Interesting Zeolite/nutrient thread in SPS forum

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. :(
 
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.
 
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.
 
G.Alexander said:
@ 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
Click to expand...

Thank you Alexander. Aufwiederhören!
 
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.
 
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.
 
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?
 
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.
 
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.
 
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.
 
Habib said:
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.
Click to expand...

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.
 
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?
 
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
 
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 4.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
 
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.
 
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.


invincible569 said:
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?
Click to expand...
 
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.
 
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