Sulphur in the reefaquarium

Dkeller_nc

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This is an old thread, but just for the heck of it I looked up the basic process since it's in my wheelhouse (chemical engineering). Here is an academic article that describes the basic process, in this case as applied to septic tank effluent.

Of specific interest to this particular thread, note the stoichiometric reaction shown as equation (1) on page 349. Approximately speaking, one proton is produced for every nitrate ion that is reduced to nitrogen gas. This, of course, acidifies the effluent, which then dissolves the limestone layer. The net effect is nitrate reduction, sulfate production, and dissolution of calcium carbonate (limestone). The overall reaction scheme is exactly as Randy has explained in the thread - in a seawater system, the net effect would be nitrate reduction, sulfate production, and, in contrast to the freshwater systems described in the literature, consumption of alkalinity.

The reason for this is straightforward. In the freshwater sewage treatment schemes, the pH in the reactor is quite low, which allows for dissolution of the limestone bed included as an inorganic carbon source for the heterotrophic bacteria. Depending on how the reactor is configured, the limestone bed also allows for restoration of a more neutral pH for the overall treatment effluent to avoid the highly negative effects of acidic discharge to the soil.

However, in our systems, the inorganic carbon required by the bacteria for growth would come from the seawater (lowering the overall alkalinity). The low pH required to dissolve calcium carbonate sufficiently to restore the alkalinity consumed by the bacteria in the reduction of nitrate would be highly undesirable.

I'm speculating here, but I would think a somewhat complicated reactor configuration would have to be put together to 1) provide effective denitrification, 2) dissolve calcium carbonate to restore the alkalinity, and finally 3) raise the pH back to tank-appropriate values. Either that, or the overall alkalinity dosing to the tank would have to increase by quite a lot (as Randy notes) to compensate for a much simpler reactor design. If this was done by 2-part dosing, I'd think the amount of extra sodium going into the water would be significant, and as the reactor effluent would be enriched in sulfate, the sulfate/chloride balance of the water would change from seawater considerably faster.

Overall, and considering the relative simplicity of nitrate reduction using the already-available anoxic zones in a reef tank by simply adding an inorganic carbon source, the system described in this thread doesn't seem to offer any advantages, and adds considerable complexity to a tank.
 

Dan_P

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This is an old thread, but just for the heck of it I looked up the basic process since it's in my wheelhouse (chemical engineering). Here is an academic article that describes the basic process, in this case as applied to septic tank effluent.

Of specific interest to this particular thread, note the stoichiometric reaction shown as equation (1) on page 349. Approximately speaking, one proton is produced for every nitrate ion that is reduced to nitrogen gas. This, of course, acidifies the effluent, which then dissolves the limestone layer. The net effect is nitrate reduction, sulfate production, and dissolution of calcium carbonate (limestone). The overall reaction scheme is exactly as Randy has explained in the thread - in a seawater system, the net effect would be nitrate reduction, sulfate production, and, in contrast to the freshwater systems described in the literature, consumption of alkalinity.

The reason for this is straightforward. In the freshwater sewage treatment schemes, the pH in the reactor is quite low, which allows for dissolution of the limestone bed included as an inorganic carbon source for the heterotrophic bacteria. Depending on how the reactor is configured, the limestone bed also allows for restoration of a more neutral pH for the overall treatment effluent to avoid the highly negative effects of acidic discharge to the soil.

However, in our systems, the inorganic carbon required by the bacteria for growth would come from the seawater (lowering the overall alkalinity). The low pH required to dissolve calcium carbonate sufficiently to restore the alkalinity consumed by the bacteria in the reduction of nitrate would be highly undesirable.

I'm speculating here, but I would think a somewhat complicated reactor configuration would have to be put together to 1) provide effective denitrification, 2) dissolve calcium carbonate to restore the alkalinity, and finally 3) raise the pH back to tank-appropriate values. Either that, or the overall alkalinity dosing to the tank would have to increase by quite a lot (as Randy notes) to compensate for a much simpler reactor design. If this was done by 2-part dosing, I'd think the amount of extra sodium going into the water would be significant, and as the reactor effluent would be enriched in sulfate, the sulfate/chloride balance of the water would change from seawater considerably faster.

Overall, and considering the relative simplicity of nitrate reduction using the already-available anoxic zones in a reef tank by simply adding an inorganic carbon source, the system described in this thread doesn't seem to offer any advantages, and adds considerable complexity to a tank.

I read an article when this thread was new that took care of the acid production by running the effluent from the sulfur column through a column of calcium carbonate. Mixing calcium carbonate with the sulfur also works but complicates calcium carbonate replenishment. So the system could be simple.

As for sulfate, each owner would have to estimate the sulfate production rate to determine if simple water changes would prevent the chloride:sulfate ratio from deviating very far from natural salt water. Maybe sulfate production is a deal breaker in some situations. If there was a simple test for sulfate and chloride, maybe this would not be an issue.

Another point to consider is whether nitrate reduction is a one time fix or an ongoing issue. Using sulfur for a one time fix would be more work than a water change or dosing vinegar. For ongoing control of nitrate, sulfur, growing algae and dosing vinegar would each have an advantage for different situations and people.

I seem to recall that there are public aquaria using this method to control nitrates. The system works but it does not seem to appeal to the current population of aquarists. I have gone so far to buy sulfur pellets from Amazon to give this a try, but my fish only system is 0:0 nitrate:phosphate right now. I might spike the aquarium water with nitrate or just set up a small offline system to observe sulfur do it’s thing on a sample of aquarium water with elevated nitrate.
 

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I read an article when this thread was new that took care of the acid production by running the effluent from the sulfur column through a column of calcium carbonate. Mixing calcium carbonate with the sulfur also works but complicates calcium carbonate replenishment. So the system could be simple.

As for sulfate, each owner would have to estimate the sulfate production rate to determine if simple water changes would prevent the chloride:sulfate ratio from deviating very far from natural salt water. Maybe sulfate production is a deal breaker in some situations. If there was a simple test for sulfate and chloride, maybe this would not be an issue.

Another point to consider is whether nitrate reduction is a one time fix or an ongoing issue. Using sulfur for a one time fix would be more work than a water change or dosing vinegar. For ongoing control of nitrate, sulfur, growing algae and dosing vinegar would each have an advantage for different situations and people.

I seem to recall that there are public aquaria using this method to control nitrates. The system works but it does not seem to appeal to the current population of aquarists. I have gone so far to buy sulfur pellets from Amazon to give this a try, but my fish only system is 0:0 nitrate:phosphate right now. I might spike the aquarium water with nitrate or just set up a small offline system to observe sulfur do it’s thing on a sample of aquarium water with elevated nitrate.

That process may be sufficient to maintain alkalinity, but then calcium will steadily rise.

The sulfate rise is not a concern unless you never do water changes (IMO). It takes a lot of sulfate to move that needle since it is massive to begin with. Salinity variations will alter sulfate more than this process.
 

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This is an old thread, but just for the heck of it I looked up the basic process since it's in my wheelhouse (chemical engineering). Here is an academic article that describes the basic process, in this case as applied to septic tank effluent.

Of specific interest to this particular thread, note the stoichiometric reaction shown as equation (1) on page 349. Approximately speaking, one proton is produced for every nitrate ion that is reduced to nitrogen gas. This, of course, acidifies the effluent, which then dissolves the limestone layer. The net effect is nitrate reduction, sulfate production, and dissolution of calcium carbonate (limestone). The overall reaction scheme is exactly as Randy has explained in the thread - in a seawater system, the net effect would be nitrate reduction, sulfate production, and, in contrast to the freshwater systems described in the literature, consumption of alkalinity.

The reason for this is straightforward. In the freshwater sewage treatment schemes, the pH in the reactor is quite low, which allows for dissolution of the limestone bed included as an inorganic carbon source for the heterotrophic bacteria. Depending on how the reactor is configured, the limestone bed also allows for restoration of a more neutral pH for the overall treatment effluent to avoid the highly negative effects of acidic discharge to the soil.

However, in our systems, the inorganic carbon required by the bacteria for growth would come from the seawater (lowering the overall alkalinity). The low pH required to dissolve calcium carbonate sufficiently to restore the alkalinity consumed by the bacteria in the reduction of nitrate would be highly undesirable.

I'm speculating here, but I would think a somewhat complicated reactor configuration would have to be put together to 1) provide effective denitrification, 2) dissolve calcium carbonate to restore the alkalinity, and finally 3) raise the pH back to tank-appropriate values. Either that, or the overall alkalinity dosing to the tank would have to increase by quite a lot (as Randy notes) to compensate for a much simpler reactor design. If this was done by 2-part dosing, I'd think the amount of extra sodium going into the water would be significant, and as the reactor effluent would be enriched in sulfate, the sulfate/chloride balance of the water would change from seawater considerably faster.

Overall, and considering the relative simplicity of nitrate reduction using the already-available anoxic zones in a reef tank by simply adding an inorganic carbon source, the system described in this thread doesn't seem to offer any advantages, and adds considerable complexity to a tank.
Thanks for the detailed analysis. :)
 

Dan_P

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That process may be sufficient to maintain alkalinity, but then calcium will steadily rise.

The sulfate rise is not a concern unless you never do water changes (IMO). It takes a lot of sulfate to move that needle since it is massive to begin with. Salinity variations will alter sulfate more than this process.

I thought that the calcium rise might be small compared to calcium consumption in reef tanks.

Two nitrates generate two protons which liberate one calcium and one CO2 from calcium carbonate. If the system generates 2 ppm of nitrate per day, that is only a 1 ppm calcium rise per day. My fish only system rarely generates nitrate that fast. I assume reef tanks would be less than that.

Not advocating sulfur, just trying understand your position.
 

Randy Holmes-Farley

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I thought that the calcium rise might be small compared to calcium consumption in reef tanks.

Two nitrates generate two protons which liberate one calcium and one CO2 from calcium carbonate. If the system generates 2 ppm of nitrate per day, that is only a 1 ppm calcium rise per day. My fish only system rarely generates nitrate that fast. I assume reef tanks would be less than that.

Not advocating sulfur, just trying understand your position.


It may be small (depending on the amount of nitrate being processed), but it is by definition unbalanced by alk consumption since you added the media to prevent the alk drop.

I’m not sure the calcium carbonate media does anything useful. Without it you must add some extra alk. With it you must add less calcium. That’s ok using a two part, but not ok if using any of the forced to be balanced methods like a CaCO3/CO2 reactor, limewater/kalkwasser, or an organic form like sodium formate or acetate.
 

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Two others concerns are that if there is any aerobic metabolism of the sulfur to sulfate, that has unlimited potential to reduce alk.

Second is whether this method will take more nitrate through it than simply the amount that would otherwise accumulate. The daily throughput of nitrate may be well above the normal accumulation rate. So diverting more of it into sulfur oxidation and less into other biological uses, may mean more alk decline than you assumed from 1 ppm per day.
 

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One interesting note about this is the history of sulfur denitrators in the hobby. I do remember some 20 years ago when they were the "hot new thing". These were a bit different than what is described in the academic article I posted earlier in that they were intentionally run in an anoxic condition, and the carbon supply for the heterotrophic bacteria was in the form of methanol injections into the reactor. They do work, but I also remember folks having a good deal of trouble tuning them so that anoxic conditions were maintained. I also remember quite a few posts that someone had nuked their tank by running more methanol into the reactor than the bacteria could consume, with the result that they heavily carbon-dosed their tank and caused a bacterial white-out.

The irony of this is that if they had removed the reactor entirely, and added small amounts of methanol to the tank, they probably would've achieved the same effect, albeit at the risk of potential direct methanol toxicity.
 
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The moderator has removed all links to our knowledgebase Makazi Baharini wiki as R2R considers it a commercial website because there is a donation button present to help maintain the website and I do participate by adding information to the Makazi Baharini wiki.
In the Makazi Baharini wiki information about BADES and different applications is available on the page baharini.eu/baharini/doku.php?id=en:badess:start

One has to register to enter the Makazi Baharini wiki and for the links to become active, by which one agree to respect the publication rights which are read only and for personal use only . Most references used in articles can be consulted and are available for reading respecting the authors and publication rights. The wiki is written in Dutch, translated pages to English may not contain the most recent information. Anybody may participate to Makazi Baharini by adding approved information and help by doing research about keeping marine and reef aquaria. The Makazi Baharini wiki does not contain any commercial information and we hope to keep it that way.

All about the history of using sulphur in marine aquaria is available in the Makazi Baharini wiki
It went wrong wen a well known firm started to commercialize a BADES system as it was a "denitrator" which had to be kept anoxic to be able to work, as that time was common practice using a carbon based "denitrator". And the internet did the rest.
Longouet, together with Hignette, pioneer of the MAAO system, later also installed at MALO , and at Rochelle, never advised to keep the sulphur reactor anoxic.( <0.5ppm DO)

Discussions about the BADES process, alkalinity, sulphate, calcium , etc , all questions are already answered by proper research. Everything about the BADES proces is known and documented. There are no secrets. Everything has been followed up in practice , has been tested and reported many times. BADES is now used in public marine reef aquaria for more than 2 decades . All the caveats are known and answered.
Now It is not about a single process, it is about what happens in a nitrifying bio-film growing on a mix of shell grit and sulphur grains. Simultanious nitrification and mixotrophic denitrification in which the used substrate plays a key role.

To remove nitrogen from the system BADES is easy to use and does NOT need a reactor called a "sulphur-denitrator"
See BADES columns, SPC system. SBNMS ( sulphur based nitrogen management system)
A SBNMS does not effect alkalinity much, less as carbon dosing which effect on alkalinity depends of the nitrogen source used . Some calcium is produced.

As I am not allowed to share information with a link to the original publication of the information and as this information can only be made public by a link to the original page by the publication rights applicable on the articles in question, I can not add much to this discussion any more.

To answer the question: True. One just has to add some elemental sulphur to remove more nitrogen from the system.
It is reported a normal nitrifying bio-film will remove +-16% of the processed nitrogen as nitrogen gas. When the nitrifying biofilm grows on sulphur grains this will increase considerably going up to 90% using BADES columns.
 
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Belgian Anthias

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Two others concerns are that if there is any aerobic metabolism of the sulfur to sulfate, that has unlimited potential to reduce alk.

Second is whether this method will take more nitrate through it than simply the amount that would otherwise accumulate. The daily throughput of nitrate may be well above the normal accumulation rate. So diverting more of it into sulfur oxidation and less into other biological uses, may mean more alk decline than you assumed from 1 ppm per day.
Such visions have lead to the banning of the bio-filter . A bio-filter does not remove or add more as the one who usses it wants it to be. One only removes nitrate over production, nitrate considered not needed for the system. The removel rate is manageable at the removal rate as desired by the user. Also, the nitrate level can be maintained at the desired nitrate level, as desired by the user. Using a SBNMS the nitrogen cycle can be closed keeping the nitrate level as desired by the user, without any daily additions .
¨What to do with nitrate produced by a bio-filter? " Nitrate is a reserve of safely stored usable nitrogen wich can be used when desired. The use of nitrate nitrogen for metabolism does add alkalinity, the use of ammonium-nitrogen does consume alkalinity, also when used by photo-autotrophs. The total availabilty of usable nitrogen is the same. The production of nitrate effects alk depending of the substrate on wich the reactions take place.
 

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Makazi Baharini wiki as R2R considers it a commercial website because there is a donation button present to help maintain the website
This sets off alarm bells, why is research/ results and history of use restricted like this, has it never been openly published for peer review?
 

Dan_P

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This sets off alarm bells, why is research/ results and history of use restricted like this, has it never been openly published for peer review?

“Autotrophic denitrification biofilters” is a good Google term to find the literature on this subject. The subject is old and is peer reviewed. The potential downside for marine aquarium use is sulfate and acid production (here it is referred to as alkalinity reduction). For a fish only system the acid production is easily remedied with a calcium carbonate treatment after the sulfur column or dosing sodium bicarbonate. I have not done any calculations to show whether the potential sulfate:chloride shift is important. Randy thinks that it might be unimportant (several posts above this one).
 

Dan_P

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Two others concerns are that if there is any aerobic metabolism of the sulfur to sulfate, that has unlimited potential to reduce alk.

Second is whether this method will take more nitrate through it than simply the amount that would otherwise accumulate. The daily throughput of nitrate may be well above the normal accumulation rate. So diverting more of it into sulfur oxidation and less into other biological uses, may mean more alk decline than you assumed from 1 ppm per day.

Does your second concern also apply to carbon dosing?
 

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“Autotrophic denitrification biofilters” is a good Google term to find the literature on this subject. The subject is old and is peer reviewed. The potential downside for marine aquarium use is sulfate and acid production (here it is referred to as alkalinity reduction). For a fish only system the acid production is easily remedied with a calcium carbonate treatment after the sulfur column or dosing sodium bicarbonate. I have not done any calculations to show whether the potential sulfate:chloride shift is important. Randy thinks that it might be unimportant (several posts above this one).
Thanks Dan for clarifying, this method seems to have several implications that need monitoring/ adjusting and to me adds to many levels of complications to be a viable method, I was considering trying this instead of my current denitrator, which is based on carbon dosing and a zero O2 chamber, but the clarification you, Randy and DCKellar have provided have helped me in my decision to not pursue this sulphur reactor.
 

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This thread is way over my pay grade, but a few months ago I built a Sulphur denitrator and installed it. The effluent dumps into my reverse undergravel filter (OK stop laughing)
The effluent comes out nitrate free and the thing doesn't seem to require any maintenance. I don't really have a nitrate problem but I like to experiment. I don't see any problems with this thing but like I said, you people have more degrees than thermometers.

I feed heavily because I want everything spawning, which they do. I also feed a lot of clams with the associated clam juice which causes my sponges to grow up the walls. I think this denitrator would be a boon to people with nitrate problems and it is cheap and requires no maintenance.

I also don't see any more need for alk or anything else but if it does, alk is also cheap.

Have a great day. :cool:
 
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Belgian Anthias

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This sets off alarm bells, why is research/ results and history of use restricted like this, has it never been openly published for peer review?
All articles in the Makazi Baharini wikki are based on approved publications and are propperly referenced. All references used can also be consulted .Most articles present in Makazi Baharini are not open to the public as the content is published with respect for all authors and publishers and the publication rights on the used information. We just collect the information and try to bring it in a readable article, information wich may be used for personal use only. We are just using information provided by others which must be credited for there work.
 

Randy Holmes-Farley

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A SBNMS does not effect alkalinity much, less as carbon dosing which effect on alkalinity depends of the nitrogen source used . Some calcium is produced

On that point, at least, you are incorrect.

Carbon dosing (with ethanol/vodka or acetic acid/vinegar) causes no changes in alkalinity that are any different than uptake and use of the same nitrogen forms (ammonia, nitrite it nitrate) by photosynthetic corals and other organisms.
 

Randy Holmes-Farley

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Does your second concern also apply to carbon dosing?

No. That concern is not that nitrate may get too low. I assume with any method that you can somehow control it properly. My concern is that causing more nitrate consumption by sulfur will have an even bigger drop in alk than is predicted by the daily accumulation rate of nitrate. For example, lowering nitrate with sulfur will potentially cause less direct consumption of nitrate by photosynthetic organisms. If the daily production is unchanged and the daily incorporation by organisms decreases, that means that more each day is following the sulfur route. Hence my suggestion that the daily accumulation rate is not a perfect measure of how much is consumed by sulfur and thereby, how much the alk is consumed by the sulfur process.

Consuming nitrate by carbon dosing causes no drop in alk, so no such concern exists for it.
 
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Belgian Anthias

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Everything about BADES has been calculated and tested two decades ago. BADES has been lab tested for over 7 years for to be used in marine and reef aquaria and first put into practice in MAAO. and later in MALO Hundreds of research papers have been published about BADES and its applications. A lot of this information is available in the Makazi Baharini wiki.
A SBNMS is not a denitrator in the sence it only is able to reduce nitrate. A denitrator adds nothing to the carrying capacity off the system. A SBNMS does remove ammonia nitrogen making it possible to manage the carrying capacity and max bio-load,
Now it is about increasing the natural denitrification capacity of a nitrifying biofilm by adding elememtal sulphur as a substrate for the growing nitrifying biofilm. About denitrators using elemental sulphur everything is known and if used correctly they work fine wich have been proved over the 20 years of practice. When speaking about a "sulphur denitrator " some are refering at the MAAO system in which BADES is used as a denitrator and seperate reactors are used for the maerl. In MAAO systems the reactors are NOT kept anoxic as often adviced on the net as guideline for using sulfur-denitrators. In MAOO systems the flow is increased as high as possible maintaining 0 nitrate in the effluent. It has been reported by Hignette the MAAO system works fine at a DO of 3ppm. BADES biofilm reactors work fine having an effluent still containing 2 ppm DO and they do not produce any supplemental sulphate by oxidation of elemental sulphur. In MAAO it is reported by Hignette most sulphate is held back in the maerl reactors. In SPC ( Sulphur Packed Columns) systems the colums are used in DO saturated water. The sulphate production is far below of what may be theoretically suspected . High flow BADES biofilm reactors do not aim for 0 nitrate in the effluent, just removing the daily nitrate overproduction, a bit more if lowering the nitrate level is desired.
When a nitrifying biofilm grows on calcium carbonate substrate the accid production will not effect alkalinity in the water column as the carbon will be retrieved from the substrate, the same when autotrophic denitrification takes place on a substrate of calcium carbonate. In a SBNMS the nitrifying biofilm grows on a mix of calcium carbonate and elemental sulphur resulting in a nitrifying biofilm which has nitrogen gas N2 as an end product and the effect on alkalinity is minimal. Calcium and all other minerals and building materials are added, depending of the chalk used. The removal rate can easely be managed as this is the case with any bio-filter.
An SBNMS can be used in normal aquarium conditions usig BADES Columns in a refuge. All information is available in the Makazi Baharini wiki with usefull references.
This is all about managing safely stored usable nitrogen wich is considered to be not needed. By some considdered to be harmfull.
What is best? Removing ammonia as fast as possible and store the nitrogen in usable nitrate in a way the removal rate of both ammonia and nitrate can be managed or wait and see what happens, limiting the bioload as much as possible.
 

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IMO, and this is just opinion, there are better and easier ways to control nutrients. Growing photosynthetic organisms such as algae and corals, for example.
 

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