growing macroalgae : needs a lot of space, must be harvested regularly, risk for sudden die off and the risk for toxics. Effluent must be sterilized
Seems pretty extreme. Do you know a single person who does that? I certainly don't.
very dangerous because all kind of bacteria are cultivated and fed, also toxic ones
Ever seen a case where a toxic bacteria driven by organic carbon dosing caused a clear problem? IMO, this is a "potential" risk that seems to not be real.
Thiobacilllus denitrificans function well in aerobic and anaerobic conditions.
I don't disagree, but since you mention it a lot, do you have evidence that this is the primary species that grows on a reef tank sulfur denitrator?
Will become your problem some day. Instead of macro algae use Halimeda; You can feed it to the animals.
VODKA, it works but don't say you where not warned.
Sulpur-denitrators where lab tested and used in public aquaria for a long time. Everything about the working is known.
http://genome.jgi-psf.org/thide/thide.home.html
http://filebox.vt.edu/users/chagedor/biol_4684/Cycles/Soxidat.html
http://mars.reefkeepers.net/USHomePage/USArticles/Soler/DenitratorSoufre.html
THE AUTOTROPHIC DENITRATATION ON SULFUR - WHAT'S THE STATUS?
http://mars.reefkeepers.net/USHomePage/USArticles/SulphurDenitrator.htm
http://www.masa.asn.au/phpBB3/viewtopic.php?f=55&t=249607l]
ref:Congrès E.U.A.C., Munich, Salzbourg & Innsbruck 1996
Mém. Inst. Océano. P. Ricard 1997, pp: 7-13
ELIMINATION DES NITRATES PAR FILTRATION
BIOLOGIQUE AUTOTROPHE SUR SOUFRE EN
AQUARIOLOGIE MARINE
Michel HIGNETTE,* Benoit LAMORT,* Marc LANGOUET,** Sébastien LEROY* et Guy MARTIN***
* Aquarium du MAAO - 293, Av. Daumesnil, 75012 Paris
** Le Grand Aquarium - La Ville Jouan - Av. du Général Patton, 35400 Saint Malo
*** Laboratoire Chimie des Nuisances et Génie de l'Environnement ENSCR - Av. du Général Leclerc, 35700 Rennes
THE AUTOTROPHIC DENITRATATION ON SULFUR
WHAT'S THE STATUS?
Last update: 12/01/99
By Marc LANGOUET ing ENSCR, Translated by Nicolas Will
In a confined space, like the one in an aquarium, the regular addition of food that necessarily contain a quantity, more or less important, of nitrogenous compounds, will, without fault, lead to a level of nitrate incompatible with the inhabitants life.
This phenomenon is now well known by most aquarists, in particular those that maintain reef aquariums. The coral's tolerance regarding nitrates is particularly small compared to other living organisms.
Various solutions were proposed to avoid this problem: water changes, algal turf scrubbers... The most common of all is probably the protein skimmer, pillar of the Berlin Method, which consists in the elimination of a maximum of nitrogenous compounds before they are transformed into nitrates.
However, this method are not without difficulties and do not always allow to easily get rid of the problem. I am mostly thinking about aquariums well or very loaded by fish or about those that are hosting corals or invertebrates needing frequent additions of food (a good number of gorgonians or beautiful corals like Tubastraea aurea, the Dendronephtya family or the Carotalcyon sagamianum).
These beautiful animals are rarely raised in aquariums because of the fact that they need to be very regularly fed (which can be automated), and this leads very quickly to high nitrate levels.
I will explain here the two original methods that I developed and which use could quickly spread.
1. Autotrophic denitratation on sulfur
An article published by MARS (18/5/98) and written by Christophe SOLER gives a good picture of the method. I will just simply give historical precision and further information. It is my ex-professor Guy Martin from Ecole Nationale Supérieure de Rennes who is at the origin of this idea; he applied it to fresh water treatment for public water.
I tested this method with seawater, which was new, especially since we didn't know if it would have toxic consequences for our animals, as soon as 1991.
It is only by the end of 1994, after three years of experiments without apparent toxicity in numerous aquariums and species present at home, that I proposed this method to Michel Hignette, curator of the MAAO aquarium. A pilot project was lunched under my care.
Since then the experiment was done on a much bigger scale, at the MAAO, as well as in the Grand Aquarium in Saint-Malo, of which I was technical and scientific director from June, 1st 1996 to mid-December 1997.
I wish to stress the fact that I am using since 1996 beads of sulfur of a 3.5-mm diameter. This form is much easier to use than bars that you have to break using a hammer.
The quantity of sulfur to use depends on the initial nitrate level at startup and on the amount of food added. I consider that a sulfur volume equal to 1% of the total water volume is enough when the initial level is below 50 mg/l (NO3-).
The water flow that must go through the sulfur column depends on the nitrate level of the water to be treated: the more nitrates, the lower the flow must be, otherwise you will find part of the nitrates will be found after the column.
At startup, you can count on 1 liter per hour and per sulfur liter in the column. Then you can adjust in the following manner:
- If the flow rate is too low, you will get a rotten egg smell at the column's exit due to a production of sulfurous hydrogen (H2S). This will rarely happen for really low flow rates.
- If the flow rate is too high, you will detect nitrites or nitrates in the output water.
- If the flow rate is correct, you should obtain 0 nitrates.
However, experiments show that the system is very tolerant regarding the flow rate, which could go up to 5 liters per hour per sulfur liter.
The water sent to the column could come from a filter derivation or directly from the aquarium. The column must allow the produced nitrogen to escape: for these reason a vertical circulation, from bottom to top, seems a better choice, with a flow-rate setting at the input, not at the output. The column's output can be open to the air. The water exiting the sulfur column can be very acidic, but after my experiments getting the gas out of the water (by using an air-stone for example) allows to get a pH close to the original. The water's acidity is then at least mainly linked to the presence of carbon dioxide; thus the idea to use this water to make a calcium reactor by making it flow in a second (and why not a third) columns, identical in size to the one containing the sulfur, but this time filled with maerl or some coral sand (the same that you are using for your sandbed).
This output water also contains sulfates in quantities slightly higher than at the input, but in 7 year of experiments it has never been observed any consequence, even in aquariums that didn't get any water changes for years. It must be noted about that subject that there was an error in the publication made with the MAAO: the sulfur level in natural seawater is near 900 mg/l; this sulfur is present under the form of about 2.65 g/l sulfate (SO4--), quantity, which by itself can explain that the system's addition in sulfate will be without any notable consequence.
2. Pr. Jaubert's method boosted by sulfur
Pr. Jaubert's method is now more and more known; I've been using it since 1994. It consists in placing nitrates reduction into nitrogen and the calcium reactor directly inside the aquarium. The reduction is done in the lower part of a thick layer (8 to 10-cm) of sand (J. Jaubert pers. comm.). This method works very well; however, it seems limited to aquariums with low fish load, or not fed very often, most probably by lack of organic elements in the sand's lowest part, a limiting factor for anaerobic bacteria development, which transforms nitrates into nitrogen by using carbonated matter (organic matter).
It also seems that only well-lit aquariums can work following this method, even if we don't have any complete explanation yet.
Finally, the substrate's surface that is covered by the rocks must not be over 25% of the total surface (J. Jaubert pers. comm.).
If, for a reason or another, nitrates are persistently present in the water, we can boost the system to make them disappear, faster, by accelerating the bacterial process by introducing organic compounds in the lower layer of sand (glucose, by example, by introducing a tube that penetrates under the layer, the other extremity sticking out of the water in the air).
To push Pr. Jaubert's method beyond its limits, i.e. in a heavily fed or under-lit aquarium, without adding glucose under the sandbed, and still conserve its advantages, i.e. its extreme simplicity, no external reactor, no flow rate to set, incorporated calcium reactor, etc. an idea came to me, a few years ago, to get rid of the limiting factor that is made of the quantity of organic compounds present in the lower layer of sand by boosting the system with a thin layer of sulfur in the form of beads at the same level. This allows the system to work in an autotrophic way instead of a carbon-heterotrophic-only way.
The device that I successfully experimented is made of a traditional floor net, from an under-gravel filter without up-lift (the water flows only naturally through the sand, just like in Pr. Jaubert's method).
I established at the end of August 1998 an experimental protocol.
I completely rebuilt a 100-liters aquarium that was established a few years back with 6 to 8-cm of coral sand and a few live rocks. It must be noted that this aquarium, even if it was setup following the Jaubert principle, had nitrate level rises during feeding periods.
Even empty of any animal and not fed for months, its nitrate level did not diminish. It is the perfect example of a scarcely lit Jaubert aquarium that does not work fast enough, most probably because of a lack of nutrients for the anaerobic bacteria present in the lower layer.
I setup the system by layering sulfur beads between the UGF plate and the sand, 1/2 cm thick, sandwiched between two plastic mosquito nets.
The 65 to 70 liters of water contained 35 mg/l of nitrate (NO3-). I reused this water to fill the new setup. Five days later the aquarium had a nitrite level above 10 mg/l. I was using live sand that was already full of aerobic bacteria. It was the first step of the transformation of nitrate into nitrite using sulfur that was starting, and not the transformation of ammoniac into nitrite like happens traditionally in a newly established tank.
On the tenth day, the nitrite level was of about 1 mg/l; the transformation of nitrite into gaseous nitrogen was on going. In a system of this type, where the water flow is produced by natural diffusion through the sandbed and not forced through a filter, it is logical that the evolution is slower than in systems using reactors.
On the eleventh day no nitrite was left and the nitrite level was below 5 mg/l.
On the Twelfth Day the nitrate level was not measurable at all (below 1 mg/l).
On the 24th day the aquarium was still without any nitrate, even if it received every day a cube of frozen artemias (around 1-cm3), which is pretty high for a 65-liters tank. The Tubastraea aurea in this aquarium for two months was nearly opened all day long, liking the strong water flow in the tank and the daily addition of food. It was the same for some Actinias equina and two Carotalcyon sagamianum specimens. The pH was around 7.7, because of Carbon dioxide present (degassing raises the pH) but this didn't look like it bothered the invertebrates. The KH was between 6 and 7. It was the same as the one from the Channel water that I used to fill the tank.
This very interesting method could perfectly be established in the sump of an existing aquarium so that the whole setup doesn't have to be rebuilt. The low pH will most probably shock some of you, but it should be noted that with Pr. Jaubert's method, the pH and KH are generally lower than those found using the Berlin method (at least in the morning concerning the pH). It is without noticeable consequence for the animals. My aquarium is not lit (only by ambient light in the room). It is not aerated by any other mean than a normal air/water interface, this interface being slowly moved because I preferred to direct current in the direction of the corals to bring then food.
In a lighted aquarium and with a good surface movement, or with an air stone, the dissolved Carbon dioxide should be eliminated in a better way, and the pH should be higher. The sulfur surface may not cover the tankÃs entire surface like I did.
I am personally convinced that this CO2 presence in the water in not necessarily a problem, but time will tell. As soon as I can lay my hands of some Dendronephtyas, gorgonians, Sphaerella krempfis, sponges, etc. I will add them to this aquarium. Feeding should be automated and more regular, simple flakes are enough to open the Tubastraea aurea.
Please send me your experiments in this field.
To be continued...
Marc LANGOUET.
6/11/98
Note 1
Autotrophic: not needing any external energy or nutrients addition
Heterotrophic: needing external energy or nutrients addition
Note 2
You can send your comments or experiments results to
Marc LANGOUET
La Guimorais
35350 St Coulomb
tél.+fax. 02 99 89 41 69 email
marc.langouet@wanadoo.fr
or to Récif France Britanny, which will forard
Pierre ZMIRO
17 rue de la gare
49440 Candé
Tél. 02 41 94 92 10
Fax 02 41 94 92 11
E-mail
FBZ@wanadoo.fr
Q&A and diverse information
Question: Marc evokes Degassing (escape of produced nitrogen) in his publication. Having no sump for my aquarium, I want to place the column below in the stand; it will then be full of water. I will fill the column with sulfur and maerl (50/50). I want to fix the output in the air, above water surface. Will it be enough for degassing? Can it work like this while being as efficient?
Marc's answer: There is no problem with a column filled with water; the water flow must be from bottom to top of the sulfur maerl column. It must be noted that this mix is not a good idea as the maerl will be transformed into puree with time, and you will have to throw away the whole because it will clog... You should better separate the sulfur and the sand because sulfur can be kept: it doesn't deteriorate.
Question: Must sulfur be regularly added?
Marc's answer: Sulfur is used, but it is very low. It corresponds to
4NO3 + 3S ->2 N2 + 3 SO4
(it is more complex, but it comes to that)
In practice I never added any sulfur in years, even less changed it.
Question: What is the exact use of the air escape? Is it fundamental?
Marc's answer: The air escape is the to help nitrogen getting away, if you work with high nitrate levels. If this level is low, this degassing will be small and I don't think this would be a problem to send this water into a calcium hydroxide reactor. The experiment is left to you.
Question: What is the cost of sulfur?
Marc's answer: Sulfur's cost is about US$2 per kg
Question: I built a reactor following MARS' plan with 2x 5-liters columns; one contains sulfur beads, the other some calcareous substrate. In 8 days, nitrate, which used to be at about 25 mg/l in my 400-liters aquarium, are now at zero at reactor's output. A month after the setup nitrates is between 0 and 5mg/l in the aquarium. It's really working!
But as nothing is easy in reefkeeping, there are other parameters changed by the sulfur reactor.
Calcium was at 410 mg/l before y using limewater as make-up water (5-liters per day, whichÃs low because my tank is closed and using fluos). After a month the level is at 490 mg/l at reactor's output! Great! Is it the substrate column doing anything?
However the pH is from 0.6 to 0.8 lower at reactor's output. In the aquarium it went down from 8.2 to 7.8 in a month (7.05 at reactor's output). How can I cleanly raise the pH without disturbing the animals? Will this pH drop ever stop? Is it because of sulfur denitratation system?
MARS' Answer: The flow rate through the reactor is not given. Maybe you can tweak that (higher or lower) to lower the acid dosing in the aquarium like in a Calcium carbonate/CO2 reactor. Also like in a calcium reactor if the substrate is too big, water flows too fast and doesn't dissolve it and doesn't lose acidity. To correct this, either lengthen the circuit or get finer substrate.
MARS' comments:
This method has now been used for a while by a good number of hobbyists who all saw their nitrates level drop. One thing to look at (beginners beware!) would be, as nitrates consumption is huge, to lower skimming quality (to be kept to remove the compounds not removed by the sulfur reactor?). Plankton would be protected. As the sulfur reactor is making acid, calcium production is allowed by adding a calcium reactor in-line. No more CO2 bottle. A number of question marks are left, but the system is charming! We can imagine small autonomous aquariums, but why not also large (>1,000-liters) ones equipped with modest and cheap skimmer (like the super skimmer) and this revolutionary system that is sending the rest to the museum?
Since we are thinking of revolutionary concepts, here is one elaborated by Christophe Soler: instead of setting up a conventional calcium reactor after the sulfur denitrator, take a kalk-reactor filled, not with coral sand, but with calcium carbonate powder. Acid water flowing slowly (5 l/h for a 500-liters tank) will dissolve easily this powder that is offering a much greater contact surface than sand. The produced calcium level should be equally greater. The internal mixing of the reactor will prevent the formation of mud. To be tested! Anyone?
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