Well, That Didn't Work...

[dasaltemelosguy]

 

Originally, I wasn’t going to post this experiment because although the end result was as expected, the process was like fumigating your house by burning it down!  The article below is unfinished, but the results were truly interesting, nonetheless. So, despite that it didn’t work, I thought you might like to see what happened…

 

Inverse Cycling

The Electrolysis of Nitrates

Most likely, there’s not a person here that is unfamiliar with cycling their aquarium and the nurturing of the beneficial bacteria to effect this.

But what’s actually occurring depends upon the scale we’re viewing it from. The process of reducing ammonia and nitrite to nitrates is, on a microscopic level, a biological event. If we look closer, as ammonia reduces to nitrite and nitrite reduces to nitrate, it’s a molecular event.

But intrinsically, it’s all a nuclear event. All of the beneficial bacteria feeding and the subsequent reduction of ammonia and nitrite to nitrates is really just electrons being shuffled around to effect change.

The force that accomplishes this is an electron’s attraction or repulsion towards other atomic particles. To that end, we can apply a greater force with externally applied electrons in the form of electricity to reverse their natural reactions. When performed in a liquid, this is known as Electrolysis.

Electrolysis inserts electrons directly into the water via electricity. As such, you may elect to employ much more power than the electron bonds in the molecules themselves have. When there’s more electronic force than the molecules have, it can split them apart. To that end, water (H2/O) splits into Hydrogen and Oxygen, Ammonia (N/H3) splits into Nitrogen and Hydrogen, and Nitrites (N/O2) and Nitrates (N/O3) split into Nitrogen and Oxygen.

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Electrolysis is commonly performed on wastewater, especially where high nitrates are a problem. These are just some of many such examples:

Recent development of electrochemical nitrate reduction to ammonia: A mini review - ScienceDirect

Electrochemical reduction of nitrate ion on various cathodes – reaction kinetics on bronze cathode | SpringerLink

Restoring the Nitrogen Cycle by Electrochemical Reduction of Nitrate: Progress and Prospects - Zeng - 2020 - Small Methods - Wiley Online Library

High-Performance Electrochemical Nitrate Reduction to Ammonia under Ambient Conditions Using a FeOOH Nanorod Catalyst | ACS Applied Materials & Interfaces

Electrocatalytic reduction of nitrate: Fundamentals to full-scale water treatment applications - ScienceDirect

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With simple home electrolysis devices like these above, we can electrify the water, infusing it with electrons to remove Hydrogen, Oxygen, and Nitrogen from the nitrates, nitrites and ammonia. The goal being a simple plug & play device and the nitrates slowly vanish.

And indeed, they did just that. As you’ll see below in images of water tests over a 7-day period, by Day-7, it removed 100% of the nitrates, nitrites and ammonia from the water using only electricity.

“The Universe Laughs While We Make Plans”

This process is roughly the opposite of what the beneficial bacteria do when converting ammonia and nitrites to nitrates, so it seemed like a logical direction to remove nitrates, would be to reverse it. But what I failed to consider is we are reversing the entire cycle.

So, nitrates are first converted back to nitrites, and nitrites are first converted back to ammonia (as it simultaneously splits the water for Hydrogen) BEFORE they’re all eventually removed!

Ultimately the ammonia becomes nitrogen and hydrogen gas and leaves the water but there’s a period of several days where there’s enormous amounts of nitrites and ammonia before they all finally vanish.

Obviously, this completely negates any use with live fish present! I suppose it could be used to remove ammonia, nitrites and nitrates from stored water, but it was my hope that it could be simply inserted into a living tank, and we’d see the nitrates slowly drop…

What follows are some unretouched images of the water tests over a 7-day period during the electrolysis of nitrates.

The starting water had no ammonia, no nitrites, a pH of 8 but nitrates were set at 40PPM.

By the end, it has no ammonia, no nitrites, no nitrates and a pH of 7.8…but it’s a very toxic path to success:

 

pH = 8, NH3 = 0, NO2 = 0, NO3 = 40

 

 

pH = 8, NH3 = 0.5, NO2 = 0.25, NO3 = 40

 

 

pH = 8, NH3 = 0.5, NO2 = 0.25, NO3 = 40

 

 

pH = 8.2, NH3 = 2, NO2 = 0.25, NO3 = 40

 

 

pH = 8.2, NH3 = 8, NO2 = 1, NO3 = 30

 

 

pH = 8.4, NH3 = 6, NO2 = 2, NO3 = 20

 

 

pH = 8.4, NH3 = 4, NO2 = 0.25, NO3 = 15

 

 

pH = 8.4, NH3 = 2, NO2 = 0, NO3 = 5

 

 

pH = 8.4, NH3 = 1.5, NO2 = 0, NO3 = 0

 

 

pH = 8.4, NH3 = 0.75, NO2 = 0, NO3 = 0

 

 

pH = 7.8, NH3 = 0, NO2 = 0, NO3 = 0

 

A minor note:

The process of electrolysis generates some heat and as such, the water varied in temperature widely. It was during this process I noticed a minor peculiarity about the API Liquid Test Kit.

The results vary slightly with the water temperature. Of the four primary tests, pH, Ammonia, Nitrite, Nitrate, all display about 5% darker per +10*. This color drift/temperature is strongest with pH.  Check out the same water tested at 75*and 85*:

Add 5% to the reading per 10*F increase.

*

So, I ended it here and didn’t polish up the images or post citations because well, it didn’t work!  

But I thought some might find it interesting!

 

 

Notes:

Hours 1-10 = 250ma, 100*

Hours 11-14 = 800ma, 120*

Hours 15-19 = 350ma, 107*

Hours 20-72 = 150ma, 103*

Hours 73-144 = 50ma, 90*

 

 

 

 

 

[Guppysnail]

I always love your experiments, even the ones that don’t work as hoped. Thank you for your work and sharing this. 

[Odd Duck]

Very interesting, even if it illustrates something that won’t work for many situations.  Hopefully it will stop someone with less experience and knowledge from doing a bad experiment with fish involved.  Knowledge of what NOT to do is sometimes even more important in saving lives than knowing what to do.

[Katherine]

This was fascinating, thank you for sharing! And thank you for the dots on the color chart under the vial photos. That made it very easy to look through at a glance.

[Beardedbillygoat1975]

Thanks for publishing. It’s been great fun following all of the work.

What I find interesting is that in Europe they used to electrify the space below and in the substrate for planted aquaria. Dupla had substrate “heating” which were coils that ran electricity through the substrate as part of the comprehensive method for keeping a successful planted tank.

From The Krib:
“1) Provide warmth in the substrate for certain plant species (Barclaya longifolia, for example). In this case the substrate should be warmer than the water. 

2) Provide warmth in the substrate to speed up biochemical processes. Reduction reactions, those which make nutrients more soluble and thereby more available to plant uptake, will take place at an accelerated rate (2-3 times faster for each 10 degrees C rise in temperature).

3) Transport nutrients from the water column into the substrate. Important nutrients are ammonium (primarily from fish waste), iron (from trace element additions), calcium, potassium and other trace elements. This will replenish substrate nutrients used by the roots and provide long term viability. 

4) Transport harmful substances out of the substrate. Decomposition byproducts may be harmful to plant roots. There is also conjecture that plants give off low level toxins (alleochemicals) to keep other plants out of their territory. Successful species of weeds have developed this into an art form. If these toxins build up due to poor circulation, the plant may harm itself and its neighbors. 

5) Provide a chelating medium that binds the reduced state of trace elements with an organic molecule, enabling the trace element to be adsorbed by root hairs. It is also conjectured that iron in the substrate (from iron-bearing materials such as laterite) can sequester phosphate, if the phosphate is able to move into the substrate. 

6) Provide a reducing rather than oxidizing environment so that trace elements are kept in their reduced state (usable by plants) or are reduced from their oxidized state. Iron especially will rapidly oxidize in water with normal levels of oxygen.”

For those new to the hobby The Krib was the place for info in the 90s and 2000s when the internet was young. It’s still stored online and is a trove of useful history.

So I think there’s more out there with this. I remember @Dean’s Fishroom was making an aquarium sterilizer like the one made by Twinstar which releases ions through current flowing through their device. So electricity is a useful bit in the hobby. 

[nabokovfan87]

On 2/17/2023 at 9:16 AM, dasaltemelosguy said:

To that end, water (H2/O) splits into Hydrogen and Oxygen, Ammonia (N/H3) splits into Nitrogen and Hydrogen, and Nitrites (N/O2) and Nitrates (N/O3) split into Nitrogen and Oxygen.

This is the part that seemed interesting to break down. I'm sure there is some math and a very technical word for it, but I just can't remember the terminology for it.

If we're talking bonds, then I think about how strong are those bonds? Some elements are happy to shed an electron while others take a lot more energy to do that.  One ion might happily spil (like hydrogen peroxide) compared to water that is very happy to not split.

I remember studying some of that stuff from school and having to do some pretty intense formulas, but for the life of me it's just one of those things where I'd have to dive in to really understand the mechanics and interactions.

With that in mind....

Ammonia seemed to build, potentially because that's our "water molecules" in the above example and other things would reduce into that by shedding electrons.

Interesting stuff for sure.

Maybe there's an experiment in there somewhere, but like you mentioned the testing changes with temperature could account for a lot of the results you saw in this trial.

[JJenna]

I'm glad that you take the time to put science to the test, fascinating read. I'll quote Winston Churchill for your efforts, "Success consists of going from failure to failure without loss of enthusiasm"

[TheSwissAquarist]

Shame that it failed, but remember that Einstein once said that Imagination was more important than knowledge. 🙂

[TheSwissAquarist]

Looks like we’re all quoting stuff 🤣🤣

[OnlyGenusCaps]

On 2/17/2023 at 11:16 AM, dasaltemelosguy said:

So, I ended it here and didn’t polish up the images or post citations because well, it didn’t work!

I wish more folks would post about their failed experiments.  There is a lot of value in that!  I used to joke with my friends back in grad school that there needed to be a "Journal of Negative Results" because of the number of errors we made on our paths to understanding our systems that resulted in more experienced scientists telling us "of course that doesn't work, we tried that years ago".

So thanks for bringing this to our collective attention today, so we don't have to try this tomorrow! 

[TheSwissAquarist]

Water change system powered by a Juwel aquarium pump out of a watering can for my 8 gal cube. Failed miserably because the pump had an unremovable nozzle which had a little pressure-checking hole. Couldn’t pump anything vertically, but horizontally was ok. Back to the drawing board! 

The culprit: 

[dasaltemelosguy]

On 2/17/2023 at 11:32 AM, Beardedbillygoat1975 said:

3) Transport nutrients from the water column into the substrate. Important nutrients are ammonium (primarily from fish waste), iron (from trace element additions), calcium, potassium and other trace elements. This will replenish substrate nutrients used by the roots and provide long term viability. 

4) Transport harmful substances out of the substrate. Decomposition byproducts may be harmful to plant roots. There is also conjecture that plants give off low level toxins (alleochemicals) to keep other plants out of their territory. Successful species of weeds have developed this into an art form. If these toxins build up due to poor circulation, the plant may harm itself and its neighbors. 

5) Provide a chelating medium that binds the reduced state of trace elements with an organic molecule, enabling the trace element to be adsorbed by root hairs. It is also conjectured that iron in the substrate (from iron-bearing materials such as laterite) can sequester phosphate, if the phosphate is able to move into the substrate. 

6) Provide a reducing rather than oxidizing environment so that trace elements are kept in their reduced state (usable by plants) or are reduced from their oxidized state. Iron especially will rapidly oxidize in water with normal levels of oxygen.”

That's really fascinating. Literally all of these points, the transference of nutrients, the reduction of toxins, the chelating, all would be affected by electricity. Perhaps strongly. I don't know enough about the biology, but it truly makes sense chemically. Particularly the chelating as that can be done with electricity. I've converted insoluble iron to bioavailable iron using electrolysis when we were doing some growth tests.

I'm old and I've never heard of The Krib! That's a great find, thank you.

On 2/17/2023 at 11:32 AM, Beardedbillygoat1975 said:

So I think there’s more out there with this. I remember @Dean’s Fishroom was making an aquarium sterilizer like the one made by Twinstar which releases ions through current flowing through their device. So electricity is a useful bit in the hobby. 

You're right. there's a few of them. All similar to the TwinStar device. I picked one up when we began testing technologies that would ultimately become Reverse Respiration. I didn't know how pests would react to electrolysis and these devices were already built so I bought one. It's very gentle though. I remember seeing pest snails literally walk across the device right through the bubbles! 

[dasaltemelosguy]

On 2/17/2023 at 4:01 PM, nabokovfan87 said:

This is the part that seemed interesting to break down. I'm sure there is some math and a very technical word for it, but I just can't remember the terminology for it.

If we're talking bonds, then I think about how strong are those bonds? Some elements are happy to shed an electron while others take a lot more energy to do that.  One ion might happily spil (like hydrogen peroxide) compared to water that is very happy to not split.

I remember studying some of that stuff from school and having to do some pretty intense formulas, but for the life of me it's just one of those things where I'd have to dive in to really understand the mechanics and interactions.

With that in mind....

Ammonia seemed to build, potentially because that's our "water molecules" in the above example and other things would reduce into that by shedding electrons.

Interesting stuff for sure.

Maybe there's an experiment in there somewhere, but like you mentioned the testing changes with temperature could account for a lot of the results you saw in this trial.

You raise some really interesting points. The strength of the molecular bonds tends to be related to the 'activity level' of the element. For example, oxygen is mildly active and so it slowly corrodes/oxidizes whereas chlorine is violently active and caustic. When an element is highly active, it forms bonds that are stronger and more difficult to break/reverse. So, you need more power to do so. So, your point about ammonia makes sense as of the big 3 in the cycle, it's the only one with hydrogen which is much more active than oxygen or nitrogen. In fact, at the end are some notes on the power used. It was during the ammonia formation at Hour-5 when it drew the most power! Thanks for raising this point. 

[dasaltemelosguy]

On 2/18/2023 at 6:29 AM, OnlyGenusCaps said:

I wish more folks would post about their failed experiments.  There is a lot of value in that!  I used to joke with my friends back in grad school that there needed to be a "Journal of Negative Results" because of the number of errors we made on our paths to understanding our systems that resulted in more experienced scientists telling us "of course that doesn't work, we tried that years ago".

So thanks for bringing this to our collective attention today, so we don't have to try this tomorrow! 

Thanks a lot.

Speaking of failures, you may remember this. You reminded me of an old experiment we once conducted in an attempt to recharge an exhausted Purigen packet without using bleach by using electrolysis. It proved untenable in that it required an enormous amount of power. In fact, it pulled so much power, I literally had to pull my car up to the vessel and use jumper cables to the electrodes!

 

After 30 minutes it nearly dissolved the copper electrodes and it had just begun recharging the Purigen. It would have been more efficient if it had filtration membranes between the electrodes not unlike dialysis but somehow running my car for two days and replacing electrodes every hour didn’t seem worth a $9 pack of Purigen! 🤑

@Guppysnail sent me the Purigen. In fact, she’s sent me used Purigen, dead algae and live leeches.  I think she’s trying to tell me something??? 😉   !🤣😆😂!

Edited February 18, 2023 by dasaltemelosguy

[OnlyGenusCaps]

On 2/18/2023 at 12:10 PM, dasaltemelosguy said:

an old experiment we once conducted in an attempt to recharge an exhausted Purigen packet without using bleach by using electrolysis.

I remember that.  I was just glad you didn't electrocute yourself with that one!  I remember waiting impatiently for a reply from you so I knew you survived.  When you moved to playing with seltzer I breathed a sigh of relief! 

[TheSwissAquarist]

On 2/18/2023 at 7:10 PM, dasaltemelosguy said:

sent me the Purigen. In fact, she’s sent me used Purigen, dead algae and live leeches.  I think she’s trying to tell me something??? 😉   !🤣😆😂!

That’s it’s time to embrace algae and leeches as great things and that they should become Christmas gifts? 🎁🤣

Edited February 19, 2023 by TheSwissAquarist