Most Effective Method of Nitrate Reduction--Methanol Dosing - The Planted Tank Forum
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post #1 of 49 (permalink) Old 01-27-2017, 04:05 PM Thread Starter
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Most Effective Method of Nitrate Reduction--Methanol Dosing

So I thought I'd share a bit of an experiment I did in my freshwater 75-gallon in regards to Nitrates that I hope other people will find helpful. I am going to try to share this in as many places as I can, as I think I'm the only one who's tried it, and it has been by far the most successful method in significantly reducing Nitrates. It's long, sorry, but I think it's really important. Basic point is that methanol is the best option if you are serious about reducing Nitrates in your freshwater aquarium long-term.
So I have a pretty heavily stocked goldfish aquarium that is also planted. I was doing ok with Nitrates for a while, since the fish were small, I was siphoning out the waste about every other day, and the tank wasn't as heavily planted as it is now (contrary to popular opinion, a planted aquarium can in certain instances INCREASE Nitrates, since rooted plants are very efficient at trapping sediment and waste, thus making it difficult to siphon and for the filters to capture it). However, the fish have grown quickly, and I had to keep them well-fed, because they kept picking at the plants. I eventually moved a couple of the big ones out into the stock tank with the pond fish, but Nitrates were still way too high (like 80 ppm+). Some of you may have seen my previous argument about whether plants, water changes, or anaerobic bacteria are more efficient/effective for reducing Nitrates, and I said the anaerobic bacteria is what is most important. Going off of that, I attempted to increase my anaerobic bacteria population, both by creating more appropriate media for them to grow on, and more importantly, adding Red Sea NO3/Po4 Remover (methanol). I was using this in my reef aquarium, and it worked really well, almost too well (I lowered the dose, even though my bioload is bigger now). The idea behind methanol dosing is it gives the bacteria a source of inorganic carbon, which is often a limiting nutrient for them. It is used in wastewater treatment, and is the most effective and safe compound to use. Everywhere I read on forums said they either didn't know if it could be used in freshwater or said not to do it (but as usual, couldn't back up their statements with legitimate research). I read; however, that most fish and plants are quite tolerant of it, and plants even usually perform better with reasonable doses. So I decided to try it (by this point, I had tried basically every product out there for reducing Nitrates...most are junk, btw, Algone and API Nitrazorb were somewhat effective, but you need to use a lot of it, and it's probably better for more moderate NO3 levels). Nitrates steadily declined, and this morning, they were at zero. Keep in mind, this is with a heavily stocked tank with goldfish, which probably produce more waste than any other aquarium fish. I did get quite a bacterial bloom, but that's the point. I've had to clean out the filter intake tubes pretty regularly just to keep them working.
If you are having a Nitrate problem, I can tell you this is by far the best way to reduce it. Aquariums are all about recreating natural processes as closely as possible. Most freshwater ecosystems have very effective Nitrate absorbtion through anaerobic bacteria found in the anoxic soils of wetlands. We need to try to recreate this as closely as possible. Water changes are NOT the best option, and can even be detrimental if you are doing large water changes frequently. It is impossible to get the parameters right each time, unless you are using pure RO or pure tap water, and if you dose CO2 (like me), you are going to have major CO2 and pH fluctuations. Plus, say you are doing 25% water changes. That means you are only reducing Nitrates by 25%, and the next day, they will most likely go back to the same levels they were before. Manually removing waste is a good idea though, but try to take out as little water as possible. If you want to use plants, you can do that, but they need to be fast-growing plants that feed from the water column (like hornwort), and you need to be using high light, high CO2, and regular dosing of Potassium and trace elements.
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post #2 of 49 (permalink) Old 01-27-2017, 05:02 PM
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Very interesting, thanks for posting.


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post #3 of 49 (permalink) Old 01-27-2017, 08:07 PM
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I think the reason a lot of people don't do this is because while it may remove nitrates it adds a lot of unknown organics. Methanol which is "cheap" over the counter stuff is not very pure, and the methods used to produce it also produce a large amount of other organic byproducts. I am sure it works, and that it probably works really well. The issue is that people are scared of the potential for the other organics to harm their: see list of expensive fish/shrimp/whatever. By the way this reaction can also be done with acetic acid (vinegar) the same way it is done with methanol. But again the same problem exists, over the counter acetic acid (vinegar) is very unpure.

For methanol, just a quick google searched showed me that most methanol products at about 8-10 dollars per gallon where about 99.8% pure. That may seem really pure to most people but in chemistry that .2% is huge. Especially because oftentimes its only ppm levels of materials that can be considered dangerous.

For the most part this isn't an issue in municipal water treatment because chlorine gas or UV light is used as well. Both of these will react with most large organic molecules and break them down into less harmful ones.
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post #4 of 49 (permalink) Old 01-27-2017, 08:42 PM
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I thought it was effective in reef tanks because the organic carbon is being dosed in conjunction with using protein skimmers?

I do wonder if the bacteria cells absorb those nitrates when they bloom with the introduction of the carbon source, but that once those bacterial cells themselves die the nutrients such as the nitrogen/nitrates will then be returned back into the water. And that will happen unless you continue dosing ever-larger amounts of carbon to feed an ever-increasing population of bacteria? And perhaps dosing carbon thus doesn't ever actually export the nitrogen out of the system if that is what is happening?

This is just my speculation however, and it could be that if it really is anaerobic bacteria that are feeding on the carbon then the nitrates will just be converted to nitrogen gas and off-gassed into the atmosphere. But anaerobic bacteria I wouldn't think would be visible as a bacterial bloom or as cloudiness, as they'd have to be buried deep in the substrate where there is no oxygen.

Food for thought...
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post #5 of 49 (permalink) Old 01-28-2017, 04:23 AM Thread Starter
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I'll give a more thourough reply and give you my sources later, but for now, first of all, did you both actually read the whole post? This wasn't some random OTC thing of methanol I got at Walmart, I was using a product by Red Sea that is highly rated and has been used by advanced reef keepers for a long time. I have used it in my reef aquarium for about a year with no issues (and I don't use a skimmer). So no, Mxx, what you are saying about nutrients rising again is just not true. This is a long-term solution, and I have had zero fluctuations in my reef aquarium. I keep SPS coral, and I hardly do any water changes (probably not a good thing I admit, but the point is this is effective). Not to be offensive, but you obviously do not completely understand the Nitrogen cycle. In anaerobic bacteria, Nitrates are reduced back into Nitrogen gas. It completely leaves the system (of the aquarium).
For some reason, people think freshwater and saltwater aquariums are completely different and there is no overlap. This is not true. Many, if not most, of the same principles apply to both. I am not saying this just as someone new in the hobby, I have had over 15 years of experience keeping both fresh and saltwater and have my background in water resources and ecology. I've worked in several water quality labs and have done work with the FWS and Greater Gallatin Watershed Council doing stream and wetland analysis and assessment. I am not saying this to be arrogant, but I do have somewhat of an idea of what I'm talking about, and again, there are peer-reviewed studies that will back me up on this.
If you want to disagree with me on this, you can, but you'll need to base it off of something other than just your opinion. And when I was talking about the bacteria bloom, this also "feeds" aerobic bacteria, not just anaerobic.
And Vohlk, I am not lying when I say this is used extensively in water treatment and waste management. Much of the research done has been related to this. One of the initial and most important processes in treatment of waste water is biological.
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post #6 of 49 (permalink) Old 01-28-2017, 04:56 AM
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My intention was not to say you where lying about it being used in waste water treatment, quiet the opposite in fact. I am very familiar with the waste water treatment process and used to work for a company designing waste water treatment facilities. I understand what you are saying completely, I was simply supplying reasons as to why it does work in water treatment. Reasons why it is much safer to use in large scale waste water treatment. There is a lot of chemistry behind it, I do not know what your chemistry background is, I presume some based on your work history, chlorine (which is used very often in waste water management) or high intensity UV light, reacts to break down or "neutralize" lots of "heavy" organic matter. Large organic molecules that make it thruough all of the biological filtration and even the settling tanks are neutralized on the way out of the waste water facility.

The problem (concern whatever you want to call it) is that the chlorine treatment/UV light treatment doesn't exist in most (freshwater tanks (some UV light is used based on filter and whatnot (UV sterilizer))), I do not own saltwater tanks, and while they are similar there is very different chemistry going on in these, (ozone generators? are these still common practice? I do not know I tried my hand at saltwater many years ago but realized my passions lied elsewhere).

My previous post can basically be summed up as saying, over the counter products are relatively impure (unless it is costing somewhere around $400+ per gallon), the impurities in this could (or could not) be dangerous when dosed regularly. But there may be more than just methanol in these mixtures I do not know, maybe they themselves have already been exposed to UV light to break down those "large" organic molecules I do not know.
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post #7 of 49 (permalink) Old 01-28-2017, 10:10 AM
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Quote:
Originally Posted by crypticmonk View Post
So I thought I'd share a bit of an experiment I did in my freshwater 75-gallon in regards to Nitrates that I hope other people will find helpful. I am going to try to share this in as many places as I can, as I think I'm the only one who's tried it, and it has been by far the most successful method in significantly reducing Nitrates. It's long, sorry, but I think it's really important. Basic point is that methanol is the best option if you are serious about reducing Nitrates in your freshwater aquarium long-term. So I have a pretty heavily stocked goldfish aquarium that is also planted. I was doing ok with Nitrates for a while, since the fish were small, I was siphoning out the waste about every other day, and the tank wasn't as heavily planted as it is now (contrary to popular opinion, a planted aquarium can in certain instances INCREASE Nitrates, since rooted plants are very efficient at trapping sediment and waste, thus making it difficult to siphon and for the filters to capture it). However, the fish have grown quickly, and I had to keep them well-fed, because they kept picking at the plants. I eventually moved a couple of the big ones out into the stock tank with the pond fish, but Nitrates were still way too high (like 80 ppm+). Some of you may have seen my previous argument about whether plants, water changes, or anaerobic bacteria are more efficient/effective for reducing Nitrates, and I said the anaerobic bacteria is what is most important. Going off of that, I attempted to increase my anaerobic bacteria population, both by creating more appropriate media for them to grow on, and more importantly, adding Red Sea NO3/Po4 Remover (methanol). I was using this in my reef aquarium, and it worked really well, almost too well (I lowered the dose, even though my bioload is bigger now). The idea behind methanol dosing is it gives the bacteria a source of inorganic carbon, which is often a limiting nutrient for them. It is used in wastewater treatment, and is the most effective and safe compound to use. Everywhere I read on forums said they either didn't know if it could be used in freshwater or said not to do it (but as usual, couldn't back up their statements with legitimate research). I read; however, that most fish and plants are quite tolerant of it, and plants even usually perform better with reasonable doses. If you are having a Nitrate problem, I can tell you this is by far the best way to reduce it. Aquariums are all about recreating natural processes as closely as possible. Most freshwater ecosystems have very effective Nitrate absorbtion through anaerobic bacteria found in the anoxic soils of wetlands. We need to try to recreate this as closely as possible.
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Originally Posted by Vohlk View Post
My intention was not to say you where lying about it being used in waste water treatment, quiet the opposite in fact. I am very familiar with the waste water treatment process and used to work for a company designing waste water treatment facilities. I understand what you are saying completely, I was simply supplying reasons as to why it does work in water treatment. Reasons why it is much safer to use in large scale waste water treatment. There is a lot of chemistry behind it, I do not know what your chemistry background is, I presume some based on your work history, chlorine (which is used very often in waste water management) or high intensity UV light, reacts to break down or "neutralize" lots of "heavy" organic matter. Large organic molecules that make it thruough all of the biological filtration and even the settling tanks are neutralized on the way out of the waste water facility.
A very interesting post (and experiment), along with some interesting comments. I guess I should keep my response to my opening sentence - but 'what the hey' - for what it is worth (hopefully my comments will not be misconstrued or considered disrespectful by anyone):

Most advanced Wastewater Treatment facilities (and their associated treatment processes) are based on desired goals. Removing (that important trio of initials) "TKN", is usually the main goal... along with the other goal of meeting permit compliance. In most instances, conventional secondary treatment (e.g., activated sludge basin & secondary clarifiers - biological nitrification in the activated sludge basin and suspended solids via the secondary clarifiers) provide adequate BOD and Suspended Solids removal. A well designed secondary treatment process will remove about 85-95% of the Biological Oxygen Demand & Suspended Solids, and about 65% Chemical Oxygen Demand from the original influent stream. Even though "considered adequate", the treated effluent still contains organic/inorganic materials, nitrogen, and phosphorus (and because of the nitrogen still present there is additional oxygen demand as a result). This could cause a Wastewater Treatment Plant to "not" meet basic compliance standards/regulations, along with permit violations.

If a higher quality effluent is needed to meet/exceed regulations, additional treatment is needed beyond secondary treatment (e.g., nutrient removal/ denitrification, tertiary). This is where methanol comes into play. Denitrification processes, usually incorporating some type of anoxic zone (e.g., basins/filters/reactors that can also include a fixed packing), are usually supplemented with a carbon source (more than often a dilute methanol solution is used, although ethanol is often used in anoxic rock tanks). Denitrification processes can become real 'gnarly' (in a hurry) for an operator. It's a difficult process and there are a lot of factors that come into play: like ph, temperature, methanol feed, etc.). Usually a well designed (municipal) wastewater treatment plant uses tertiary treatment for removing SS, COD, phosphorus, metals... while chlorine and UV are usually used for disinfection (Fecal Coliform).

I've got a lot of respect for the OP thinking outside of the box (with your methanol experiment and giving it a try), but more importantly: sharing your observations and results.
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post #8 of 49 (permalink) Old 01-28-2017, 04:28 PM
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Now slow down there, and if you don't want to discuss it or listen to the suggestions of other then don't post it in a forum, nor make presumptions of others knowledge.

Yes, read the entire post, and yes, do thoroughly understand the nitrogen cycle.

I've done carbon dosing in my reef tank a few years back as well, both with vinegar and carbon pellets, although discontinued it when I wasn't happy with the side-effects.

And I was trying it in my planted tank too then, although I wasn't seeing a change in nitrates. When I researched the use of carbon dosing in freshwater the indication I got from others was that it only works in conjunction with protein-skimming, and I didn't have a sufficiently deep sand-bed there to achieve denitrification either I realized, so I discontinued that as well.

So how long have you been doing that carbon-dosing in your FW tank, how much have you been dosing, what have been your nitrate levels as a result, and have you seen any other side effects apart from a bit of cloudiness?

Many people do suggest that the Redsea product is a waste of money however, and to just use white vinegar which is a few dollars a gallon, or vodka.
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post #9 of 49 (permalink) Old 01-28-2017, 04:43 PM
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Quote:
Originally Posted by crypticmonk View Post
So I thought I'd share a bit of an experiment I did in my freshwater 75-gallon in regards to Nitrates that I hope other people will find helpful. I am going to try to share this in as many places as I can, as I think I'm the only one who's tried it, and it has been by far the most successful method in significantly reducing Nitrates. It's long, sorry, but I think it's really important. Basic point is that methanol is the best option if you are serious about reducing Nitrates in your freshwater aquarium long-term.
So I have a pretty heavily stocked goldfish aquarium that is also planted. I was doing ok with Nitrates for a while, since the fish were small, I was siphoning out the waste about every other day, and the tank wasn't as heavily planted as it is now (contrary to popular opinion, a planted aquarium can in certain instances INCREASE Nitrates, since rooted plants are very efficient at trapping sediment and waste, thus making it difficult to siphon and for the filters to capture it). However, the fish have grown quickly, and I had to keep them well-fed, because they kept picking at the plants. I eventually moved a couple of the big ones out into the stock tank with the pond fish, but Nitrates were still way too high (like 80 ppm+). Some of you may have seen my previous argument about whether plants, water changes, or anaerobic bacteria are more efficient/effective for reducing Nitrates, and I said the anaerobic bacteria is what is most important. Going off of that, I attempted to increase my anaerobic bacteria population, both by creating more appropriate media for them to grow on, and more importantly, adding Red Sea NO3/Po4 Remover (methanol). I was using this in my reef aquarium, and it worked really well, almost too well (I lowered the dose, even though my bioload is bigger now). The idea behind methanol dosing is it gives the bacteria a source of inorganic carbon, which is often a limiting nutrient for them. It is used in wastewater treatment, and is the most effective and safe compound to use. Everywhere I read on forums said they either didn't know if it could be used in freshwater or said not to do it (but as usual, couldn't back up their statements with legitimate research). I read; however, that most fish and plants are quite tolerant of it, and plants even usually perform better with reasonable doses. So I decided to try it (by this point, I had tried basically every product out there for reducing Nitrates...most are junk, btw, Algone and API Nitrazorb were somewhat effective, but you need to use a lot of it, and it's probably better for more moderate NO3 levels). Nitrates steadily declined, and this morning, they were at zero. Keep in mind, this is with a heavily stocked tank with goldfish, which probably produce more waste than any other aquarium fish. I did get quite a bacterial bloom, but that's the point. I've had to clean out the filter intake tubes pretty regularly just to keep them working.
If you are having a Nitrate problem, I can tell you this is by far the best way to reduce it. Aquariums are all about recreating natural processes as closely as possible. Most freshwater ecosystems have very effective Nitrate absorbtion through anaerobic bacteria found in the anoxic soils of wetlands. We need to try to recreate this as closely as possible. Water changes are NOT the best option, and can even be detrimental if you are doing large water changes frequently. It is impossible to get the parameters right each time, unless you are using pure RO or pure tap water, and if you dose CO2 (like me), you are going to have major CO2 and pH fluctuations. Plus, say you are doing 25% water changes. That means you are only reducing Nitrates by 25%, and the next day, they will most likely go back to the same levels they were before. Manually removing waste is a good idea though, but try to take out as little water as possible. If you want to use plants, you can do that, but they need to be fast-growing plants that feed from the water column (like hornwort), and you need to be using high light, high CO2, and regular dosing of Potassium and trace elements.
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Originally Posted by Mxx View Post
Now slow down there, and if you don't want to discuss it or listen to the suggestions of other then don't post it in a forum, nor make presumptions of others knowledge.

Yes, read the entire post, and yes, do thoroughly understand the nitrogen cycle.

I've done carbon dosing in my reef tank a few years back as well, both with vinegar and carbon pellets, although discontinued it when I wasn't happy with the side-effects.

And I was trying it in my planted tank too then, although I wasn't seeing a change in nitrates. When I researched the use of carbon dosing in freshwater the indication I got from others was that it only works in conjunction with protein-skimming, and I didn't have a sufficiently deep sand-bed there to achieve denitrification either I realized, so I discontinued that as well.

So how long have you been doing that carbon-dosing in your FW tank, how much have you been dosing, what have been your nitrate levels as a result, and have you seen any other side effects apart from a bit of cloudiness?

Many people do suggest that the Redsea product is a waste of money however, and to just use white vinegar which is a few dollars a gallon, or vodka.


Good day , interesting test , I was thinking about trying this as well as I have high NO# levels in my planted tanks. I would also like some more info on your test , what was you NO3 level at start of test , what was the dosing schedule ( how many ML/Gallon X week ) how long did it take to get NO3 Level from ??ppm to where you are at now and how are you maintaining this NO3 Level , Did this affect your PO4 levels ????
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post #10 of 49 (permalink) Old 01-29-2017, 02:17 AM Thread Starter
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post #11 of 49 (permalink) Old 01-29-2017, 03:50 AM
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Good day , interesting test , I was thinking about trying this as well as I have high NO# levels in my planted tanks. I would also like some more info on your test , what was you NO3 level at start of test , what was the dosing schedule ( how many ML/Gallon X week ) how long did it take to get NO3 Level from ??ppm to where you are at now and how are you maintaining this NO3 Level , Did this affect your PO4 levels ????


Do you have this info , would love to see more details on it, Thanks for taking the time to post your results.
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post #12 of 49 (permalink) Old 01-29-2017, 05:32 AM
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Just be be clear on myself if I wasn't from the beginning. I am not disagreeing with the chemistry of how methanol reacts to denitrify the water column. My concern would lie with the purity of the methanol and the other "free" organics that come with. It is just a concern, it does not mean that using methanol will not work (obviously it will) but it is also a potential risk. It's not the methanol I would worry about but potential other materials.
Its a bit of a luck of the draw with what exactly else is in there with the methanol, could be water, could be other materials. In the article you posted they where using analytical grade methanol. This is one of the most expensive methanol's you can buy. (about $84.80 for 2.5 liters from sigma aldrich, or that works out to about $128 a gallon(the really pure stuff is ridiculous(%12.70 a mL)) Most aquariast's I imagine would not be using that purity, and would likely be getting the much cheaper much less pure options.

It's probably not the fact that it doesn't work, but the fact that it has the potential to go wrong which would push people away from the idea. Probably the same reason why people probably wouldn't be comfortable pouring vinegar into their fish tanks. But alas, maybe times will change.
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post #13 of 49 (permalink) Old 01-29-2017, 01:33 PM
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Just be be clear on myself if I wasn't from the beginning. I am not disagreeing with the chemistry of how methanol reacts to denitrify the water column. My concern would lie with the purity of the methanol and the other "free" organics that come with. It is just a concern, it does not mean that using methanol will not work (obviously it will) but it is also a potential risk. It's not the methanol I would worry about but potential other materials.
Its a bit of a luck of the draw with what exactly else is in there with the methanol, could be water, could be other materials. In the article you posted they where using analytical grade methanol. This is one of the most expensive methanol's you can buy. (about $84.80 for 2.5 liters from sigma aldrich, or that works out to about $128 a gallon(the really pure stuff is ridiculous(%12.70 a mL)) Most aquariast's I imagine would not be using that purity, and would likely be getting the much cheaper much less pure options.

It's probably not the fact that it doesn't work, but the fact that it has the potential to go wrong which would push people away from the idea. Probably the same reason why people probably wouldn't be comfortable pouring vinegar into their fish tanks. But alas, maybe times will change.


From post #1 , in this test he was using Red Sea NO3/Po4 Remover , I would take it that since this is made for fish tanks that it would be safe to use, I watch a video on this product and it is made up of different compounds to do a complete job.
I have been having problems with high NO3 in all three of my planted tanks ( 230G // 72G & a 36 G ) I have tried different product to get the NO3 down, none work, I just redid my filters set up in all my tanks using Biohome Ultimate trying to get my filter doing what the tread is talking about.
Its funny as I had already placed an order for Red Sea NO3/Po4 Remover before seeing and reading this post, I will report back once I start using it .
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post #14 of 49 (permalink) Old 01-29-2017, 04:15 PM
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The science of what you guys are discussing is way over my head, as are a lot of things. I'm just curious as to the motivation to control nitrates with an additive. Is it to reduce or eliminate the need to perform water changes? Is it to support a bio-load the tank wouldn't otherwise be able to handle even with regular water changes at a reasonable interval? Possibly the water source has a high level of nitrates to start with so additional reduction measures are needed? Just wondering.

There is much evidence that even low-tech, non-co2, low light set ups can be very efficient at removing nitrates as long as there is a manageable bio-load. Even with small and infrequent water changes in some cases. When I perform a water change that reduces nitrates by 25% they do not return to the starting point in one day, as you suggest. I can keep my nitrates in a fairly predictable range doing water changes every 2 weeks. In other words it takes about 2 weeks for the nitrates to return to the original level after a water change. If I change less water or wait longer nitrates build, if I change more water or do it at shorter intervals the nitrate level drops accordingly, all else remaining the same.
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post #15 of 49 (permalink) Old 01-29-2017, 04:56 PM
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Can't you accomplish Nitrate reduction by doing regular water changes?

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