Nutrient Pulse Reactor (DIY DyMiCo filter)

Ah, good point. I was thinking the knee was the point where oxygen was depleted and the filter was transitioning to nitrate. But it is actually the point where nitrate is exhausted and the bacteria are standing in front of the open cupboard and wondering what else is there to eat? :)

More common ground :) That's what I mentioned to Aaron in the previous post. The nitrate knee is exactly the bacteria making up their minds what to eat (simply put: it takes some time to switch to SO4).

Yes, based on the fact the knee signals that sulfate reduction has started, it is very beneficial to end the cycle as soon as a knee is confirmed.

That is what I believe will be the biggest challenge in getting the algorithm correct. Making it able to adapt to the nutrient loading of the system. Being able to establish the amount of N by the time period it takes to reduce it would be very helpful. The DyMiCo manual stresses the need for the flush pump to be restricted to a specific flow range. I assume this is because they are doing something similar.

Also they (DyMiCo), state that the max on time for the flsuh pump is 16 minutes per hour. I am guessing that this is tied to the max processing ability for their fully cycled filter running at 100% efficiency. The fow rate the user is instructed to restrict the flush pump is different between the model 700 & 2000 filter, so this cap of 16 minutes of flush pump activation can be true for both filter models as they are returing water at different rates. This could also be a potential signal for adjusting the operation of the filter. If we can establish the limit of the processig capabilities of an NPR of a given size, the algorithm could attempt to shorten the cycle period until the limit is reached based on the flow rate. Then again what you have already proposed may reach this same end point in a more elegant fashion. :)

I presume as well that the reason is to be sought in their algorithm. The two other reasons I mentioned before might come into play too but the flow seems overly emphasized in the manual if those were the only reasons (plankton preservation and preventing filter going aerobic).

Hence volume being a factor in their algorithm seems very plausible but so far I don't see a reason why it would be necessary. I've started to think about the logic flow diagram for the algorithm and in a nutshell I think about something as simple as:
1. determine the minimum ORP point
2. determine the maximum ORP point
3. flush the filter X seconds
4. wait for ORP peak
5. adapt X if ORP goes above ORP high target (1)
5. dose Y ml of carbon
6. wait for nitrate knee or accelerated descent or ORP minimum
7. adapt Y depending on time between 3 and 6 versus previous cycles (2)
8. once a week goto 1 else goto 3

(1) high target is a function of the ORP range and empiric constants
(2) adaptation depends on sign of factor and an empiric constant z:
if at start or reset necessary (once a week/month/...)
Y = 0
factor = +1
else if time is equal within boundaries or time > previous
factor = factor x -1 (invert)
Y = Y + (factor x z)

The above has two evolutive parts:
- the time to flush the filter which evolves with the resulting ORP after a cycle (lower ORP at the end will yield a longer flush next cycle)
- the dosed C evolves with the length of the cycle:
an equal time result in a higher or lower C depending on what happened last cycle
a longer time and we were augmenting C = diminish C
a longer time and we were diminishing C = augment C
that way the algorithm aims for a C in balance but once found continuously moves C up and down to allow it to drift if the bio-load changes
To be sure that the amount of C dials in correctly a reset happens periodically and the system dials the C back in

With this evolutive adaptation I imagine the filter should be able to adapt to any flow rate, filter volume, tank volume, media bio-mass capacity, bio-load and so on.

This is just a first quick brainstorm on how it could function. It needs fine tuning, safeguards and analytical routines which I'm pondering about. I'll make a flowchart once most of it sorts out.

In addition to the primary nutrients, N & P, it would be very helpful if the filter can also impact DOC. Some of these compounds will likely be dealt with in due course of normal filter operations. Others might require some encouragement for the bacteria to reduce them. The DyMiCo manual mentions that the plankton that are now able to survive and thrive can reduce the DOC. I am not aware of any tests for DOC available for hobbyists. I guess we could develop a visual test, kind of like the secchi sticks for estimating phyto plankton density. Only this would be for detecting the yellowing of the tank water from DOC by viewing 2 side by side vessels (1 tank, 1 RODI) from above over a background of varying shades of yellow (for the vessel filled with RODI).

Anyway best learn to walk before we run.

Dennis

One of the studies that I linked before was about forgoing an external carbon source and using the waste water as source of C (to diminish operational costs). They were able to accomplish similar denitrification so it sure seems like a possibility. They didn't mention what they thought the bacteria fed on but DOCs seems like the only candidate (certainly not POCs). Of course this necessitates that the bacteria are C deficient as the ethanol or acetate added as external source would surely be preferred opposed to consuming complex molecules such as amino acids or sugars. Hence another important reason to optimize the C dosage in function of denitrification and aim for that balance. Another idea might be to occasionally adapt a cycle to skip the C dosage, dose a lower amount or dose later to induce starving bacteria that go for DOCs in the cupboard. Anyways, this will require copious field testing and surely falls in the category "˜running' opposed to "˜walking' ;-)

Kr,

Klaus
 
Well, not much to report. As Klaus predicted. Disregard the varying height of one probe vs the other. Apex screws the scale up. They are pretty much the same.

I am back to the normal hour flush / dose.

Interesting reading this morning. I am not opposed to KNO3 dosing. How much and are there un-intended consequences?

Aaron

Aaron, dosing potassium nitrate relates to information I crossed regarding carbon dosing. Dosing C is done to lower N and P which it does marvelously if you read up about it. Resorting to dosing KNO3 has, afaik two reasons:
Once all N is consumed this becomes the limiting factor, bio-mass stops growing even though there is ample C available. The excess P in the system remains leading to numerous posts such as : 'dosing vodka/vinegar, zero nitrate and high phosphate'. Dosing KNO3 gives the bacteria something to feed on, consuming P in the process lowering phosphates.
Dosing C can be too efficient and leave corals (and/or the zooxanthellae) that need some N starving.

In your case N might be limiting as you have low nutrients. Here we're not looking for N for the bacteria to consume but as a source for the denitrification process. So the principle is the same but the application of N is different. If we were looking to reduce P then I'd tell you to aim for the Redfield ratio of 106C:16N:1P but since we're not talking about growing bacteria there is no other option than to experiment I believe.

Regarding side effects I see a positive and a negative one:
- on the positive side, if N is limiting you should still grow more bacteria and hence be reducing P
- if the N though is consumed by growing bacteria that may result in a bloom and aggressive, exponential blooms have been known to leave a tank without oxygen killing everything in the process. So, as with C dosing you want to go slow and steady, staying with a dose until stabilization before upping the amount.

Lastly as your tank is without skimmer I'd be careful as well as any bacteria excess will not be removed from your system...
I would go for a raise of 1 ppm / day to start with. You can refer to the following post for an indication on how to determine your dosage (let me know if you need help) :
http://www.reefcentral.com/forums/sh...81&postcount=2

Goal should be to get detectable nitrate levels of 2-5 ppm. That might take a while as the dosed nitrates will probably be consumed by your system and filter at first.

Of course there are other means of achieving detectable nitrates as well. This is also a good read:
http://www.reefcentral.com/forums/sh...php?p=23394296

Keep us posted

Klaus
 
I of course meant a dose of 1 ppm / day, not raising the NO3 by 1 ppm / day which would be a lot of KNO3 in a short period of time. Sorry for the confusion...
 
I have a couple of questions regarding how we get to Sulfate and H2S. I have read that the redox cascade goes: oxygen, nitrate, iron then sulfate. Is that incorrect?

Also, based on the data last night, why did those curves flatten out (in the wrong direction) instead of dropping sharply producing the signature “knee”? Regardless of how much nitrate was available, there should have been a change in more favorable to less favorable electron exchanges, which is really what the ORP probe is “seeing”, correct? I went back and looked at that original curve (third page of the post) and there is a very distinct change between 8.5 and 10 (-100 to -175 mV). If the bio-mass stops growing when you run out of N, why do we have issues with H2S?

I got error 404 file not found on those links. Is that just on my end?

With regard to the KNO3, I assume there may also be an increase in potassium levels too?
 
I have a couple of questions regarding how we get to Sulfate and H2S. I have read that the redox cascade goes: oxygen, nitrate, iron then sulfate. Is that incorrect?

Iron actually comes before nitrate. Take a look at the wikipedia page for anaerobic respiration. There is a list of the oxidation in order of preference. The preference is due to the amount of energy the oxidation offers. At the top, obviously, is O with the highest redox potential. Several other molecules follow on the list before we get to nitrate and sulfate. They however do not play an important role opposed to these 3 as the concentrations are negligible in salt water. The reason this order exists is the amount of energy the oxidation yields. Apparently if O is 100% energy, NO3 yields 83% energy while SO4 only yields 6% energy. Bacteria prefer by consequence O and once that's depleted NO3. Making the switch to SO4 can be regarded as a last resort as it yields marginal energy. One could say it's bacteria going into survival mode.

Something I learned today: this is not similar in sulfur denitrifying reactors. These reactors operate under constant anaerobic circumstances with different species of bacteria. If these bacteria are exposed to oxygen, they perish. The bacteria that concern us are capable of living in aerobic circumstances and thrive in anaerobic circumstances (for instance Paracoccus denitrificans).

Also, based on the data last night, why did those curves flatten out (in the wrong direction) instead of dropping sharply producing the signature "œknee"? Regardless of how much nitrate was available, there should have been a change in more favorable to less favorable electron exchanges, which is really what the ORP probe is "œseeing", correct? I went back and looked at that original curve (third page of the post) and there is a very distinct change between 8.5 and 10 (-100 to -175 mV). If the bio-mass stops growing when you run out of N, why do we have issues with H2S?

My guess is that there isn't enough N present to see the knee clearly. It's only an educated guess though as it seems a possible explanation of the slight bend we see in the curve of your recent graphs. Essentially my presumption is that with little N present, bacteria are forced to switch to SO4 early once the O is consumed. The available N is still consumed of course but as there is no distinctive moment when a lot of bacteria run out of N, there is no signature knee produced.
That's why I suggested the NO3 dosing to see if that would yield the knee. If not, we'ld have to look further. Remember I contemplated a possibility that we wouldn't clearly notice a nitrate knee due to the system design balancing on aerobic versus anaerobic. Only more data and more setups will tell.

I got error 404 file not found on those links. Is that just on my end?

Yeah, I got the same issue. Probably because I didn't encapsulate the urls in a proper tag. Here goes again:

The link regarding calculating the amount to dose:
http://www.reefcentral.com/forums/showpost.php?p=7413281&postcount=2

A nice read regarding the reasoning behind dosing nitrates for sps colors :)
http://www.reefcentral.com/forums/showthread.php?p=23394296

With regard to the KNO3, I assume there may also be an increase in potassium levels too?

Yes absolutely but it's negligible as the concentration of K in NSW is around 400 ppm. KNO3 is about 40% K in molecular weight so dosing to raise NO3 by 1 ppm will raise your K by 0.4 ppm which is peanuts. If you'ld like an alternative however, CaNO3 works out fine too...

Gr,

Klaus
 
I have a couple of questions regarding how we get to Sulfate and H2S. I have read that the redox cascade goes: oxygen, nitrate, iron then sulfate. Is that incorrect?

Also, based on the data last night, why did those curves flatten out (in the wrong direction) instead of dropping sharply producing the signature "œknee"? Regardless of how much nitrate was available, there should have been a change in more favorable to less favorable electron exchanges, which is really what the ORP probe is "œseeing", correct? I went back and looked at that original curve (third page of the post) and there is a very distinct change between 8.5 and 10 (-100 to -175 mV). If the bio-mass stops growing when you run out of N, why do we have issues with H2S?

I got error 404 file not found on those links. Is that just on my end?

With regard to the KNO3, I assume there may also be an increase in potassium levels too?

I agree those curves looked odd. I was wondering what ORP level they actually relate to. If you are hitting very low ORP values (like < -350) than you may already be past the knee, we just did not detect it and you are firmly in anoxic territory. This is where the H2S04 rears its smelly head.

Keep in mind that the biomass uses all the compounds (O, NO3, FeO2, SO4) for respiration. So even though we are out of N (NO3, NO2) , you still have an active biomass that is attempting to survive, so it will move on to the lesser elements that take more energy (C) to convert to oxygen. Sure the biofilter can't expand without N, but the existing biofilter can still reduce the sulfate to H2SO4.

Dennis
 
Forgot to answer this question:

If the bio-mass stops growing when you run out of N, why do we have issues with H2S?

Once the bacteria consumed the NO3 they switch to SO4. The resulting product when they consume NO3 is N2, the resulting product when they consume SO4 is H2S. Not only is this toxic, the filter is at that point consuming SO4 which doesn't do anything for the tank. So it primarily isn't related to the growth of bio-mass but more about what the bio-mass already present is dining on :)
 
The Redox Cascade
Worldwide and especially in coastal areas including coral reefs, benthic sediments are the primary site of the diagenesis and remineralization that have been discussed above (Galloway et al. 2004). One reason for their primacy is the simple fact that organic wastes (which consist of dead organisms, feces, and nutrient-rich marine snow) end up in and make up the sediment layer; the majority of organic matter decomposition is simply where the organic matter ends up.

When organic matter ends up being deposited to the sediment, it immediately begins to undergo diagenesis. First and foremost, organic matter is consumed and metabolized using aerobic respiration, which uses oxygen as the terminal electron acceptor ("TER" in equation 1). However, the amounts of organic matter typically exceed the levels of oxygen, so organisms then begin to use "substitute" electron receptors in place of oxygen. The first of these is nitrate, via denitrification, which is thermodynamically not as "profitable" for organisms as aerobic respiration. This is why denitrification is always associated with anoxic sediments or water: oxygen is thermodynamically a favorable electron acceptor, and nitrate is only used as a last resort.

Once both nitrate and oxygen have been consumed, any remaining organic material continues to be broken down by energetically less favorable terminal electron acceptors according to a well-established cascade, continuing next with iron reduction, and finally with sulfate reduction. In most cases, organic matter is consumed long before sulfate is depleted, so our discussion can end with that step. Collectively, all of these metabolic pathways are termed the redox cascade, referring to the cascade of less desirable terminal electron acceptors as heterotrophic organisms consume organic matter in the sediment.
 
I agree those curves looked odd. I was wondering what ORP level they actually relate to. If you are hitting very low ORP values (like < -350) than you may already be past the knee, we just did not detect it and you are firmly in anoxic territory. This is where the H2S04 rears its smelly head.

Keep in mind that the biomass uses all the compounds (O, NO3, FeO2, SO4) for respiration. So even though we are out of N (NO3, NO2) , you still have an active biomass that is attempting to survive, so it will move on to the lesser elements that take more energy (C) to convert to oxygen. Sure the biofilter can't expand without N, but the existing biofilter can still reduce the sulfate to H2SO4.

Dennis

Are we talking about H2S or sulfuric acid (H2SO4)?

The ORP shown in the graph seems to be bottoming out around -225 mV (pH of 11.0)
 
The latest probe comparison. There is definitely some variance.

Orange graph uses the scale on the left.
Green graph, the right.

Guess which one is the newer probe?

Aaron
 

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The Redox Cascade
Worldwide and especially in coastal areas including coral reefs, benthic sediments are the primary site of the diagenesis and remineralization that have been discussed above (Galloway et al. 2004). One reason for their primacy is the simple fact that organic wastes (which consist of dead organisms, feces, and nutrient-rich marine snow) end up in and make up the sediment layer; the majority of organic matter decomposition is simply where the organic matter ends up.

When organic matter ends up being deposited to the sediment, it immediately begins to undergo diagenesis. First and foremost, organic matter is consumed and metabolized using aerobic respiration, which uses oxygen as the terminal electron acceptor ("TER" in equation 1). However, the amounts of organic matter typically exceed the levels of oxygen, so organisms then begin to use "substitute" electron receptors in place of oxygen. The first of these is nitrate, via denitrification, which is thermodynamically not as "profitable" for organisms as aerobic respiration. This is why denitrification is always associated with anoxic sediments or water: oxygen is thermodynamically a favorable electron acceptor, and nitrate is only used as a last resort.

Once both nitrate and oxygen have been consumed, any remaining organic material continues to be broken down by energetically less favorable terminal electron acceptors according to a well-established cascade, continuing next with iron reduction, and finally with sulfate reduction. In most cases, organic matter is consumed long before sulfate is depleted, so our discussion can end with that step. Collectively, all of these metabolic pathways are termed the redox cascade, referring to the cascade of less desirable terminal electron acceptors as heterotrophic organisms consume organic matter in the sediment.

The iron in your quote is refering to iron hydroxide Fe(OH)2 which is readily available in sediment (coming from perished bio-mass) and acts as a terminal electron acceptor in denitrification (anaerobic). I was referring to ferric iron which is an electron donor in aerobic conditions. Either way it's insignificant as the Fe in the watercolumn is marginal: 3-4 ppb and will play no role in a NPR...
 
Are we talking about H2S or sulfuric acid (H2SO4)?

The ORP shown in the graph seems to be bottoming out around -225 mV (pH of 11.0)

anaerobic consumption of sulphate yields H2S (the rotten egg niceness).

So far all charts I've seen with a nitrate knee situate the knee around -100mV (usually a tad lower). With the characteristics of ORP measurement in mind I'd expect a knee to present itself in the -50 to -150 mV range which, with some leeway, puts us in the denitrifying range.
 
In other news ...

In other news ...

Miracles is ready to install my tank!! I still need to drop by the factory to inspect it before delivery. The 8 inches of snow in my side yard might be a problem though. I plan on making a video for Derrick so he can have an idea of the route they would have to navigate to my walkout and the elevations involved.

Potentially the install could take place next week! My prediction of before Christmas was a bit optimistic, but hopefully not off by much.

Dennis
 
Miracles is ready to install my tank!! I still need to drop by the factory to inspect it before delivery. The 8 inches of snow in my side yard might be a problem though. I plan on making a video for Derrick so he can have an idea of the route they would have to navigate to my walkout and the elevations involved.

Potentially the install could take place next week! My prediction of before Christmas was a bit optimistic, but hopefully not off by much.

Dennis

Can't wait to see it. Are you going to post on it's install?

Just out of curiosity, how big and how much does it weigh? I am assuming you will try to move it with a fork truck? That may be tricky in the snow.

Aaron
 
Aaron, dosing potassium nitrate relates to information I crossed regarding carbon dosing. Dosing C is done to lower N and P which it does marvelously if you read up about it. Resorting to dosing KNO3 has, afaik two reasons:
Once all N is consumed this becomes the limiting factor, bio-mass stops growing even though there is ample C available. The excess P in the system remains leading to numerous posts such as : 'dosing vodka/vinegar, zero nitrate and high phosphate'. Dosing KNO3 gives the bacteria something to feed on, consuming P in the process lowering phosphates.
Dosing C can be too efficient and leave corals (and/or the zooxanthellae) that need some N starving.

In your case N might be limiting as you have low nutrients. Here we're not looking for N for the bacteria to consume but as a source for the denitrification process. So the principle is the same but the application of N is different. If we were looking to reduce P then I'd tell you to aim for the Redfield ratio of 106C:16N:1P but since we're not talking about growing bacteria there is no other option than to experiment I believe.

Regarding side effects I see a positive and a negative one:
- on the positive side, if N is limiting you should still grow more bacteria and hence be reducing P
- if the N though is consumed by growing bacteria that may result in a bloom and aggressive, exponential blooms have been known to leave a tank without oxygen killing everything in the process. So, as with C dosing you want to go slow and steady, staying with a dose until stabilization before upping the amount.

Lastly as your tank is without skimmer I'd be careful as well as any bacteria excess will not be removed from your system...
I would go for a raise of 1 ppm / day to start with. You can refer to the following post for an indication on how to determine your dosage (let me know if you need help) :
http://www.reefcentral.com/forums/sh...81&postcount=2

Goal should be to get detectable nitrate levels of 2-5 ppm. That might take a while as the dosed nitrates will probably be consumed by your system and filter at first.

Of course there are other means of achieving detectable nitrates as well. This is also a good read:
http://www.reefcentral.com/forums/sh...php?p=23394296

Keep us posted

Klaus

I ran a test yesterday, using the original test apparatus and tank. The nitrate in this system is 12ppm but the curve did the same thing. it got down to around -200 mV and then just rolled off. There was now obviously moment when it switched over from NO3. Is it possible that instead of running out of NO3, I am running out of carbon?
 
I did another test this morning. Instead of dosing the carbon immediately after the flush cycle had settled, I waited 10 minutes.

Here is the result:

On the next cycle, I plan to dose just after the flush and then again at the 10 minute (top) of the cycle to see what effect that has on the curve.

Aaron
 

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Can't wait to see it. Are you going to post on it's install?

Just out of curiosity, how big and how much does it weigh? I am assuming you will try to move it with a fork truck? That may be tricky in the snow.

Aaron

The tank is 120" x 36" x 30" (10 ft x 3 ft x 2.5 ft). Not sure how much is weighs. The 300 DD I was going to get was 465 lbs, and that is a lot smaller and only using 12 mm glass. My tank uses 18 mm glass and is 40% longer. I would estimate 800 - 1000 lbs. I have no idea how they are going to move it. I assume they will use a fork lift to remove it from the truck, then they are going to have to carry it by hand over my lawn, down a small hill, into my pool area, along the pool deck and finally back out of the pool area through some patio doors. Miracles said it would take 12 guys to get it into the house. I am a bit worried about the snow. Not the kind of thing you want to be moving with any sort of slippery surface involved. Probably be a lot easier just to get a big boom crane in to drop it right in to my pool area. Then they could just use a heavy duty wheeled platform to roll it into the house and finally move it onto the stand.

I will post on the install, and do have a build thread on here somewhere that I will also update.

Dennis
 
This is the comparison of the probes. I finally got both on the same scale so it is easier to see. There is quiet a bit of difference, especially near the zero to higher mV ranges. The curves look different too. This may be a result of the way Apex is visually rounding the data.

I still don't have an obvious nitrate knee, at least visually to me, even with a second dose of carbon.

Aaron
 

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