Interesting Zeolite/nutrient thread in SPS forum

Randy Holmes-Farley said:
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 said:
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.
 
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.
 
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 said:
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)
 
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
 
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.
 
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.
 
Habib said:
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!
 
Ger said:
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.
 
Jörg Kokott said:
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.
 
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.
 
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. :)
 
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. :)
 
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.
 
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
 
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
 
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 Ã"šÃ‚± 1) Ã"šÃ‚°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.
 
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