Dr. Kevin Novak Anoxic Filtration System.

[Randy Holmes-Farley]

Cool! Thank you for the correction about ammonia binders and the update on the science.

I wonder if that company ever considered that ammonia is a big issue in cell culture as well. The cell culture market is absolutely huge, especially with the newer vaccine manufacturing procedures.

It's not nearly as effective in seawater as in fresh, but clinoptilolite is the traditional zeolite known to bind some ammonia from seawater:

Korean Accounting Review

 

[flampton]

It's not nearly as effective in seawater as in fresh, but clinoptilolite is the traditional zeolite known to bind some ammonia from seawater:

Korean Accounting Review

Interesting as I've tried clinoptilite in cell culture. Crashed the culture even when presaturated with potassium. Likely was binding up something we weren't measuring and releasing the potassium. Didn't look much further because we're just trying to eek out a slightly longer cell survival (read unfunded 'experiment').

---------------------//////
I wish there was text to that paper, as I'm not sure the author discusses that the binding is concentration dependent. For people who want to understand, I'll breakdown what this paper tell us.(obviously just from the figures)

The overall summary that pertains to our aquariums is If you add ammonium to a concentration of 200ppm, 10g/liter clinoptilite(zeolite) will reduce this level to about 100ppm at pH 8.0 in five hours.

That's an impressive amount, a reduction of the concentration by 100ppm!

Yet after ten hours it will still only be 100ppm. (The paper uses rate, but this is clearly poor translation as rate can't be a percentage)

Now zeolites don't bind ions completely static, so some of the ammonium is being released but at the same rate more is being bound so the overall level remains 100ppm. If you were too add more potassium to the experimental aquarium you would find the ammonium will increase in the water.

However the one variable the author doesn't change is ammonium concentration, which would quite accurately show this binding is concentration dependent.

If the author used 2ppm ammonium you would think oh that would be easy to lower, as it just reduced the concentration by 100ppm in the first experiment. However what the author would find is that they would be very lucky to see that original 50% decrease, however let's say it's perfect it would still only reduce it to 1ppm ammonium. So the ammonia in relation would still be at toxic levels.

And btw this is with a huge amount of zeolite.

The recommended amount of zeolites for the commercial system is 1liter per 100 gallons.

If you used the experimental amount (assuming 10g/liter at a density ~0.8g/ml) it would be about ~4.7 liters of zeolites/ 100 gallons.

However what this paper does show is that I shouldn't have use absolutes. Ammonium can bind to clinoptilite in seawater, its just not going to be at a useful level.

 

[threebuoys]

So, as a hobbyist who does not want to be doctor of chemistry ( and is certainly not qualified to understand all that's been said) is my take away from this thread...
No market chemical product or filtration method has been proven to be able to bind and remove ammonia in sufficient quantities (without unreasonably large quantities of the adsorbent) to be useful in controlling nitrogen in saltwater aquariums, and that the most reliable methods of denitrification in aquariums remains either 1>waterchanges, 2> biological plant processes (refugium/algae scrubbers), or 3>consumption by corals within the aquarium?

 

[HomebroodExotics]

I feel like y’all are missing a giant part of this filter. It’s not likely just the zeolite that’s binding the ammonia. There’s bacteria that grows in the basket, on the zeolite that consumes the ammonia and nitrates. I don’t see y’all talking about bacteria at all.

 

[Randy Holmes-Farley]

So, as a hobbyist who does not want to be doctor of chemistry ( and is certainly not qualified to understand all that's been said) is my take away from this thread...
No market chemical product or filtration method has been proven to be able to bind and remove ammonia in sufficient quantities (without unreasonably large quantities of the adsorbent) to be useful in controlling nitrogen in saltwater aquariums, and that the most reliable methods of denitrification in aquariums remains either 1>waterchanges, 2> biological plant processes (refugium/algae scrubbers), or 3>consumption by corals within the aquarium?

Yes, but I'd add that ammonia can be complexed/reacted to reduce the toxicity, as by Amquel or Seachem Prime

http://reefkeeping.com/issues/2007-02/rhf/index.php

Treatments for Elevated Ammonia: Hydroxymethanesulfonate
Various types of compounds are used in commercial products to bind ammonia in marine aquaria. One is hydroxymethanesulfonate (HOCH2SO3-). It is a known ammonia binder16 patented for aquarium use by John F. Kuhns17 and sold as Amquel by Kordon and ClorAm-X by Reed Mariculture, among others.

Ammonia's reaction with hydroxymethanesulfonate is mechanistically complicated, possibly involving decomposition to formaldehyde and reformation to the product aminomethanesulfonate (shown below).16 The simplified overall reaction is believed to be:

NH3 + HOCH2SO3- --> H2NCH2SO3- + H2O

What ultimately happens to the aminomethanesulfonate in a marine or reef aquarium is not well established, but it does appear to be significantly less toxic than ammonia, and more than likely it is processed by bacteria into other compounds.

Marineland Bio-Safe claims to contain sodium hydroxymethanesulfinic acid (HOCH2SO2-). I do not know if that is a typographical error, or if Marineland really uses this slightly different compound.

Note: products containing hydroxymethanesulfonate hamper the ability to test for ammonia when using certain types of test kits (see above). Presumably, the H2NCH2SO3- formed is still reactive with the Nessler reagents, even though it is not ammonia.

Treatments for Elevated Ammonia: Hydrosulfite and Bisulfite
A second type of compound used in commercial products (such as Seachem Prime) that claim to bind ammonia in marine aquaria is said to contain hydrosulfite (could be either HSO2- or - O2S-SO2-) and bisulfite (HSO3-). These compounds are well known dechlorinating agents, reducing Cl2 to chloride (Cl-), which process is also claimed to occur in these products. It is not apparent to me whether these ingredients actually react with ammonia in some fashion, or whether unstated ingredients in these products perform that function. Seachem chooses to keep the ingredients of their product secret, so aquarists cannot determine for themselves what is taking place, and how suitable it might be. Nevertheless, many aquarists seem to have successfully used products such as these to reduce ammonia's toxicity.

Note: products such as Seachem Prime hamper the ability to test for ammonia when using certain types of test kits (see above). Presumably, the product formed is still reactive with the Nessler reagents, even though it is not ammonia.

Treatments for Elevated Ammonia: Clinoptilolite
Few filter media are capable of binding ammonia from seawater. The zeolite clinoptilolite (a sodium aluminosilicate) is capable of binding ammonia from freshwater, but the sodium ions in seawater displace much of the ammonia. In fact, the ammonia binding capacity of clinoptilolite in freshwater can be regenerated by rinsing it with salty water. Consequently, its capacity to bind ammonia in seawater is very low, if any, so it is not a very useful product for marine systems.

 

[Randy Holmes-Farley]

I feel like y’all are missing a giant part of this filter. It’s not likely just the zeolite that’s binding the ammonia. There’s bacteria that grows in the basket, on the zeolite that consumes the ammonia and nitrates. I don’t see y’all talking about bacteria at all.

Sure we are. In post #45, all of these things I mention are bacterial driven processes (e.g., denitrification) already being used by reefers for this purpose. There is nothing special in the OP mention of heterotrophic denitrification by bacteria than all of the products and methods below using the exact same bacterial processes.

There are loads of different commercial media designed to accomplish denitrification (e.g., siporax, Marinepure, etc.) as well as different organics that boost the process (NOPOX, vinegar, vodka, biopellets, etc.) and some more sophisticated devices to facilitate it (carbon denitrators). And, of course, there has been decades discussion of the best way to use sand beds and porous live rock to accomplish this, such as reverse flow, plenums, remote sand beds, slow flow, fast flow, different depths, etc.)

 

[Randy Holmes-Farley]

Here's another study of clinoptilolite/ammonia in seawater:

http://aquaticcommons.org/9181/1/aquabyte%204.pdf

 

[HomebroodExotics]

Here's another study of clinoptilolite/ammonia in seawater:

http://aquaticcommons.org/9181/1/aquabyte%204.pdf

Randy I really appreciate all your input here as I am really trying to understand all these processes. As of now (correct me if I'm wrong), we have shown that 1) zeolite can attract ammonia, though not very efficiently in saltwater but it does, 2) it looks like most of these experiments of the zeolite absorbing ammonia is a function of the zeolite, correct? or is this bacteria on the zeolite, I have a hard time believing that bacteria colonize the zeolite in a 24 hour test to remove ammonia. I feel like I'm missing something here. 3) in order to get results for a filter like this we have to wait 30 plus days for the bacteria to colonize the zeolite basket for the real filtration benefits to kick in.

There is 2 conversations going on, 1) the ammonia absorption abilities of zeolite in saltwater and 2) will this filter work, which seems to be yes it will but we don't know to what extent. Correct me if I'm missing something please.

 

[Randy Holmes-Farley]

Randy I really appreciate all your input here as I am really trying to understand all these processes. As of now (correct me if I'm wrong), we have shown that 1) zeolite can attract ammonia, though not very efficiently in saltwater but it does, 2) it looks like most of these experiments of the zeolite absorbing ammonia is a function of the zeolite, correct? or is this bacteria on the zeolite, I have a hard time believing that bacteria colonize the zeolite in a 24 hour test to remove ammonia. I feel like I'm missing something here. 3) in order to get results for a filter like this we have to wait 30 plus days for the bacteria to colonize the zeolite basket for the real filtration benefits to kick in.

There is 2 conversations going on, 1) the ammonia absorption abilities of zeolite in saltwater and 2) will this filter work, which seems to be yes it will but we don't know to what extent. Correct me if I'm missing something please.

IMO, there's no real doubt that the Novak system mentioned will allow denitritication in a reef tank. So does live rock, sand and a dozen other variations of the method using all sorts of different porous materials, either boosted or not by organic carbon dosing. There's no reason (evidence), IMO, to think it is an improvement over other systems, but it's certainly a fine thing to try if someone has a substantial nitrate problem and thinks they want to try a different implementation of denitrification.

Clinoptilolite (unlike most zeolites and related materials) has pores in it that are about the same size as an ammonium ion, and it can get into those pores and bind in them. In seawater, other things similarly get into those pores and take up many of the binding sites (sodium, potassium, etc.), reducing the capacity to bind ammonium relative to fresh water.

Ammonium does not appreciably bind to ANY exposed flat surfaces in seawater. There is no justification to think that ammonia binding in these pores is more bioavailable to nearby bacteria. Bound ammonia in a zeolite is unavailable to organisms.

 

[dryworm]

I'm surprised we are still talking about this.

Is anyone suggesting this process is any different than the denitrification processes that reefers have been using for many decades?

You can skip the first 10 minutes of the video but he eventually gets around to explaining the difference between dissimilatory denitrification and assimilatory denitrification. I have no idea if he is right or wrong about the subject.

The methods you mention may work the same but they each have their problems. DSB are nutrient sinks, dialing in the correct dosage for carbon dosing. the denitrification bricks are expensive and are brittle and breakdown and need to be replaced. I can buy BCB baskets for a dollar at the Dollar Tree store. I can get 25lbs of Special Kitty liter for five dollars at Walmart. It's easy to implement in a sump and it doesn't break down for years. I think Dr. Novak said 10 years in one of his videos.

​

 

[Randy Holmes-Farley]

You can skip the first 10 minutes of the video but he eventually gets around to explaining the difference between dissimilatory denitrification and assimilatory denitrification. I have no idea if he is right or wrong about the subject.

The methods you mention may work the same but they each have their problems. DSB are nutrient sinks, dialing in the correct dosage for carbon dosing. the denitrification bricks are expensive and are brittle and breakdown and need to be replaced. I can buy BCB baskets for a dollar at the Dollar Tree store. I can get 25lbs of Special Kitty liter for five dollars at Walmart. It's easy to implement in a sump and it doesn't break down for years. I think Dr. Novak said 10 years in one of his videos.

​

I haven't watched his video, but reef tanks certainly already accomplish assimilatory denitrifiction (simple uptake of nitrate by growing organisms) and dissimilatory denitrification (where the organism does not hold onto the N).

The latter is of at least two types:

1. Conversion of nitrate back to ammonia
and
2. Conversion of nitrate to N2.

There are multiples pathways to accomplish these, and they all likely happen to some extent.

 

[Righteous]

As Randy has mentioned, there’s nothing new here.

Check out Seachem Matrix (they even make a version for ponds). It’s basically pumice stone which supports anerobic denitrification. Worked pretty well in a little freshwater tank I used to have.

But I think we should ask, why should we care? It seems for most of the hobby at this point, denitrificairon is a non issue... if it was, you wouldn’t see so many people dosing nitrate into their tanks on a daily basis. I don’t even understand who uses those marinepure blocks. As for “binding ammonia”... please no... I dose ammonia and my corals love it.

And in the the freshwater world, most serious hobbyists now have some forms of plants in their tank which just suck down the nitrates.

So this whole miraculous system just comes across like a solution to a problem no one has. Maybe I’m a little jaded... I left for vacation and came back to some dinos starting because my nitrate plummeted. No fancy Anoxic filtration required!

 

[Hermie]

And in the the freshwater world, most serious hobbyists now have some forms of plants in their tank which just suck down the nitrates.

So this whole miraculous system just comes across like a solution to a problem no one has. Maybe I’m a little jaded... I left for vacation and came back to some dinos starting because my nitrate plummeted. No fancy Anoxic filtration required!

Since R2R isn't a freshwater site so I don't want to get into a debate about it, however I will say, anoxic filtration is not represented as miraculous by Dr. Novak, he simply describes the science behind it and gives people applications they can use in their own tanks. And plants sucking down nitrates is a deeper subject. It's not that simple. That's like saying, grow a ball of chaeto and you won't have a nitrate problem. Well how difficult is it for some people to grow chaeto? A lot of people can't for various reasons. Many different reasons.

 

[HomebroodExotics]

Plants actually do a really bad job of removing nitrates. They prefer ammonia and have roots for feeding in substrate. But anyway.

 

[Righteous]

Since R2R isn't a freshwater site so I don't want to get into a debate about it, however I will say, anoxic filtration is not represented as miraculous by Dr. Novak, he simply describes the science behind it and gives people applications they can use in their own tanks. And plants sucking down nitrates is a deeper subject. It's not that simple. That's like saying, grow a ball of chaeto and you won't have a nitrate problem. Well how difficult is it for some people to grow chaeto? A lot of people can't for various reasons. Many different reasons.

Well that still doesn’t answer why it’s any different than any other media or live rock that supports heterotrophic denitrification.

And not only is the whole ammonia binding thing dubious in salt water, it doesn’t even seem like a worthwhile goal. As many hobbyists have noted, corals thrive best when there are well fed fish in the tank. Coral reefs are pretty nutrient poor places, so corals have evolved to utilize that fish pee pretty well.

In fact it’s been noted that curbing large fish capture is important in coral reef conservation for this very reason.

Fishing down nutrients on coral reefs - Nature Communications

Coral reefs are productive ecosystems due to high levels of nutrient recycling in which fishes play a critical role. This study shows fishing can reduce the amount of nutrients supplied and stored by fishes to coral reefs by nearly half, even when the number of fish species present is largely...

www.nature.com

Unravelling the different causes of nitrate and ammonium effects on coral bleaching - Scientific Reports

Mass coral bleaching represents one of the greatest threats to coral reefs and has mainly been attributed to seawater warming. However, reduced water quality can also interact with warming to increase coral bleaching, but this interaction depends on nutrient ratios and forms. In particular...

www.nature.com

 

[Righteous]

Plants actually do a really bad job of removing nitrates. They prefer ammonia and have roots for feeding in substrate. But anyway.

“Really bad” is perhaps subjective. At the risk of getting off subject, (and off forum subject, lol) freshwater aquarium plants are carbon limited. And while they do tend to prefer ammonia, if you inject CO2 in your planted tank, you’re not gonna have nitrates left in your tank. In fact most aquarium plant ferts supply both ammonium and nitrate. I speak from experience

 

[Hermie]

And not only is the whole ammonia binding thing dubious in salt water, it doesn’t even seem like a worthwhile goal. As many hobbyists have noted, corals thrive best when there are well fed fish in the tank. Coral reefs are pretty nutrient poor places, so corals have evolved to utilize that fish pee pretty well.

In fact it’s been noted that curbing large fish capture is important in coral reef conservation for this very reason.

Fishing down nutrients on coral reefs - Nature Communications

Coral reefs are productive ecosystems due to high levels of nutrient recycling in which fishes play a critical role. This study shows fishing can reduce the amount of nutrients supplied and stored by fishes to coral reefs by nearly half, even when the number of fish species present is largely...

www.nature.com

Unravelling the different causes of nitrate and ammonium effects on coral bleaching - Scientific Reports

Mass coral bleaching represents one of the greatest threats to coral reefs and has mainly been attributed to seawater warming. However, reduced water quality can also interact with warming to increase coral bleaching, but this interaction depends on nutrient ratios and forms. In particular...

www.nature.com

Tell that to the Zeovit people.

Novak's basket design does not specify zeolites.

 

[Hot2na]

Basically Dr Novak focuses on maximizing denitrification processes in freshwater systems. Do the applications work in saltwater?

Plenums + biocenosis baskets

yup they do....I have used plenums in various tanks for the last 25 yrs with good longterm results.....as for stuff in baskets in slow moving areas in the sump - nothing new there...I've seen that touted elsewhere long before Novak copied it...Biohome media, siporax,eheim substrate pro , etc - in a low flow area of the sump will do the same thing

 

[Randy Holmes-Farley]

Tell that to the Zeovit people.

I have told them many times over many years. Sometimes in their own forum, but most often to zeovit users elsewhere.


The ammonia claim by the zeovit people (that the zeolite helps attract ammonia to bacteria) is not sensible science. Even if ammonia bound to a zeolite surface (it does not, it binds in pores unavailable to bacteria), their claim makes no sense.

here's an example from 2008:

Reef Central Online Community - View Single Post - Zeolite rocks

Reef Central is dedicated to the marine reef aquarium hobby. Learn about reef aquarium setup and maintenance, and view coral and marine fish photos. Visit our online community and discuss and chat with hobbyists of all levels from beginner to advanced.

www.reefcentral.com

"
Finally, the real nonsense about the Zeo claim. How does a bacteria remove or get to a ammonia ion in a zeolite in the first place. They claim the bacteria live in the pores of the rock.

I won't even give the theory that much credit. It makes no sense whatsoever at the molecular level.

If any ammonia binds to a zeolite, then the concentration locally in the water near the zeolite is depleted in ammonia, at least for some time until it is replace by more ammonia that drifts in from the water column. Once it drifts back in, the concentration is the same as it was in the absence of any zeolite. Even 1 nanometer from the zeolite surface, the ammonia concentration is not a single teeny tiny bit higher than the bulk water, so here is no more available ammonia then without a zeolite.

It is the concentration of ammonia in the water that the bacteria can sense, and take up either passively by diffusion of NH3 across the cell membrane, or actively by some sort of active transport protein. In both cases, the ammonia must move to the bacteria surface. It is ridiculous to think that bacteria would push their cell membranes back and forth over the zeolite surface trying to collect ammonia that is bound to it, rubbing across it like a bear rubs its back on a tree."

 

[N.Sreefer]

Plants actually do a really bad job of removing nitrates. They prefer ammonia and have roots for feeding in substrate. But anyway.

Interactions between nitrate and ammonium in their uptake, allocation, assimilation, and signaling in plants

Highlight. Mixtures of nitrate and ammonium are beneficial in terms of plant growth, as compared to nitrate or ammonium alone. Interactions between these t

academic.oup.com