X3NiTH
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What's not to love about this combination -
Algae - B12 - UV - TiO2 - Ascorbic Acid
Let's join some dots!
A DIY project or commercial device pops out at the end of this.
Commercial devices for the elimination of algae fall into either a UV unit or a Twinstar, neither have been demonstrably proven to be effective on their own in eliminating all algae. From memory there's been some DIY efforts in recreating home versions of the Twinstar using stainless steel mesh but not definitely proven as effective as the Twinstar who's operation is surrounded in mystery and the fancy electronics and timing routines it has is supposed to be part of that magic, it also differs in that it's using Titanium and Platinum in the mesh, so it's not cheap and it's appears to be degradable as a function of the unit (intentional or unintentional is not determined), this seems to be the annoyance over the expense when it's just electrolysis producing O2, or is it?
Where am I going with all this, please bear with me.
Okay if the electrode on the Twinstar is degrading what's it degrading into, there's lots of oxygen in the mix due to the electrolysis so it's a high oxidation zone, if the Titanium degrades in a high redox we get TiO2 (this is a white precipitate, evidenced in operation by many users, a precipitate assumed to be minerals from the water (I'm not assuming it's all TiO2 but there's a great probability it's a component), also the instructions are to clean the replaceable (degrading) mesh periodically, many posts here about what solution to use to shift said precipitate).
What would TiO2 precipitate in solution do to algae?
Firstly what's TiO2 and more importantly what has this to do with Algae?
https://en.m.wikipedia.org/wiki/Titanium_dioxide
Interesting, what does this have to do with algae?
Assuming the 'site' is important, for it to be effective against algae it needs to be in the cell wall as this is the 'site' that is going to come into contact with any free TiO2 precipitate in solution if it's going to do any algae killing.
What algae has Proline and where is it 'sited'?
"Differences in the Occurrence and Distribution of Hydroxyproline-Proteins Among the Algae"
Inta B. Gotelli and Robert Cleland, American Journal of Botany ,Vol. 55, No. 8 (Sep., 1968), pp. 907-914
http://www.jstor.org/stable/2440555?seq=1#page_scan_tab_contents
This may go some way to explain why the Twinstar is claimed to be effective against algae (by TiO2 precipitate cleaving the proline on the algae cell wall thus disrupting and killing the algae) but from users experience not all species as evidenced from the pictures around of algae covered devices. It would be interesting to see if the species Twinstar doesn't kill are the ones that lock their proline away inside or have none to begin with like red algae which is what BBA is, I know my BBA is red as it goes bright red if I kill it with fire (not real fire but H2o2, it is a rocket fuel after all)
Okay is there any other applications for water purification out there using TiO2, specifically with submerged meshes like the Twinstar.
"Immobilized photocatalyst on stainless steel woven meshes assuring efficient light distribution in a solar reactor"
A. S. El-Kalliny, S. F. Ahmed, L. C. Rietveld, and P. W. Appel
http://www.drink-water-eng-sci.net/7/41/2014/dwes-7-41-2014.pdf
Now we have added UV to the mix, the other algae killer and where the mention at the beginning of this post becomes relevant! But wait now it's also in combination with TiO2 for water purification. So Twinstar are missing a trick here by not encapsulating their device and maximising the effect by feeding it UV between 300-400nm.
Right then photocatalytic reactions using TiO2 and UV, this is where things get interesting!
Let's add Vitamin B12 into the mix, since that's what's also being discussed here in these forums as a causal factor for algae growth as a nutrient from waste products either by plant decay releasing nutrients into the water column or excreted by bacteria, how does that react to TiO2, does it react with and degrade the B12?
The answer surprisingly is yes! TiO2 doesn't do it alone you specifically need to do this under UV conditions for effective degradation in B12.
"TiO2‐assisted Photocatalytic Degradation of Vitamin B12 in Aqueous Solution:Influencing Factors, Kinetics, and Reaction Investigations"
Guo, Weimin; Shen, Xingcan; Wang, Lanling; Liang, Hong; Zhang, Laijun
http://www.chemeurope.com/en/public...ors-kinetics-and-reaction-investigations.html
This paper directly links with the previous paper in application of TiO2 in the presence specifically of UV except that B12 removal is not mentioned in the previous paper as to be the desired effect but it is described more generally as for clearing organic pollutants (organic pollutants I am assuming to mean algae and the things they like to eat to grow, including B12, after all you don't want algae growing and clogging the solar water purifier which is what the paper is discussing in regards to TiO2 and UV).
I have only read the abstract of the above paper and don't have access to the full paper, it would be very interesting to know what influence the pH has on the reaction and if it varies, is there an optimum value? Also does the pH correlate in the same ranges as the next paper containing some glorious bell curve pH plots in a very interesting range.
We are looking to eliminate (or get to trace levels) B12 lets see what else has an impact on its degradation.
"Effect of Ascorbic Acid on the Degradation of Cyanocobalamin and Hydroxocobalamin in Aqueous Solution: A Kinetic Study"
Iqbal Ahmad, Kiran Qadeer, [...], and Izhar Ahmad Ansari
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC4179674/#!po=53.4483
This article was an especially interesting read, to make it relevant with the previous papers and talk of UV firstly here is the wiki on Cyanocobalamin (B12) -
https://en.m.wikipedia.org/wiki/Cyanocobalamin
Relevant part is -
In the Ascorbic Acid article the second diagram shows the absorption spectra used to determine B12 and its coenzymes, where it relates to this discussion is that were not trying to measure B12 but kick it where it hurts and initially that's in the UV part of the spectra that is going to degrade B12 the fastest, the reaction continues on degrading the coenzymes further when the Ascorbic acid is added, but it's absorption peak is at 265nm which is only ever so slightly above the low pressure range of commercial UV water sterilisation lamps (250-260nm) definitely in the range of mid power bulbs (250-350nm) (cite - http://www.uvsterilizerreview.com/2007/12/uv-lamps.html) so may cause the Ascorbic acid to degrade, any light wavelength approaching the absorption peak at 265nm will see degradation happen, going to 250nm will just hit it harder (and the B12), however noted from the second diagram B12 has a hefty absorption spike at 350nm which is at the extreme blue end of UV and hence further away from the absorption peak for Ascorbic acid so using this wavelength may be more beneficial as we still get to degrade the B12 at a decent rate with UV but hang on to the Ascorbic acid for longer allowing it to mop up the coenzymes.
If the Ascorbic acid is slow to degrade under UV at commercial steriliser wavelengths near its absorption peak and remains present in the water at concentrations enough to still have an effect on mopping up B12 coenzymes say for at least a 12hr period (there's a reason I'm saying 12hr but I'll get to that later as I'm skipping over something noted in the last article), at least be degraded enough to be organically unavailable to algae as a nutrient, then we can blast the B12 quicker than using 350nm. 350nm might be all that's needed though to get a reaction going in degrading B12 and that's easier to do than UVC which is down at 250/260nm which is way more harmful, 350nm is right near the middle of disco lighting UVA levels which range 315nm-400nm.
What's the connection, go back to Abstract 2 and the TiO2 mesh
I would say 350nm is smack bang in the middle of that efficiency range and just so happens to coincide with the B12 absorption peak. Or is it not a coincidence?
The bit I skipped in the last paper is what phosphate does to the reaction and specifically how it is stymied above pH6 (same happens below pH4 but that's not in the range of a typical aquarium but I'll include it because there are a few that will be), from the diagrams you will note the bell curve plots and efficacy of degradation of B12, please also note the statement in the paper that Ascorbic acid is 20-100 times more effective against B12 that has already been reduced to a coenzyme such as B12b.
If you're EI bells are ringing at this point mine were also. There's no Ascorbic Acid in EI but you will have made the connection if you know that to mix the Micro and Macro up into a single solution you need to add it to stop the two reacting and precipitating out the Iron in the presence of Phosphate, that's a pity Ascorbic acid was looking so promising until Phosphate crashed the party and stymied the reaction. You can now make the connection to where I'm going with the 12hr interval mentioned above. We need to keep the Ascorbic Acid away from the Phosphate literally in both time and space if we are to maintain its efficacy in degrading B12 and its coenzymes when it gets dosed into the tank. This means separate dosing bottle for the Phosphate on its own and all the rest in another bottle with added Ascorbic Acid dosed daily 12hrs apart (weekly water change as usual EI). That's a dose before lights on and one after lights off, but which bottle to dose before and which one after? You'll want to dose the Micro Macro Ascorbic Mix (sans Phosphate) for the light period because you're going to want to have co2 running and the pH down as low as possible near pH6 (pH5 is max efficiency) when it's dosed so that any remaining Phosphate that isn't taken up by plants when dosed overnight won't completely stymie the reaction in the morning.
A pH profile of between 5 and 6 for co2 in an aquarium is entirely feasible, pH6 and 30ppm of co2 (optimum) doable with a KH of 9 providing the tank has an Acidic bias (current description of my water parameters under EI and Co2@30ppm with unhealthy plants attached to bogwood which is still releasing tannins after 5years) (Ascorbic acid will do that also). From the article above in the decomposition formula Carbonate is an essential component of the chemical reaction Ascorbic Acid uses to be able to degrade B12, so hitting an optimum pH5 can't be done with co2 alone by reducing the KH to Zero (or trace) and you can t just drive the pH to 5 using co2 with a higher KH (above 4) as the co2 concentration goes into lethal levels (if animals are present). A bit of Voodoo is going to be required to work out the optimum KH needed to reach as near pH5 as possible and maintain 30ppm co2 via an acidic bias by adding humic acids (decayed plant matter, hopefully not the ones you're trying to keep healthy and alive) Ascorbic Acid addition itself will do this but I don't know at what level it would be detrimental to plants in the aquarium (I know it can be used as an algae killing dip for plants that may be more sensitive to the brute force of H2o2), the article above is describing B12 medicinal supplements and its efficacy in the maintaining of non degraded B12 in the presence of Ascorbic Acid and the reason phosphate is being discussed is how it can be used to buffer the pH to stymie the degradation reaction for longer shelf life, we want the opposite we don't want the B12 so we need the Ascorbic Acid to be as close to non buffered as possible. Active substrates may have a role to play here for maintaining balance in this equation for reducing the pH.
Sorry if that's a lot to take in but if you put it all together it spits out another algae preventative device that may either be internal to the tank or external to the tank (mother of all canister filters).
The device is a unit that is integrally illuminating UV (?UVA@350nm) across a photocatalytic medium with TiO2 present on its surface that is allowed to come into contact with flowing aquarium water. The TiO2 is to perform cleaving of Proline cell walled Algae species and the UVA@350nm is to aid starving Proline free algae (BBA specifically) of nutrients by the degrading of B12 (released by cell breakdown in unhealthy plants and produced by bacterial metabolic processes as waste products) in an effort to make B12 unavailable as a nutrient. The optimum reaction conditions for this effect will be best performed in an aquarium with the presence of Ascorbic Acid addition through use of a plant fertilisation regime that allows contact time for phosphate nutrient from inhibiting Ascorbic Acid degrading B12 and coenzymes to be limited, efficacy of this source for B12 degradation can be optimised by maintaining aquarium water between pH4 and pH6, with pH5 being the effective peak reaction condition. Carbonates are required within the Aquarium water for this chemical reactive B12 degradation process with Ascorbic Acid.
Care must be taken if using co2 concentration to balance the pH as declining KH used up naturally over time in bacterial biological processes and as a consequence of this reaction will cause the concentration of co2 in ppm to decline relevant to a fixed pH point if using a pH co2 controller. This KH effect can be limited to a certain degree through re addition of lost carbonates by testing and supplement additive or by utilising water changes with water at a known level for KH (the amount of carbonates needed to perform this reaction optimally is not yet determined, ratio of Carbonates to Ascorbic Acid added in ppm level to degrade B12 at trace levels may be negligible, the intended initial concentration of Ascorbic Acid to be used is at the dosing level as it would be available if mixing EI fertilisers into one solution).
Photocatalytic TiO2 with UVA at 350nm as a device for the planted tank in combating algae, doable or already done via two separate devices (UV steriliser and Twinstar) that are helping but are not working optimally for maximum efficiency by being combined together in one unit. The adjusting of dosed fertilisation method to take into account Ascorbic Acid reactions that reach the optimum reaction conditions for B12 degradation, totally doable, caveat with care.
Can it be done DIY?
I'm not entirely sure the device has to be active using electrolysis, ala Twinstar, although thats going to make the reaction faster by increasing the Redox in the area of reaction (inside the device) by oxygen production and allowing TiO2 to precipitate into the water column through degradation of Titanium and Platinum mesh. (Still mega bucks for electrode replacements).
If this can be done passively and electrolysis is not needed and only the presence of a large surface area medium coated in TiO2 that is not opaque to exposure of lots of UVA, all that is needed then is a TiO2 coated plastic mesh for water to pass over and through, then something like this plastic TiO2 coated hernia mesh will do the trick-
http://www.biocer-gmbh.de/en/produkte/tio2mesh/
Not sure if the plastic in the above product is UV resistant (at least for 350nm), if it degrades in UVA then it will be a routine replacement part for a passive device (maybe that could be an intentional design feature to get TiO2 particles into aqueous suspension to increase the reaction (present with electrolysis) or it could be used to get into the long term use product with a short term perishable replaceable part micro transaction game), being made of plastic that's going to be leagues cheaper than Titanium and Platinum metal mesh, mind you the above product is a medical one so it's probably just as expensive or more so than the replaceable Twinstar parts.
But really, if it can be passive then a cheaper source for TiO2 plastic mesh could probably be found (more than ever so likely from China). I dare say you could even DIY this part yourself by spray painting mesh with white matte acrylic paint, specifically one that uses TiO2 as the White pigment (which is nearly all of them or at least a very large percentage), you want as really high percentage of TiO2 to binder so the TiO2 can come into contact with as much water as possible, obviously gloss is out due to the lower surface area and why matte paint is needed for this, more binder more gloss. Why spray the paint on and not just paint it with a brush? Well if you've ever painted a plastic model kit with matte paint using a brush it doesn't always turn out quite so matte as you would like it to, but if you fire the same paint through an airbrush (correctly thinned) you get a finer deposition of paint with much more matte (larger surface area absorbing more light).
Coincidentally the approach to getting TiO2 on the Hernia Mesh above is a technique called vapour deposition or sputtering, a bit like airbrushing but with the added excitement of the need for lots of volts and plasma, that's a whole different ball game than white paint and out the realm of casual DIY. For a biologically pure sample of substructure with a layer of TiO2 to the atomic level then Vapour Deposition is the technique of choice. That's how the Hernia Mesh is done -
"What do we know about titanized polypropylene meshes? An evidence-based review of the literature"
F. Ko ̈ckerling • C. Schug-Pass
http://download.springer.com/static...9eb0978d5b261b0a589aa0235decc58e947f39f8a4818
Look at Figure 1. Very much like spray painting except using high voltages and plasma to do the painting, can't really casually DIY that at the kitchen table.
We're after the maximum surface area we can get TiO2 into contact with water to maximise its potential so if we used TiO2 nanotubes (do exist) with vapour deposition then the surface area is going to be huge, TiO2 also repels water meaning that aquarium surface interface nutrient films can come directly into contact with the TiO2 without water wetting its surface (possibly aids the protein cleaving action when water isn't between the TiO2 and the protein being cleaved).
But you could do this on the kitchen table (actually better done outdoors or in a well ventilated area due to Hydrogen being produced as part of the reaction)
"Synthesis of high surface area TiO2 coatings on stainless steel by electrophoretic deposition"
Daniel Schiemann, Pierre Alphonse, Pierre-Louis Taberna.
Synthesis of high surface area TiO2 coatings on stainless steel by electrophoretic deposition. Journal of Materials Research, Cam- bridge University Press (CUP), 2013, vol. 28 (n 15), pp. 2023-2030. <10.1557/jmr.2013.169>. <hal-01167306>
https://hal.archives-ouvertes.fr/hal-01167306/document
Appears we don't need an expensive Titanium Platinum Mesh for electrolysis if it's the TiO2 that does the job like the paper far above, just coat stainless mesh the same way as above.
What about TiO2 nanotubes (more surface area) can you grow them on a kitchen table?
"Ultrafast Room-Temperature Crystallization of TiO2 Nanotubes Exploiting Water-Vapor Treatment"
Andrea Lambert, Angelica Chiodoni, Nadia Shahzad, Stefano Bianco, Marzia Quaglio & Candido F. Pirri
http://www.nature.com/articles/srep07808
If I was to DIY this can I source these materials easily that are already prefabricated and all that is required is assembly (or disassembly first if repurposing something else off the shelf)
Firstly is there anyone out there commercially doing this kind of thing with TiO2 and UV that we could get straight from the shelf?
http://www.overstock.com/Home-Garde...h-UV-Light-and-TiO2-Mesh/3867004/product.html
Okay I'm stopping here because nobody is missing this TiO2 and UV shenanigans, except for the majority of the Aquarium Trade, maybe not Twinstar their first device probably generated TiO2 precipitate in a high Redox zone, their new devices may combine some of what I've just talked about above, it's still an active unit, I'm pretty sure this can be done passively with no need for the electrolysis bit, you just need to pass the water through a device like a filter (nothing new there).
I'm thinking a Hydor type device for an inline with TiO2 mesh internally illuminated by UV light, plug and play no need for any electrolysis.
So where's all the Aquarium Algae buster machines, are all the manufacturers late to the table with this or are they hard at work building this thing and it's close to everybody doing one and not just Twinstar.
It's not like Algae is a minor annoyance, it can be devastatingly bad news, BBA in particular, the advice to remove affected leaves strands you up a creek if you're left with one leaf on the plant and it's got BBA you can't remove this without damaging the plant.
I might try DIY this, in the first instance I am going to modify my EI (not the values of concentrations) to allow me to keep Ascorbic Acid away from the Phosphate, I'm going to get a replacement bulb for my UV unit and plug it back in the loop. This way I can take advantage of the Ascorbic Acids ability to degrade the B12 Algae food. I may source some UV LED lights in the 350nm range and use that either above the tank illuminating the whole water column (24/7 maybe not practical) or stick it in the cabinet and shine it through the side of my Co2 reactor (20" Watts), it may also be worth getting some of this TiO2 mesh and sticking it in the reactor right where UV illuminates the best.
If I had a 3d printer I'd be prototyping!
Food for thought
🙂
Algae - B12 - UV - TiO2 - Ascorbic Acid
Let's join some dots!
A DIY project or commercial device pops out at the end of this.
Commercial devices for the elimination of algae fall into either a UV unit or a Twinstar, neither have been demonstrably proven to be effective on their own in eliminating all algae. From memory there's been some DIY efforts in recreating home versions of the Twinstar using stainless steel mesh but not definitely proven as effective as the Twinstar who's operation is surrounded in mystery and the fancy electronics and timing routines it has is supposed to be part of that magic, it also differs in that it's using Titanium and Platinum in the mesh, so it's not cheap and it's appears to be degradable as a function of the unit (intentional or unintentional is not determined), this seems to be the annoyance over the expense when it's just electrolysis producing O2, or is it?
Where am I going with all this, please bear with me.
Okay if the electrode on the Twinstar is degrading what's it degrading into, there's lots of oxygen in the mix due to the electrolysis so it's a high oxidation zone, if the Titanium degrades in a high redox we get TiO2 (this is a white precipitate, evidenced in operation by many users, a precipitate assumed to be minerals from the water (I'm not assuming it's all TiO2 but there's a great probability it's a component), also the instructions are to clean the replaceable (degrading) mesh periodically, many posts here about what solution to use to shift said precipitate).
What would TiO2 precipitate in solution do to algae?
Firstly what's TiO2 and more importantly what has this to do with Algae?
https://en.m.wikipedia.org/wiki/Titanium_dioxide
Interesting, what does this have to do with algae?
Assuming the 'site' is important, for it to be effective against algae it needs to be in the cell wall as this is the 'site' that is going to come into contact with any free TiO2 precipitate in solution if it's going to do any algae killing.
What algae has Proline and where is it 'sited'?
"Differences in the Occurrence and Distribution of Hydroxyproline-Proteins Among the Algae"
Inta B. Gotelli and Robert Cleland, American Journal of Botany ,Vol. 55, No. 8 (Sep., 1968), pp. 907-914
http://www.jstor.org/stable/2440555?seq=1#page_scan_tab_contents
This may go some way to explain why the Twinstar is claimed to be effective against algae (by TiO2 precipitate cleaving the proline on the algae cell wall thus disrupting and killing the algae) but from users experience not all species as evidenced from the pictures around of algae covered devices. It would be interesting to see if the species Twinstar doesn't kill are the ones that lock their proline away inside or have none to begin with like red algae which is what BBA is, I know my BBA is red as it goes bright red if I kill it with fire (not real fire but H2o2, it is a rocket fuel after all)
Okay is there any other applications for water purification out there using TiO2, specifically with submerged meshes like the Twinstar.
"Immobilized photocatalyst on stainless steel woven meshes assuring efficient light distribution in a solar reactor"
A. S. El-Kalliny, S. F. Ahmed, L. C. Rietveld, and P. W. Appel
http://www.drink-water-eng-sci.net/7/41/2014/dwes-7-41-2014.pdf
Now we have added UV to the mix, the other algae killer and where the mention at the beginning of this post becomes relevant! But wait now it's also in combination with TiO2 for water purification. So Twinstar are missing a trick here by not encapsulating their device and maximising the effect by feeding it UV between 300-400nm.
Right then photocatalytic reactions using TiO2 and UV, this is where things get interesting!
Let's add Vitamin B12 into the mix, since that's what's also being discussed here in these forums as a causal factor for algae growth as a nutrient from waste products either by plant decay releasing nutrients into the water column or excreted by bacteria, how does that react to TiO2, does it react with and degrade the B12?
The answer surprisingly is yes! TiO2 doesn't do it alone you specifically need to do this under UV conditions for effective degradation in B12.
"TiO2‐assisted Photocatalytic Degradation of Vitamin B12 in Aqueous Solution:Influencing Factors, Kinetics, and Reaction Investigations"
Guo, Weimin; Shen, Xingcan; Wang, Lanling; Liang, Hong; Zhang, Laijun
http://www.chemeurope.com/en/public...ors-kinetics-and-reaction-investigations.html
This paper directly links with the previous paper in application of TiO2 in the presence specifically of UV except that B12 removal is not mentioned in the previous paper as to be the desired effect but it is described more generally as for clearing organic pollutants (organic pollutants I am assuming to mean algae and the things they like to eat to grow, including B12, after all you don't want algae growing and clogging the solar water purifier which is what the paper is discussing in regards to TiO2 and UV).
I have only read the abstract of the above paper and don't have access to the full paper, it would be very interesting to know what influence the pH has on the reaction and if it varies, is there an optimum value? Also does the pH correlate in the same ranges as the next paper containing some glorious bell curve pH plots in a very interesting range.
We are looking to eliminate (or get to trace levels) B12 lets see what else has an impact on its degradation.
"Effect of Ascorbic Acid on the Degradation of Cyanocobalamin and Hydroxocobalamin in Aqueous Solution: A Kinetic Study"
Iqbal Ahmad, Kiran Qadeer, [...], and Izhar Ahmad Ansari
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC4179674/#!po=53.4483
This article was an especially interesting read, to make it relevant with the previous papers and talk of UV firstly here is the wiki on Cyanocobalamin (B12) -
https://en.m.wikipedia.org/wiki/Cyanocobalamin
Relevant part is -
In the Ascorbic Acid article the second diagram shows the absorption spectra used to determine B12 and its coenzymes, where it relates to this discussion is that were not trying to measure B12 but kick it where it hurts and initially that's in the UV part of the spectra that is going to degrade B12 the fastest, the reaction continues on degrading the coenzymes further when the Ascorbic acid is added, but it's absorption peak is at 265nm which is only ever so slightly above the low pressure range of commercial UV water sterilisation lamps (250-260nm) definitely in the range of mid power bulbs (250-350nm) (cite - http://www.uvsterilizerreview.com/2007/12/uv-lamps.html) so may cause the Ascorbic acid to degrade, any light wavelength approaching the absorption peak at 265nm will see degradation happen, going to 250nm will just hit it harder (and the B12), however noted from the second diagram B12 has a hefty absorption spike at 350nm which is at the extreme blue end of UV and hence further away from the absorption peak for Ascorbic acid so using this wavelength may be more beneficial as we still get to degrade the B12 at a decent rate with UV but hang on to the Ascorbic acid for longer allowing it to mop up the coenzymes.
If the Ascorbic acid is slow to degrade under UV at commercial steriliser wavelengths near its absorption peak and remains present in the water at concentrations enough to still have an effect on mopping up B12 coenzymes say for at least a 12hr period (there's a reason I'm saying 12hr but I'll get to that later as I'm skipping over something noted in the last article), at least be degraded enough to be organically unavailable to algae as a nutrient, then we can blast the B12 quicker than using 350nm. 350nm might be all that's needed though to get a reaction going in degrading B12 and that's easier to do than UVC which is down at 250/260nm which is way more harmful, 350nm is right near the middle of disco lighting UVA levels which range 315nm-400nm.
What's the connection, go back to Abstract 2 and the TiO2 mesh
I would say 350nm is smack bang in the middle of that efficiency range and just so happens to coincide with the B12 absorption peak. Or is it not a coincidence?
The bit I skipped in the last paper is what phosphate does to the reaction and specifically how it is stymied above pH6 (same happens below pH4 but that's not in the range of a typical aquarium but I'll include it because there are a few that will be), from the diagrams you will note the bell curve plots and efficacy of degradation of B12, please also note the statement in the paper that Ascorbic acid is 20-100 times more effective against B12 that has already been reduced to a coenzyme such as B12b.
If you're EI bells are ringing at this point mine were also. There's no Ascorbic Acid in EI but you will have made the connection if you know that to mix the Micro and Macro up into a single solution you need to add it to stop the two reacting and precipitating out the Iron in the presence of Phosphate, that's a pity Ascorbic acid was looking so promising until Phosphate crashed the party and stymied the reaction. You can now make the connection to where I'm going with the 12hr interval mentioned above. We need to keep the Ascorbic Acid away from the Phosphate literally in both time and space if we are to maintain its efficacy in degrading B12 and its coenzymes when it gets dosed into the tank. This means separate dosing bottle for the Phosphate on its own and all the rest in another bottle with added Ascorbic Acid dosed daily 12hrs apart (weekly water change as usual EI). That's a dose before lights on and one after lights off, but which bottle to dose before and which one after? You'll want to dose the Micro Macro Ascorbic Mix (sans Phosphate) for the light period because you're going to want to have co2 running and the pH down as low as possible near pH6 (pH5 is max efficiency) when it's dosed so that any remaining Phosphate that isn't taken up by plants when dosed overnight won't completely stymie the reaction in the morning.
A pH profile of between 5 and 6 for co2 in an aquarium is entirely feasible, pH6 and 30ppm of co2 (optimum) doable with a KH of 9 providing the tank has an Acidic bias (current description of my water parameters under EI and Co2@30ppm with unhealthy plants attached to bogwood which is still releasing tannins after 5years) (Ascorbic acid will do that also). From the article above in the decomposition formula Carbonate is an essential component of the chemical reaction Ascorbic Acid uses to be able to degrade B12, so hitting an optimum pH5 can't be done with co2 alone by reducing the KH to Zero (or trace) and you can t just drive the pH to 5 using co2 with a higher KH (above 4) as the co2 concentration goes into lethal levels (if animals are present). A bit of Voodoo is going to be required to work out the optimum KH needed to reach as near pH5 as possible and maintain 30ppm co2 via an acidic bias by adding humic acids (decayed plant matter, hopefully not the ones you're trying to keep healthy and alive) Ascorbic Acid addition itself will do this but I don't know at what level it would be detrimental to plants in the aquarium (I know it can be used as an algae killing dip for plants that may be more sensitive to the brute force of H2o2), the article above is describing B12 medicinal supplements and its efficacy in the maintaining of non degraded B12 in the presence of Ascorbic Acid and the reason phosphate is being discussed is how it can be used to buffer the pH to stymie the degradation reaction for longer shelf life, we want the opposite we don't want the B12 so we need the Ascorbic Acid to be as close to non buffered as possible. Active substrates may have a role to play here for maintaining balance in this equation for reducing the pH.
Sorry if that's a lot to take in but if you put it all together it spits out another algae preventative device that may either be internal to the tank or external to the tank (mother of all canister filters).
The device is a unit that is integrally illuminating UV (?UVA@350nm) across a photocatalytic medium with TiO2 present on its surface that is allowed to come into contact with flowing aquarium water. The TiO2 is to perform cleaving of Proline cell walled Algae species and the UVA@350nm is to aid starving Proline free algae (BBA specifically) of nutrients by the degrading of B12 (released by cell breakdown in unhealthy plants and produced by bacterial metabolic processes as waste products) in an effort to make B12 unavailable as a nutrient. The optimum reaction conditions for this effect will be best performed in an aquarium with the presence of Ascorbic Acid addition through use of a plant fertilisation regime that allows contact time for phosphate nutrient from inhibiting Ascorbic Acid degrading B12 and coenzymes to be limited, efficacy of this source for B12 degradation can be optimised by maintaining aquarium water between pH4 and pH6, with pH5 being the effective peak reaction condition. Carbonates are required within the Aquarium water for this chemical reactive B12 degradation process with Ascorbic Acid.
Care must be taken if using co2 concentration to balance the pH as declining KH used up naturally over time in bacterial biological processes and as a consequence of this reaction will cause the concentration of co2 in ppm to decline relevant to a fixed pH point if using a pH co2 controller. This KH effect can be limited to a certain degree through re addition of lost carbonates by testing and supplement additive or by utilising water changes with water at a known level for KH (the amount of carbonates needed to perform this reaction optimally is not yet determined, ratio of Carbonates to Ascorbic Acid added in ppm level to degrade B12 at trace levels may be negligible, the intended initial concentration of Ascorbic Acid to be used is at the dosing level as it would be available if mixing EI fertilisers into one solution).
Photocatalytic TiO2 with UVA at 350nm as a device for the planted tank in combating algae, doable or already done via two separate devices (UV steriliser and Twinstar) that are helping but are not working optimally for maximum efficiency by being combined together in one unit. The adjusting of dosed fertilisation method to take into account Ascorbic Acid reactions that reach the optimum reaction conditions for B12 degradation, totally doable, caveat with care.
Can it be done DIY?
I'm not entirely sure the device has to be active using electrolysis, ala Twinstar, although thats going to make the reaction faster by increasing the Redox in the area of reaction (inside the device) by oxygen production and allowing TiO2 to precipitate into the water column through degradation of Titanium and Platinum mesh. (Still mega bucks for electrode replacements).
If this can be done passively and electrolysis is not needed and only the presence of a large surface area medium coated in TiO2 that is not opaque to exposure of lots of UVA, all that is needed then is a TiO2 coated plastic mesh for water to pass over and through, then something like this plastic TiO2 coated hernia mesh will do the trick-
http://www.biocer-gmbh.de/en/produkte/tio2mesh/
Not sure if the plastic in the above product is UV resistant (at least for 350nm), if it degrades in UVA then it will be a routine replacement part for a passive device (maybe that could be an intentional design feature to get TiO2 particles into aqueous suspension to increase the reaction (present with electrolysis) or it could be used to get into the long term use product with a short term perishable replaceable part micro transaction game), being made of plastic that's going to be leagues cheaper than Titanium and Platinum metal mesh, mind you the above product is a medical one so it's probably just as expensive or more so than the replaceable Twinstar parts.
But really, if it can be passive then a cheaper source for TiO2 plastic mesh could probably be found (more than ever so likely from China). I dare say you could even DIY this part yourself by spray painting mesh with white matte acrylic paint, specifically one that uses TiO2 as the White pigment (which is nearly all of them or at least a very large percentage), you want as really high percentage of TiO2 to binder so the TiO2 can come into contact with as much water as possible, obviously gloss is out due to the lower surface area and why matte paint is needed for this, more binder more gloss. Why spray the paint on and not just paint it with a brush? Well if you've ever painted a plastic model kit with matte paint using a brush it doesn't always turn out quite so matte as you would like it to, but if you fire the same paint through an airbrush (correctly thinned) you get a finer deposition of paint with much more matte (larger surface area absorbing more light).
Coincidentally the approach to getting TiO2 on the Hernia Mesh above is a technique called vapour deposition or sputtering, a bit like airbrushing but with the added excitement of the need for lots of volts and plasma, that's a whole different ball game than white paint and out the realm of casual DIY. For a biologically pure sample of substructure with a layer of TiO2 to the atomic level then Vapour Deposition is the technique of choice. That's how the Hernia Mesh is done -
"What do we know about titanized polypropylene meshes? An evidence-based review of the literature"
F. Ko ̈ckerling • C. Schug-Pass
http://download.springer.com/static...9eb0978d5b261b0a589aa0235decc58e947f39f8a4818
Look at Figure 1. Very much like spray painting except using high voltages and plasma to do the painting, can't really casually DIY that at the kitchen table.
We're after the maximum surface area we can get TiO2 into contact with water to maximise its potential so if we used TiO2 nanotubes (do exist) with vapour deposition then the surface area is going to be huge, TiO2 also repels water meaning that aquarium surface interface nutrient films can come directly into contact with the TiO2 without water wetting its surface (possibly aids the protein cleaving action when water isn't between the TiO2 and the protein being cleaved).
But you could do this on the kitchen table (actually better done outdoors or in a well ventilated area due to Hydrogen being produced as part of the reaction)
"Synthesis of high surface area TiO2 coatings on stainless steel by electrophoretic deposition"
Daniel Schiemann, Pierre Alphonse, Pierre-Louis Taberna.
Synthesis of high surface area TiO2 coatings on stainless steel by electrophoretic deposition. Journal of Materials Research, Cam- bridge University Press (CUP), 2013, vol. 28 (n 15), pp. 2023-2030. <10.1557/jmr.2013.169>. <hal-01167306>
https://hal.archives-ouvertes.fr/hal-01167306/document
Appears we don't need an expensive Titanium Platinum Mesh for electrolysis if it's the TiO2 that does the job like the paper far above, just coat stainless mesh the same way as above.
What about TiO2 nanotubes (more surface area) can you grow them on a kitchen table?
"Ultrafast Room-Temperature Crystallization of TiO2 Nanotubes Exploiting Water-Vapor Treatment"
Andrea Lambert, Angelica Chiodoni, Nadia Shahzad, Stefano Bianco, Marzia Quaglio & Candido F. Pirri
http://www.nature.com/articles/srep07808
If I was to DIY this can I source these materials easily that are already prefabricated and all that is required is assembly (or disassembly first if repurposing something else off the shelf)
Firstly is there anyone out there commercially doing this kind of thing with TiO2 and UV that we could get straight from the shelf?
http://www.overstock.com/Home-Garde...h-UV-Light-and-TiO2-Mesh/3867004/product.html
Okay I'm stopping here because nobody is missing this TiO2 and UV shenanigans, except for the majority of the Aquarium Trade, maybe not Twinstar their first device probably generated TiO2 precipitate in a high Redox zone, their new devices may combine some of what I've just talked about above, it's still an active unit, I'm pretty sure this can be done passively with no need for the electrolysis bit, you just need to pass the water through a device like a filter (nothing new there).
I'm thinking a Hydor type device for an inline with TiO2 mesh internally illuminated by UV light, plug and play no need for any electrolysis.
So where's all the Aquarium Algae buster machines, are all the manufacturers late to the table with this or are they hard at work building this thing and it's close to everybody doing one and not just Twinstar.
It's not like Algae is a minor annoyance, it can be devastatingly bad news, BBA in particular, the advice to remove affected leaves strands you up a creek if you're left with one leaf on the plant and it's got BBA you can't remove this without damaging the plant.
I might try DIY this, in the first instance I am going to modify my EI (not the values of concentrations) to allow me to keep Ascorbic Acid away from the Phosphate, I'm going to get a replacement bulb for my UV unit and plug it back in the loop. This way I can take advantage of the Ascorbic Acids ability to degrade the B12 Algae food. I may source some UV LED lights in the 350nm range and use that either above the tank illuminating the whole water column (24/7 maybe not practical) or stick it in the cabinet and shine it through the side of my Co2 reactor (20" Watts), it may also be worth getting some of this TiO2 mesh and sticking it in the reactor right where UV illuminates the best.
If I had a 3d printer I'd be prototyping!
Food for thought
🙂
