Sulphur in the reefaquarium

If everyone could just cool off here, I'm looking to do a little experimental citizen science here and settle some things :P

I'm going to use ~1L of sulfur split among 5 "sulfur sausages" in my sump. I don't have any coral yet, and I have regular alkalinity monitoring with a kH guardian.

My nitrate testing capability isn't great right now, but I have between 25-50 ppm nitrate in the display tank. I'd like to be a scoach lower than that, and think this should provide some pretty interesting results, one way or another.
 
You are correct that I have never used a sulfur reactor, but I understand the chemical processes involved. I have also never vacationed in Wuhan China. Do I need to in order to think it not the best plan?

In the future, people are going to read this and wonder... what the heck is going on in Wuhan :P
 
There is no way to avoid the imbalance. Either alk is depleted, or if you dissolve calcium carbonate to supply that alkalinity, calcium rises.

I think I understand. I intend to let the sulfur microbe action deplete alk, but then replenish it via automated alk monitoring and dosing.
 
You are correct that I have never used a sulfur reactor, but I understand the chemical processes involved. I have also never vacationed in Wuhan China. Do I need to in order to think it not the best plan?

A BADES System may not be the best solution for nitrogen management, other far less well understood ways for nutrient management are advised and promoted as safe to use.
Based on official publications I think there is a lot more risk in going on vacation driving a car, assuming the given information is correct. Owning a car is promoted everywhere!

After some decades of practical use and much research all over the world, about everything concerning BADES is known and well understood. The risks and side effects are known and can easily be avoided or and corrected. A BADESS user may have full control over the nitrate removal rate and nitrate level. BADES may correct the nutrient inbalance created by the use of a skimmer.

What would be the best plan for effectively remove nitrate from a mixed reef aquarium, not considering a BADESS?
For example to correct the nitrate/phosphate ratio from 100:1 to 10:1 ?
 
A BADES System may not be the best solution for nitrogen management, other far less well understood ways for nutrient management are advised and promoted as safe to use.
Based on official publications I think there is a lot more risk in going on vacation driving a car, assuming the given information is correct. Owning a car is promoted everywhere!

After some decades of practical use and much research all over the world, about everything concerning BADES is known and well understood. The risks and side effects are known and can easily be avoided or and corrected. A BADESS user may have full control over the nitrate removal rate and nitrate level. BADES may correct the nutrient inbalance created by the use of a skimmer.

What would be the best plan for effectively remove nitrate from a mixed reef aquarium, not considering a BADESS?
For example to correct the nitrate/phosphate ratio from 100:1 to 10:1 ?

I’m not a fan of ratios bring an appropriate way to make decisions. For both of your ratios, nitrate may be too high (say, 1000 ppm), too low (0.000001 ppm), it just right (say, 1-10 ppm). What, if anything, I would do about it depends on where on that spectrum the actual values are.
 
In the future, people are going to read this and wonder... what the heck is going on in Wuhan :p

I hope that is true!
 
I’m not a fan of ratios bring an appropriate way to make decisions. For both of your ratios, nitrate may be too high (say, 1000 ppm), too low (0.000001 ppm), it just right (say, 1-10 ppm). What, if anything, I would do about it depends on where on that spectrum the actual values are.
The question was not about ratio's , it is about effectively removing nitrate to restore the nutrient balance. Removing a lot of nitrate without risking phosphate starvation. I rephrase my question, how to lower the nitrate level safely from 20ppm to 2ppm having a phosphate level of 0,2ppm?
 
I think I understand. I intend to let the sulfur microbe action deplete alk, but then replenish it via automated alk monitoring and dosing.
having made and used over five different sulfur denitrator and have one right now homemade show pictures in a minute. Unless the water flows through your project the results may take longer like months.
I don't just talk the talk, I walk the talk

Screenshot_2020-02-01-07-12-19.png Screenshot_20200204-045226.png Screenshot_20200204-045242.png
 
It is not possible to make correct calculations regarding the calcium production and the influence on carbonate hardness based on the nitrate level, on the difference between the supply and the output of a BADES System. One can only make a difficult estimate.


It depends not only on the BADES process but also on other sulfur sources. An important part of the nitrate is used and is needed for the oxidation of HS, originating from anaerobic remineralization and sulfate reduction, partial and complete sulfide oxidation whereby sulfur and/or sulfate is produced depending on the nitrate supply.
As with heterotrophic denitrification, the combined autotrophic denitrification by means of sulfur derivatives, the reduction of sulfate to sulfide, the oxidation of sulfide and the reduction of nitrate has the same positive effect on alkalinity by increasing it by 3.57mg CaCO3. (VanRijn2005) ref: http://www.baharini.eu/baharini/doku.php?id=nl:badess:theorie:de_neveneffecten#alkaliniteit
That sulfur or sulfate is formed during the oxidation of sulfide is determined by the sulfide/nitrate ratio in the biofilm. (Fang2010) At an N: S ratio of 8: 5 sulfate is formed, at a ratio of 2: 5 sulfur (SherEnCo2008) ref: http://www.baharini.eu/baharini/doku.php?id=nl:badess:theorie:de_neveneffecten#waterstofsulfide
This is to underline the importance that sufficient nitrate is present in an oxygen-free seawater containing reactor and that the pursuit of 0 nitrate in the effluent is not such a good idea. The use of a sulfur denitrator is accompanied by proper and difficult flow management and is therefore not recommended by me.


A BADES reactor is NOT kept anoxic and 0 nitrates in the outflow is not pursued, it is not necessary!
Aerobic and anaerobic remineralization, nitrification, autotrophic and heterotrophic denitrification, DNRA, these are all processes that influence the environment, the oxygen demand and the denitrification capacity of a biofilm. And the substrate on which the biofilm grows plays a major role.
Making a calculation based on just one of the many processes can never lead to a correct reflection of reality.
It is also very important that the correct data is used as a basis.
For example, one cannot calculate the correct Ca production using the BADES process since no Ca is produced in this process.
The process can result in Ca being produced if use can be made of the acids produced to dissolve calcium carbonate. In that case, alkalinity as a carbon source has already been used. and use is made of H + production after the process and pH transition has taken place.
2 H2O + 5 S + 6 NO3 - → 3 N2 + 5 SO42 - + 4 H + (HolmesFarley2003) ref: https://www.advancedaquarist.com/2003/8/chemistry
According to this formula, I arrive at a Ca production of ± 4.3 grams per 10 grams of nitrate converted to nitrogen gas if all H + production can be used to dissolve calcium carbonate. I am not a chemist, it is an estimate. The formula used does not take into account the build-up of the necessary biomass. If we add the cell structure for which ammonia is used, this is according to Batchelor and Lawrence
55S 50NO 3 38H 2 O 20 CO 2 4 NH 4 → 4 C 5 H 7 N 2 O 25 N 2 55 SO 4 64H. Almost twice as much H + is produced here and possibly twice as much Ca. Later this was corrected to 11 S 10 NO3 - 4.1 HCO3 - 0.5 CO2 1.71 NH4 2.5 H2O -> 0.92 C5H7NO2 11 SO4 - 5.4 N2 9.62 H and then we get almost half more H + production. To make correct calculations, one must not only have knowledge of the processes but also opt for the most realistic. ref:http://www.baharini.eu/baharini/dok...ie:stikstofkringloop#autotrofe_denitrificatie


In a BADESS we try to use Calcium Carbonate as a carbon source and we cannot use the above formulas as in these formulas alkalinity is used as a carbon source.
I use the formula of Zhang, the designer of the SLAD system. 55S + 44CaCO 3 + 50NO 3- + 18H2O + 4NH4 + → 4 C5H7O2N + 25N 2 + 55SO4 2- + 44Ca 2+ + 24HCO3- (TCZhang2004) ref:http://www.baharini.eu/baharini/doku.php?id=en:makazi:het_water:slad_systeem&rev=1580734860 As one can see, no H + is produced here, but Ca and bicarbonate are produced directly. According to this formula, I get 5.68 grams of calcium per 10 grams of nitrate converted by the BADES process. A big difference with the calculation according to Holmes Farley. Added to this is the production of the nitrification process, whereby a BADES System can possibly meet the calcium demand.

The practice will be completely different from the theoretical approach as only a part of the nitrate is removed by the BADES process and many other processes influence the result.

It is therefore useless to try to make all kinds of calculations on which one cannot really rely on practice. The reality will be somewhere in the middle.

To use BADES, no special and expensive equipment or making all kinds of calculations is required, not even a reactor. Common sense only. A good BADES system will have little influence on the alkalinity in the system and will produce calcium . Calcium is also produced by autotrophic processes in an aquarium without BADES. The usual measures for correction are sufficient.
For easy management of the nitrate level, I recommend a separate filter, reactor or refugium.

I strongly discourage the use of an anoxic reactor, a sulfur denitrator, unless people know what they are doing. In that case it works very well for lowering a high nitrate content, but the result deteriorates and the risks increases as the nitrate content decreases. The amount of oxygen to be removed remains the same, which means that with a lower nitrate content, insufficient nitrate can be supplied, resulting in sulfate reduction.
The intention is to remove daily nitrate overproduction on a daily basis with a low nitrate content, it must be possible to adjust the flow to the nitrate content so that the same amount can be removed on a daily basis, or slightly more to lower the level. The lower the nitrate content, the more flow is needed, the more oxygen is supplied, to remove the same daily nitrate overproduction daily. This is not possible with a sulfur denitrator which is kept anoxic.
 
I'm going to try what you're saying because I think there is some potential with passive sulfur column, but the Zhang equation shows roughly a 2:1 ratio of produced Ca to HCO3. Theoretically over time, this will necessarily produce an excess of calcium, which comes with it's own set of problems. Which is why I want to try running it without the CaCO3 in the column.
 
I'm going to try what you're saying because I think there is some potential with passive sulfur column, but the Zhang equation shows roughly a 2:1 ratio of produced Ca to HCO3. Theoretically over time, this will necessarily produce an excess of calcium, which comes with it's own set of problems. Which is why I want to try running it without the CaCO3 in the column.
In that case, alkalinity will be consumed and pH influenced, something I would prefer to avoid.
Theoretically, in a reef aquarium corrections must be made for calcium consumption, production and precipitation. Each setup will have its own set of problems to solve, to provide a stable living environment needed.
 
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When using BADES rolls ref: http://www.baharini.eu/baharini/doku.php?id=en:badess:bades:bades-kolommen a lot of ammonia-nitrogen may be processed to leave the aquarium as Nitrogen gas. It is very effective. This means the availability of nitrogen changes drastically in an established tank. That is why I advise to use such BADES-rolls in a refuge and make the flow to or from the refuge manageable. This way the nitrogen removal rate will become manageable, limiting drastic changes. Start with a small roll, one may add as many BADES-rolls as needed. One should keep the nitrate level measurable at all times.
1581336341660.png

As such a BADES-roll is very effective and removes ammonia-nitrogen, a much higher bio-load can be supported.
All BADES Systems need enough nitrate to operate, to keep all processes going, and are based on the daily nitrogen overproduction. ref: http://www.baharini.eu/baharini/doku.php?id=en:badess:start
1581336400194.png
 
The question was not about ratio's , it is about effectively removing nitrate to restore the nutrient balance. Removing a lot of nitrate without risking phosphate starvation. I rephrase my question, how to lower the nitrate level safely from 20ppm to 2ppm having a phosphate level of 0,2ppm?

organic carbon dosing is one way.

Growth of algae is another. I don’t think phosphate will become limiting in this scenario, but if it does, some phosphate dosing will solve it.
 
It is not possible to make correct calculations regarding the calcium production and the influence on carbonate hardness based on the nitrate level, on the difference between the supply and the output of a BADES System. One can only make a difficult estimate.


It depends not only on the BADES process but also on other sulfur sources. An important part of the nitrate is used and is needed for the oxidation of HS, originating from anaerobic remineralization and sulfate reduction, partial and complete sulfide oxidation whereby sulfur and/or sulfate is produced depending on the nitrate supply.
As with heterotrophic denitrification, the combined autotrophic denitrification by means of sulfur derivatives, the reduction of sulfate to sulfide, the oxidation of sulfide and the reduction of nitrate has the same positive effect on alkalinity by increasing it by 3.57mg CaCO3. (VanRijn2005) ref: http://www.baharini.eu/baharini/doku.php?id=nl:badess:theorie:de_neveneffecten#alkaliniteit
That sulfur or sulfate is formed during the oxidation of sulfide is determined by the sulfide/nitrate ratio in the biofilm. (Fang2010) At an N: S ratio of 8: 5 sulfate is formed, at a ratio of 2: 5 sulfur (SherEnCo2008) ref: http://www.baharini.eu/baharini/doku.php?id=nl:badess:theorie:de_neveneffecten#waterstofsulfide
This is to underline the importance that sufficient nitrate is present in an oxygen-free seawater containing reactor and that the pursuit of 0 nitrate in the effluent is not such a good idea. The use of a sulfur denitrator is accompanied by proper and difficult flow management and is therefore not recommended by me.


A BADES reactor is NOT kept anoxic and 0 nitrates in the outflow is not pursued, it is not necessary!
Aerobic and anaerobic remineralization, nitrification, autotrophic and heterotrophic denitrification, DNRA, these are all processes that influence the environment, the oxygen demand and the denitrification capacity of a biofilm. And the substrate on which the biofilm grows plays a major role.
Making a calculation based on just one of the many processes can never lead to a correct reflection of reality.
It is also very important that the correct data is used as a basis.
For example, one cannot calculate the correct Ca production using the BADES process since no Ca is produced in this process.
The process can result in Ca being produced if use can be made of the acids produced to dissolve calcium carbonate. In that case, alkalinity as a carbon source has already been used. and use is made of H + production after the process and pH transition has taken place.
2 H2O + 5 S + 6 NO3 - → 3 N2 + 5 SO42 - + 4 H + (HolmesFarley2003) ref: https://www.advancedaquarist.com/2003/8/chemistry
According to this formula, I arrive at a Ca production of ± 4.3 grams per 10 grams of nitrate converted to nitrogen gas if all H + production can be used to dissolve calcium carbonate. I am not a chemist, it is an estimate. The formula used does not take into account the build-up of the necessary biomass. If we add the cell structure for which ammonia is used, this is according to Batchelor and Lawrence
55S 50NO 3 38H 2 O 20 CO 2 4 NH 4 → 4 C 5 H 7 N 2 O 25 N 2 55 SO 4 64H. Almost twice as much H + is produced here and possibly twice as much Ca. Later this was corrected to 11 S 10 NO3 - 4.1 HCO3 - 0.5 CO2 1.71 NH4 2.5 H2O -> 0.92 C5H7NO2 11 SO4 - 5.4 N2 9.62 H and then we get almost half more H + production. To make correct calculations, one must not only have knowledge of the processes but also opt for the most realistic. ref:http://www.baharini.eu/baharini/dok...ie:stikstofkringloop#autotrofe_denitrificatie


In a BADESS we try to use Calcium Carbonate as a carbon source and we cannot use the above formulas as in these formulas alkalinity is used as a carbon source.
I use the formula of Zhang, the designer of the SLAD system. 55S + 44CaCO 3 + 50NO 3- + 18H2O + 4NH4 + → 4 C5H7O2N + 25N 2 + 55SO4 2- + 44Ca 2+ + 24HCO3- (TCZhang2004) ref:http://www.baharini.eu/baharini/doku.php?id=en:makazi:het_water:slad_systeem&rev=1580734860 As one can see, no H + is produced here, but Ca and bicarbonate are produced directly. According to this formula, I get 5.68 grams of calcium per 10 grams of nitrate converted by the BADES process. A big difference with the calculation according to Holmes Farley. Added to this is the production of the nitrification process, whereby a BADES System can possibly meet the calcium demand.

The practice will be completely different from the theoretical approach as only a part of the nitrate is removed by the BADES process and many other processes influence the result.

It is therefore useless to try to make all kinds of calculations on which one cannot really rely on practice. The reality will be somewhere in the middle.

To use BADES, no special and expensive equipment or making all kinds of calculations is required, not even a reactor. Common sense only. A good BADES system will have little influence on the alkalinity in the system and will produce calcium . Calcium is also produced by autotrophic processes in an aquarium without BADES. The usual measures for correction are sufficient.
For easy management of the nitrate level, I recommend a separate filter, reactor or refugium.

I strongly discourage the use of an anoxic reactor, a sulfur denitrator, unless people know what they are doing. In that case it works very well for lowering a high nitrate content, but the result deteriorates and the risks increases as the nitrate content decreases. The amount of oxygen to be removed remains the same, which means that with a lower nitrate content, insufficient nitrate can be supplied, resulting in sulfate reduction.
The intention is to remove daily nitrate overproduction on a daily basis with a low nitrate content, it must be possible to adjust the flow to the nitrate content so that the same amount can be removed on a daily basis, or slightly more to lower the level. The lower the nitrate content, the more flow is needed, the more oxygen is supplied, to remove the same daily nitrate overproduction daily. This is not possible with a sulfur denitrator which is kept anoxic.

I guess I have more confidence in my ability to calculate alkalinity loses than you have in yours. I think it is incredibly simple that any nitrate removed by a sulfur denitrator will deplete alkalinity by a known amount and if you replace that lost alkalinity by dissolving calcium carbonate, you boost calcium by a known amount. Obviously, some nitrate will be used in other ways that will have a different impact on alkalinity.
 
organic carbon dosing is one way.

Growth of algae is another. I don’t think phosphate will become limiting in this scenario, but if it does, some phosphate dosing will solve it.

I am pretty sure phosphorus will become the limiting factor in my proposed scenario if an assimilation method is used.
In case of, corrections often come too late!!!!!
Growth of algae does not correct the nutrient balance as not only nitrogen is removed when harvested, so it is not really a direct solution for my question.
Adding phosphate is a very bad idea as it may cause other essential nutrients to become the limiting factor wich even maybe worse.
The scenario may be responsible for a lot of problems and coral decay if organic carbon is dosed (promoting fast growth) to lower the nitrate level. To balance the nitrate level with the phosphate present( 0,2ppm), as proposed in my example, +- 1,8 ppm of phosphate is needed to lower the nitrate level from 20ppm to 2ppm using an assimilation method, and all other essentials. Only 0,2 ppm is available.

Using a BADES System the nitrogen content can easily be managed as desired and a lot less phosphate and other essentials are needed.

For the moment, an algae filter in a refuge is my preferred nutrient management method for LNS, using modified F2 media, this way compensating for the unbalance created by a skimmer and limiting the risk for nutrition problems. The removal rate is low, not suitable to correct the nutrient balance in a high nutrient mixed reef aquarium with a skimmer.
We look into the use of bio-floc technology in a refuge. Bio-floc can be harvested and reused and the nutrient uptake is a lot faster as when using algae.
 
I am pretty sure phosphorus will become the limiting factor in my proposed scenario if an assimilation method is used.
In case of, corrections often come too late!!!!!
Growth of algae does not correct the nutrient balance as not only nitrogen is removed when harvested, so it is not really a direct solution for my question.
Adding phosphate is a very bad idea as it may cause other essential nutrients to become the limiting factor wich even maybe worse.
The scenario may be responsible for a lot of problems and coral decay if organic carbon is dosed (promoting fast growth) to lower the nitrate level. To balance the nitrate level with the phosphate present( 0,2ppm), as proposed in my example, +- 1,8 ppm of phosphate is needed to lower the nitrate level from 20ppm to 2ppm using an assimilation method, and all other essentials. Only 0,2 ppm is available.

Using a BADES System the nitrogen content can easily be managed as desired and a lot less phosphate and other essentials are needed.

For the moment, an algae filter in a refuge is my preferred nutrient management method for LNS, using modified F2 media, this way compensating for the unbalance created by a skimmer and limiting the risk for nutrition problems. The removal rate is low, not suitable to correct the nutrient balance in a high nutrient mixed reef aquarium with a skimmer.
We look into the use of bio-floc technology in a refuge. Bio-floc can be harvested and reused and the nutrient uptake is a lot faster as when using algae.

The reason I suggest organic carbon dosing is that it is well demonstrated by reefers that it mostly lowers nitrate with little impact on phosphate.

i expect that a reef tank with 0.2 ppm phosphate in the water will supply far more than that if you try to drive phosphate to 0.02 ppm as it desorbs from rock and sand surfaces, but in the absence of any rock or sand, one might need to dose phosphate to lower nitrate from 20 ppm to 2 ppm using a balanced uptake method like algae.
 
I guess I have more confidence in my ability to calculate alkalinity loses than you have in yours. I think it is incredibly simple that any nitrate removed by a sulfur denitrator will deplete alkalinity by a known amount and if you replace that lost alkalinity by dissolving calcium carbonate, you boost calcium by a known amount. Obviously, some nitrate will be used in other ways that will have a different impact on alkalinity.
A sulfur denitrator is not recommended by me to be used in a life support system!

If one forgets to add what is necessary, removing oxygen present, bio-load, nitrification, remineralisation, the use of sulfur derivates etc.. If one limits it all to one thing, it becomes pretty simple, which it isn't. In practice, the results are a lot different from what can be retrieved from what you consider to be incredibly simple.
 
The reason I suggest organic carbon dosing is that it is well demonstrated by reefers that it mostly lowers nitrate with little impact on phosphate.

i expect that a reef tank with 0.2 ppm phosphate in the water will supply far more than that if you try to drive phosphate to 0.02 ppm as it desorbs from rock and sand surfaces, but in the absence of any rock or sand, one might need to dose phosphate to lower nitrate from 20 ppm to 2 ppm using a balanced uptake method like algae.

It was a simple question, with an answer not based on assumptions.
 
ok. I think my recommendations are straightforward solutions.
About using BADES in a reef aquarium I do not think so, it is not a solution at all if given info is not close to reality.
This does not mean the provided information is incorrect, the recommendation may be not correct or and incomplete to retrieve the desired results in a present situation.
 

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