of ammonia in solution can cause dramatic increases in cation exchange capactiy, presumably because the zeolite prefers the complex ions created by the presence of the ammine ligand (-NH3) over the orginally uncomplexed ions in solution.

---------------


In a zeolite ion exchange the rate controlling step is the so-called particle diffusion process. This means that the rate of exchange depends upon the diffusion of cations, water molecules or cation-water complexes, through the zeolite framework.

At very low external cation concentrations the rate-controlling step to zeolite cation exchange can shift to the solution phase. Now the rate of exchange is depenent upon progress through the Nernst Layer of orientated water molecules close to each zeolite partilce surface. This is called "film diffusion" and is easily recongnized as how the rate of diffusion is affected by the speed of agitation.

Randy

Yes, but my concern reflects the fact that sodium in seawater is so much higher in concentration than any of those other ions.

You would think that the Law of Mass Action would apply here :confused:

[Habib]

I did a few quick experiments with a zeolite , if I assume that the information from the supplier is correct and is actually zeolite and not something else.

The amount used was approx. 10 gram of zeolite per 100 milliliter of water so that would equate to approx. 2 pounds (1 kilo) per 2.5 gallons (10 liter).

It lowered the ammonia concentration in both tapwater and seawater.

The effect in seawater was much lower but still significant.

For both seawater and freshwater the time to see the effects was many hours.

I also measured nitrite and nitrate and it can be excluded that the decrease in ammonia was caused by transformation to nitrite or nitrate.

I can't exclude that the observed decrease in ammonia was due to incorporation into bateria because neither the waters nor the zeolite and containers were sterile and also not the set up.

However, the samples using zeolite were compared with controls.


Since they were just quick experiments I would not feel comfortable to give the amounts of ammonia removed.

[invincible569]

Habib, thanks for running this quick test. :) So it does what people have been saying. Thats good to hear.

[Randy Holmes-Farley]

The amount used was approx. 10 gram of zeolite per 100 milliliter of water so that would equate to approx. 2 pounds (1 kilo) per 2.5 gallons (10 liter).


How large was the ammonia drop? That is one hefty load of zeolite. My new 90 gallon tank would, at that rate, use 72 pounds of zeolite. :lol:

[slow_leak]

Both links of the analysis are dead

[kennyangel]

This post isn't off topic, yet related:

I've been told that there is a thread here on Reef-Central where someone uses only one of those "Potions" sold by Thomas Pohl and still is receiving "good" results (brighter corals with less zooxanthellae).
An analysis of this liquid has shown that there is some kind of weed-ex in it wich will simply kill algae.

I don't claim this to be true, for it was just a rumour about a thread, but I wasn't able to find such a thread. If anyone knows about it please drop me a line.


On Topic:

Regardless what Zeoliths do in saltwater environments it might just be that Thomas Pohl has experimented and discouvered a method that "somehow" works, modified and eventually brought it to the market. It may well be that he doesn't know what's happening at all and that indeed the zeoliths are a futile fragment remaining from a trial and error analysis.
This is only speculation of course. You can reach incredible colourful corals with his system and that is what counts to some extend.

[GTR]

I remember claims of Al, Fe and urine but not a weed killer unless is was in jest and I just ignored it (but I doubt that could happen :lol: ).

SteveU

[Randy Holmes-Farley]

Regardless what Zeoliths do in saltwater environments it might just be that Thomas Pohl has experimented and discouvered a method that "somehow" works, modified and eventually brought it to the market. It may well be that he doesn't know what's happening at all and that indeed the zeoliths are a futile fragment remaining from a trial and error analysis.
This is only speculation of course. You can reach incredible colourful corals with his system and that is what counts to some extend.

Perhaps. I personally wouldn't add something that I did not understand how or why it worked, unless I had great trust in someone who did, or I had an overriding interest in the observable effects (like coloration) regardless of other possible effects.

[Heinz]

<a href=showthread.php?s=&postid=7514267#post7514267 target=_blank>Originally posted</a> by kennyangel
some kind of weed-ex


2.4D or round up, i should have known :)
or maybe Basagran, hmmm, there are so many to chose from :D

[invincible569]

<a href=showthread.php?s=&postid=7514613#post7514613 target=_blank>Originally posted</a> by Randy Holmes-Farley
Regardless what Zeoliths do in saltwater environments it might just be that Thomas Pohl has experimented and discouvered a method that "somehow" works, modified and eventually brought it to the market. It may well be that he doesn't know what's happening at all and that indeed the zeoliths are a futile fragment remaining from a trial and error analysis.
This is only speculation of course. You can reach incredible colourful corals with his system and that is what counts to some extend.

Perhaps. I personally wouldn't add something that I did not understand how or why it worked, unless I had great trust in someone who did, or I had an overriding interest in the observable effects (like coloration) regardless of other possible effects.

That's the difference in human personality. Its like a company who is on the cutting edge of technology.. they may lose or they may win from it.

[Randy Holmes-Farley]

Yes, although you can be cutting edge, and still have your clients know what the product is, even if you do not know all there is to know about how it works.

In my field, pharmaceuticals, that is a hallmark that has made the industry successful in moving away from snake oils.

[Genetics]

<a href=showthread.php?s=&postid=7514329#post7514329 target=_blank>Originally posted</a> by GTR
I remember claims of Al, Fe and urine but not a weed killer unless is was in jest and I just ignored it (but I doubt that could happen :lol: ).

SteveU

Isn't urine a form of weed killer? :D

I know this thread is rather extinct but what can I say I find it rather interesting. Personally, I had never had any true interest in zeovite. None of the information seemed to make sense so I wasn't going to invest in something that can be looked at as snake oil. However, the more I find myself interested in nitrate and phosphate control within the reef environment this has become more of a focal point for me.

To be honest this is still of topic for what I'm truly interested in at the moment but have had a decent time filtering through the papers and ideas presented here. I couldn't help but ponder something I've seen on multiple RC threads and wonder if it may help on what is clinoptilolite actually accomplishing?

Randy's last statement on pharmaceuticals is really the reason I'm posting. I'm proposing two hypotheticals here on how zeovite may have had reasons to be placed in saltwater. One came after reading the publications about waste water one may assume that the zeolite would actually help remove ammonia beneficially. So you put it in your tank during cycling to decrease the initial swing but its shown not to work well in saltwater. But overtime you find that you see an added benefit to the tank so you keep it.

Or.... zeolite's ability to sequester ions (the ones around and above ammonia) are actually the key. What if its introduction is just to keep any negative effects of heavy metals you may be adding to the tank from all the zeo additives?

On RC people have complained of low potassium levels when running a zeo system. If this zeolite has an affinity for such then wouldn't the decrease indicate that it is sequestering a sufficient amount out of the water? So anything above it would also be reduced overtime within the system.

Cs > Rb > K > NH4 > Ba > Sr > Na > Ca > Fe > Al > Mg > Li

Anyways, random thoughts.

[Reefer08]

So has it been proven that the zeolites directly reduce ammonia NH3 and ammonium NH4+? Supposedly these zeolites are supposed to reduce these first two chemicals in the nitratification cycle before they lead to nitrite and nitrate. I would like to know if anyone can verify these claims??

Thanks

[slow_leak]

I believe those claims are correct in Fresh Water systems. It is typical to see zeolites in uncycled goldfish bowls still. I thought it was still highly questioned in reef systems. It is a pourous substance that can grow bacteria however, just like live rock. There are 40 types of natural occurring zeolites so refuting a vendor claim becomes tedious and unnecessary.

However anecdotal evidence is Vodka dosing and amino acid dosing is reported very promising so far even without zeolite.

I am more on the bleeding edge of this trend. I use KNO2 at levels of 2ppm to control cyano that is often reported in Vodka dosing.

Could someone clarify any other differences between Vodka dosing with amino acids and Omega fatty acids without zeolite compared with the packaged products of Zeovit, or Ultralith.

[slow_leak]

I meant nitrate not nitrite

[eggiel]

<a href=showthread.php?s=&postid=15365630#post15365630 target=_blank>Originally posted</a> by Reefer08
So has it been proven that the zeolites directly reduce ammonia NH3 and ammonium NH4+? Supposedly these zeolites are supposed to reduce these first two chemicals in the nitratification cycle before they lead to nitrite and nitrate. I would like to know if anyone can verify these claims??

Thanks

I dont want to say its has been proven but i did the test
Using zeovit for a year now and seeing good results i challenge to do the 14 day cycle in a new setup

Results were not seeing p04 or no3 during the cycle
Testing every other day with Hanna photometer and Lamotte
Adding corals and fish slowly

Dosing Zeostart, Zeobak, Sponge Power and Zeolithes

The water was 100% from RO/DI

Sustrate was brand new non live crush coral rinse with RO/DI

Rock was precured

Zeolithes absorb ammonia and ammonium the first 2 in the netrification cycle so that the possibilty why we dont get to see nitrate

Zeoliths dont absorb fosfate or nitrate the bacteria is the one in charge to consume it and elimante it by exportion thru protein skimming. Thats what I understand

[slow_leak]

that's interesting.

I guess the next challenge is to see if the same results can be obtained without zeolite. For example a carefully controlled and dosed carbon source, and bacteria source from zeovit or prodibio.

[slow_leak]

that's interesting.

I guess the next challenge is to see if the same results can be obtained without zeolite. For example a carefully controlled and dosed carbon source, and bacteria source from zeovit or prodibio.

I think the NPK ratios in ultra low nutrient systems can favor cyanobacteria growth. Have you seen this in your tank?

[eggiel]

<a href=showthread.php?s=&postid=15367699#post15367699 target=_blank>Originally posted</a> by slow_leak
that's interesting.

I guess the next challenge is to see if the same results can be obtained without zeolite. For example a carefully controlled and dosed carbon source, and bacteria source from zeovit or prodibio.

I think the NPK ratios in ultra low nutrient systems can favor cyanobacteria growth. Have you seen this in your tank?

starting up the same system with out the zeoliths
just dosing
That will be an other test

Cyano will only appear if overdosing the carbon source
just like with vodka
Thats why is recomended to test fosfate and nitrate so the dosing could be adjusted

Yes seen it in my tank and adjusting the dosing and siphoning it cleared up

[slow_leak]

What exactly did you use for carbon? and how much?

I suspect cyano can also appear when nitrates are the limiting factor for instead of phosphate. I am doing smething like your second test, without zeolite but also dosing KNO3 for awhile if things go favorable.
Only in the range of 2ppm.

[eggiel]

Zeo start 0.2ml when I started now only 0.1 ml everyday

[slow_leak]

Is that a Sugar/Ethanol/Vinegar solution or something else?

I have Salifert Amino Acids, Selecon Omega3's and, and solution above. I also use Prodibio Digest. Sort of a perversion of Dr. Pohls recipe, but essentially the same.

The only difference is Zeolite free and N:P ratio in manipulated by feeding extra nori, potassium nitrate is adjusted as well.

Single solution is added containing 2 week quantity of carbon source and nitrates. Digest and amino acids are added manually.
A dilution is dosed with bulk reef supply Drew's doser. I use Lamotte Nitrate and Hana LR Phosphate tester.

Cost is a fraction of zeolite and dosing is very accurate. I test and adjust every 2 weeks solution. Nitrates have not risen yet to 2ppm (less than 5 and greater than 0).

Vodka Sugar Vinegar = Free
AM Selecon = 11 for several months
Salifert AA = 12 for 1/2 year
Digest = 17 / 3month supply
KNO3 = 8 for one pound/ lifetime supply

I'll post before and after in a september.

[eggiel]

Cool
My results right now on my 75 gallon tank using full zeovit system is 0 P04 and 0 No3 using the same test kits as mention before

I have bottles since I started a year ago still using them the only bottle I have to buy twice is the bacteria

Colors and growth are great lets see in about six more months