PO4x4 = iron based polymer?

[Acrotrdco]

Just found this new product called PO4x4, it said it's a "unique chemical engineered polymer based mini pellets" that has all the advantages of GFO but will not leak iron ion into the water column, and will not clump together, etc.

It can also be "generated" by using the "regeneration powder" which is corrosive, sounds pretty much like regenerating GFO with NaOH!

Any idea what this might be, and if their claim of GFO will leak iron ion into water column is true? (i.e. they claimed "Almost every other iron based GFO is releasing iron-ions to the water up to 10 times more than natural seawater levels. This is tested and confirmed at the university of Wageningen, Holland. The tests were done with a inductively coupled plasma mass spectrometer.")

[Randy Holmes-Farley]

It is just a polymer coated version of regular GFO pellets. You can regenerate normal GFO, and I'm not convinced the iron release part is true or any different than regular GFO. No polymer coating is selective to passage of phosphate and not iron. They probably took the idea that physical chunks do not break off as readily, and intentionally or unintentionally "misinterpreted" that to read as iron.

I do not doubt that GFO releases soluble iron. I also do not consider that a problem. I add iron to my system. :)

[jtma508]

Being the perennial 'early-adopter' I ordered some of this recently. Still going through Customs I'm told. I'll let you know if it really does out-perform regualr old BRS GFO.

[Randy Holmes-Farley]

FWIW, there are other brands that also sell such products and have been around a while. One, which seemingly stole the picture I drew of a phosphate molecule for their label, is shown in this link:

http://www.polyplab.com/3-opti-phos.php

"Opti-Phos is a revolutionary phosphate removal media made from hydrous ferric oxide (HFO) infused into a synthetic bead."

Note the label:

http://www.polyplab.com/pub/ftp/articles/Opti-Phos.jpg

and the picture from one of my phosphate articles:

Phosphate and the Reef Aquarium
http://reefkeeping.com/issues/2006-09/rhf/index.php


http://reefkeeping.com/issues/2006-09/rhf/images/Phosphate%20Figure%201.jpg

[Acrotrdco]

Thanks Randy, in that case, I might try getting some after my GFO ran out, to see how they behave in a GFO reactor.

Cheers.

[Randy Holmes-Farley]

OK, if you get it, let us know how it works out. :)

[Acrotrdco]

Just got my package today, here's my report:

Packaging - you can see the beads, very uniform size.
https://lh4.googleusercontent.com/_NY50WtBKN8U/Tc7Ll2n6ZbI/AAAAAAAAHVI/7wxwqm5u5W0/s720/DSC_6457.JPG

Checking my PO4 before testing the PO4x4, using low-range test with my Salifert test kit (using double sample and tester volume), I guess I could say it's between 0.00 and 0.015ppm :)
https://lh5.googleusercontent.com/_NY50WtBKN8U/Tc7LmbgRb-I/AAAAAAAAHVM/1Xw8Hl-y1qQ/s720/DSC_6462.JPG

Opened package, used about 50ml and added about 150ml RO/DI water, surprised how clear it is, I don't really need to rinse it! :)
https://lh5.googleusercontent.com/_NY50WtBKN8U/Tc7Lnhz83uI/AAAAAAAAHVY/OxRclc4qhRo/s720/DSC_6468.JPG

Putting it in a mesh bag and throw it into my reactor, replacing the GFO I was using.

That's it for now, it'll take weeks if not months to test out how well this PO4x4 works, and if it stand up to its claims :)

[Randy Holmes-Farley]

:thumbsup:

Thanks for the update. :)

[2thdeekay]

What size are the beads? Are they uniformly round? Thanks!

[HighlandReefer]

Does this article represent the mechanisms that these products are using to remove phosphate?


Hybrid anion exchanger for trace phosphate removal from water and wastewater
http://www.sciencedirect.com/science?_ob=ArticleURL&_udi=B6V73-4N2M69D-1&_user=10&_coverDate=04%2F30%2F2007&_rdoc=1&_fmt=high&_orig=gateway&_origin=gateway&_sort=d&_docanchor=&view=c&_searchStrId=1751994412&_rerunOrigin=scholar.google&_acct=C000050221&_version=1&_urlVersion=0&_userid=10&md5=47d12da267841d85a6a80e3de75c5a47&searchtype=a


Lee M. Blaneya, Suna Cinara and Arup K. SenGupta, a,

aDepartment of Civil and Environmental Engineering, Lehigh University, 13 East Packer Avenue, Bethlehem, PA 18015, USA

Received 30 October 2006; revised 20 December 2006; accepted 3 January 2007. Available online 16 February 2007.

Abstract

Throughout recent decades, the wastewater treatment industry has identified the discharge of nutrients, including phosphates and nitrates, into waterways as a risk to natural environments due to the serious effects of eutrophication. For this reason, new tertiary treatment processes have abounded; these processes generally utilize physico–chemical and biological methods to remove nutrients from secondary wastewaters. The disadvantages of such methods involve larger reactor volumes, operating costs, and waste sludge production; furthermore, complete nutrient removal is unattainable due to thermodynamic and kinetic limitations. The subject study presents the development and performance of a new phosphate-selective sorbent, referred to as hybrid anion exchanger or HAIX. HAIX combines durability and mechanical strength of polymeric anion exchange resins with high sorption affinity of hydrated ferric oxide (HFO) toward phosphate. HAIX is essentially a polymeric anion exchanger within which HFO nanoparticles have been dispersed irreversibly. Laboratory studies show that HAIX selectively removes phosphate from the background of much higher concentrations of competing sulfate, chloride and bicarbonate anions due to the combined presence of Coulombic and Lewis acid–base interactions. Experimental results demonstrate that HAIX's phosphate–sulfate separation factor is over two orders of magnitude greater than that of currently available commercial ion exchange resins. Additionally, optimal HAIX performance occurs at typical secondary wastewater pH conditions i.e., around 7.5. HAIX is amenable to efficient regeneration and reuse with no noticeable loss in capacity.

[2thdeekay]

Does this article represent the mechanisms that these products are using to remove phosphate?

I wondered that too. :) Is it (bead)-CH2-N(CH3)2 / FeO(OH) or something else?

[Randy Holmes-Farley]

It may be, but I thought it is simply encapsulated GFO (but don't know that for sure). The anion resins are not useful for phosphate in seawater (I've tried the best known phosphate binding polymer resin). :)

[dzhuo]

Did you really end up not having to wash the media before using it in a reactor?

[HighlandReefer]

Thanks for your input Randy. ;)

The articles I have been readings all reference to use the HAIX at around a pH of 7.1-7.5. I'm not sure why or if they are effective at normal reef pH.

[Randy Holmes-Farley]

The biggest problem with organic polymers to bind phosphate in seawater is the huge competition for binding sites from chloride and sulfate coupled with a relatively poor affinity for phosphate. :)

[HighlandReefer]

With this information, I am having problems understanding how using a polymer for encapsulating ferric oxide can improve performance for removing phosphate in our reef tank. I can find no studies specific to phosphate. It seems that these polymers are more used for removing arsenic with some mention of strontium.

[Acrotrdco]

Did you really end up not having to wash the media before using it in a reactor?

Well I did rinse it with RO/DI water once, that's it. If I were using Rowaphos / GFO I'd have to rinse it at least half a dozen times before I could use them in my sump.

What size are the beads? Are they uniformly round? Thanks!

About half the size of caviar, or if you know what's the size of masago (if you like sushi), that's about the same size.

Read here:
http://en.wikipedia.org/wiki/Tobiko

[2thdeekay]

About half the size of caviar, or if you know what's the size of masago (if you like sushi), that's about the same size.
Read here:
http://en.wikipedia.org/wiki/Tobiko

Thanks Acro! Helpful details always nice. :) Masago/tobiko is a family favorite. :thumbsup:

[Acrotrdco]

Randy,

Answering your question regarding whether PO4x4 would not leak iron ion into the water column, one of our local reefer QQ had perform the tests:

He took sample from 3 different sources, from left to right: Rowaphos, common GFO, PO4x4
http://www.reef.hk/forum/uploads/monthly_05_2011/post-3-0-16002700-1305443161_thumb.jpg

then soak it in distilled water, wait for 24 hours then measure the iron concentration in the distilled water.

Sample size (the small red cap is about 3.6ml volume, weights 1.68g) -
Rowaphos: 3.19g (0.87 g/ml)
http://www.reef.hk/forum/uploads/monthly_05_2011/post-3-0-80278000-1305443199_thumb.jpg

Common GFO - 2.22g (0.62g / ml)
http://www.reef.hk/forum/uploads/monthly_05_2011/post-3-0-51297700-1305443220_thumb.jpg

PO4x4 - 2.50g (0.69g / ml)
http://www.reef.hk/forum/uploads/monthly_05_2011/post-3-0-54131700-1305443240_thumb.jpg

After mixing with distilled water, you can see the cloudiness of the samples:
http://www.reef.hk/forum/uploads/monthly_05_2011/post-3-0-66627400-1305443259_thumb.jpg

24 hours later

http://www.reef.hk/forum/uploads/monthly_05_2011/post-3-0-01919600-1305554172_thumb.jpg

As you can see, the Rowaphos sample is still pretty cloudy, and the particle still haven't settle yet, in order to speed this up, the sample is being filtered with a filter paper, but the result isn't that great:

After filtering:
http://www.reef.hk/forum/uploads/monthly_05_2011/post-3-0-20360800-1305554214_thumb.jpg

Another 24 hours later
From left to right: new Rowaphas sample rinsed thoroughly with RO/DI water, original Rowaphas sample filtered, GFO sample filtered, PO4x4 sample filtered.
http://www.reef.hk/forum/uploads/monthly_05_2011/post-3-0-70583300-1306073786_thumb.jpg

Using Hanna HI 721 colorimeter:
http://www.reef.hk/forum/uploads/monthly_05_2011/post-3-0-58310400-1306073797_thumb.jpg

[Acrotrdco]

Here're the results:

Original Rowaphos sample filtered:
http://www.reef.hk/forum/uploads/monthly_05_2011/post-3-0-75412100-1306073807_thumb.jpg

New Rowaphos sample rinsed with RO/DI thoroughly
http://www.reef.hk/forum/uploads/monthly_05_2011/post-3-0-52965500-1306073817_thumb.jpg

As you can see, the difference between the two samples are pretty obvious:
http://www.reef.hk/forum/uploads/monthly_05_2011/post-3-0-09557700-1306073827_thumb.jpg

Common GFO sample:
http://www.reef.hk/forum/uploads/monthly_05_2011/post-3-0-38902100-1306073836_thumb.jpg

PO4x4 sample:
http://www.reef.hk/forum/uploads/monthly_05_2011/post-3-0-46681400-1306073847_thumb.jpg

So I think their claim of not leaking iron ion into water column is actually... true! :)

[2thdeekay]

Yes, nobody denied GFO leaches iron ions, it's a moot point. :)


I do not doubt that GFO releases soluble iron. I also do not consider that a problem. I add iron to my system. :)

@ ocean pH, Fe ions don't stay in solution well, and get utilized by organisms fairly quickly. At the ocean's surface, Fe is very low, @ ~0.000006 ppm. So, to imply that there is a problem with leaking iron ions equivalent to 10x the concentration of seawater is most likely pointless.

Are those extra iron ions harmful, or beneficial to your system? That's the real question!

Iron in a Reef Tank
http://www.advancedaquarist.com/issues/aug2002/chem.htm

Iron: A Look At Organisms Other Than Macroalgae
http://www.advancedaquarist.com/2002/10/chemistry

[Randy Holmes-Farley]

I think there are some potential issues here, not least of which is that the test you are using may well detect particulates as soluble iron. The same way a calcium kit will. They may all have the same levels of soluble iron, just different levels of particulates.

That said...

So I think their claim of not leaking iron ion into water column is actually... true!

True? What value does the meter read on the starting DI water? 0.05 ppm is a LOT of iron! I realize that you used a lot of GFO in a small amount of water, but bear in mind that the NSW level of iron is on the order of 0.000006 ppm, so even accounting for dilution effects, that is a lot if real and accurate. :)

[dzhuo]

Thx for doing this Acrotrdco! The test is very informative. It's very surprise to see how clean PO4x4 is which is really what I am mostly interested about; rinsing GFO media is not fun at all.

Other than the iron leaching aspect of PO4x4, how are your general impression with this product so far? Have you seen your phosphate drop?

[Acrotrdco]

er.. ok let me rephase myself better.

Rowaphos, common GFO and PO4x4 all leaks iron ion into the water column, but PO4x4 leaks less, comparing to the others.

Cool? :)

Thx for doing this Acrotrdco! The test is very informative. It's very surprise to see how clean PO4x4 is which is really what I am mostly interested about; rinsing GFO media is not fun at all.

Other than the iron leaching aspect of PO4x4, how are your general impression with this product so far? Have you seen your phosphate drop?

My PO4 was at 0.015 level before using PO4x4 (I was using Rowaphos), and after switching to 50ml of PO4x4, I have not measured any change in my PO4, and I've been feeding quite heavily lately since I've introduced a few new fishes to my tank, trying to make them to start feeding on frozen food.

[Randy Holmes-Farley]

Well, yes and no. We need to be very careful what we conclude. :)

Release of particles, no matter how small, does not imply any availability of the iron for uptake into organisms (like microalgae or corals), or availability to function as a catalyst for precipitation of CaCO3. It may simply be solids that will settle out in the tank like fine sand.


For many purposes, it is the true soluble iron that is the concern. To separate out the solids, one could probably centrifuge them out, or remove them by ultrafiltration as through a dialysis membrane.

So to that extent, I'm not sure one can make a conclusion about the differences, if any, in such an experiment, except that there is the potenntial for more total iron to get into the system from the uncoated ones.

To expand a bit why I'm concerned, the methods used in such an iron test will usually involve binding the iron to a dye. Strongly binding it so one can be sure that all available iron is bound. Under these circumstances, iron may be dissolved off of particles and appear as soluble iron when in reality, it was originally present as a particle.

The same sort of thing is well known to happen in calcium and alkalinity tests, where solids dissolve during the testing, but which do not reflect real available calcium or alkalinity in the water.

[Acrotrdco]

Thanks Randy.

I agree with you that the methods used in these hobby-grade iron tests will never be able to 100% accurately measure the actual concentration of iron in the water column, even Hanna lists the spec of their colorimeter as:

HI 721 spec :
Range : 0.00 to 5.00 ppm
Resolution : 0.01 ppm
Accuracy : +-0.04 ppm +-2% of reading

But given that all the 4 tests were done using very similar approach to minimize the margin of error, then like you said "there is the potenntial for more total iron to get into the system from the uncoated ones. "

I also agree with 2thdeekay that the actual concentration of iron in the ocean is a lot lower, I've read research paper that actually performed tests on adding iron into the ocean to grow photoplankton, to absorb more CO2 into the ocean.

There's also an unproven claim by Russ George, stating “Give me half a tanker of iron and I will give you an ice age.”
http://www.abovetopsecret.com/forum/thread484475/pg1

Answering 2thdeekay's question:
"Are those extra iron ions harmful, or beneficial to your system? That's the real question!"

I've no doubt the extra iron isn't harmful, or even beneficial since it'll enhance the green pigment in some of my SPS's, so I don't mind having a little extra iron at all.

I'll conclude this report by saying, I pleasantly enjoyed the fact that I don't need to rinse the PO4x4 prior to adding them to my system, it absorbs PO4 just as well as GFO does. It's even a lot more reactor-friendly than GFO's because of its pellet-like property. Also there is the potential for PO4x4 to leak less iron ion into the water column, which is fine for those who might be experiencing some algae problem and wanted to get their iron concentration lower.

:)

[Randy Holmes-Farley]

As long as you like the results of using it, there's certainly no reason to not do so. :)

[jtma508]

I just started using it myself. For sure, not having to rinse is a big plus but I also find that the granules seem to stay better suspended in the reactor which would presumably present a larger surface area to the water flow. I also noticed with regular GFO (BRS) that after awhile the GFO would cake-up and water wouldn't flow quite as uniformly through the mass.

[SimonSKL]

I am also excited about the claim that this product can be regenerated 20 times or more using the regeneration buffer which will be coming out soon.

[2thdeekay]

I am also excited about the claim that this product can be regenerated 20 times or more using the regeneration buffer which will be coming out soon.

I'm curious to see if anyone has compared it to BA's Phosphat-R? I wouldn't be surprised if it is a clone product, from same mfr.

[dzhuo]

How does the product holding up? Update?

[MaLi]

Nice discussion gentlemen. Thanks for sharing.

Here is a practical observation: About 3 months ago I replaced a GFO reactor (using High capacity BRS) with an Algae Scrubber. Though my Elos Phosphate test was always showing zero I had to clean the glass every three days or so. Now, after 3 months the need for cleaning drifted to almost a week. It is known that diatoms thrive on Iron so at this time I suspect the needed Iron was coming from GFO. Time will further tell, but this is not a coincidence.

Nothing has changed on other water parameters and the ATS is still not working as it should.

cheers,
Marian

[Randy Holmes-Farley]

I'd not seen any information suggesting that diatoms need iron more than any other algae. What have you read?

[jtma508]

I've been using it for just about a month now after having used BRS GAC for about 3yrs. I'll tell you that the granules tend to stay suspended (with regular GAC it would tend to cake and slow the reactor after awhile). I have noticed significantly reduced diatom blooms since I've been using it.

[2thdeekay]

Do you mean BRS's GFO? Updates?

I've been using it for just about a month now after having used BRS GAC for about 3yrs. I'll tell you that the granules tend to stay suspended (with regular GAC it would tend to cake and slow the reactor after awhile). I have noticed significantly reduced diatom blooms since I've been using it.

[jtma508]

yea, sorry GFO. Still seems to be doing what it's supposed to.

[Plato]

Been using for about a month now. Liking it more than gfo. It is performing very well. Excited about the ability to regenerate. The beads look like resin beads from a di cartridge or water softener.

[dzhuo]

Any update on this product?

[glweek]

id like to know as well

[Isayso]

id like to know as well

yes me too:) im about to order some

[xtlosx]

Hate to resurrect this, but any longer term updates? Looking to try some over the regular BRS high capacity GFO.

[Randy Holmes-Farley]

The OP is apparently banned from RC, so there may not be any updates from him or her. :)

[Plato]

Well I have used them for quite a while. The cost and mess to regenerate for me was not worth the mess. Also noted my chaeto started to shrink in my fuge. Not from less PO4 but probably from lack of Fe, my tank ran around .4 to .8 on Red Sea or Hanna colorimeter. Same as on GFO. I have switched back to high capacity GFO as it is more cost effective and less trouble for me. I experienced my reactor clogging and needing more frequent service. Could be due to tiny size of beads. Now back on GFO my chaeto requires frequent harvesting.

[tmz]

FWIW, if the concerns are fine particulates and a need for excessive gfo rinsing , BRS HC gfo which is quite dense, 1.75 times as dense as granulalted gfo, gives little dust with minimal einsing and holds up well in a reactor. It also stands up to the regeneration process well.

[xtlosx]

Interesting. I've been using high capacity GFO for a while, and figured I would try something new as I still am battling a phosphate issue even through all of this. We'll see how it goes, just ordered a bag.

[mgrmax]

Interesting. I've been using high capacity GFO for a while, and figured I would try something new as I still am battling a phosphate issue even through all of this. We'll see how it goes, just ordered a bag.

Please keep us updated about the progress. I've been using Rowaphos and have contemplated switching.

[xtlosx]

Please keep us updated about the progress. I've been using Rowaphos and have contemplated switching.

So have been using about a little under a cup since Monday, phosphates were .08, then the next day, not even 24 hrs and was down to .05. Doing great, glass is still spotless. PE on my SPS was overnight twice as big... so they are obviously feeling good.

My tank is laden with phosphates and have been battling an issue for a long time, but so far so good. I think the "wave" action of the polymer vs tumbling of the pellet GFO is where I'm getting the best results from. Half of my old GFO would always clump up at some point and be rendered useless, but with this, it just waves and is all basically suspending and constantly moving.

So far, so good!

[mgrmax]

So have been using about a little under a cup since Monday, phosphates were .08, then the next day, not even 24 hrs and was down to .05. Doing great, glass is still spotless. PE on my SPS was overnight twice as big... so they are obviously feeling good.

My tank is laden with phosphates and have been battling an issue for a long time, but so far so good. I think the "wave" action of the polymer vs tumbling of the pellet GFO is where I'm getting the best results from. Half of my old GFO would always clump up at some point and be rendered useless, but with this, it just waves and is all basically suspending and constantly moving.

So far, so good!

Thanks for the update. How long will that cup last before you have to replace it?

[xtlosx]

Thanks for the update. How long will that cup last before you have to replace it?

Well, just tested this morning.. .00 and at this rate, I won't be changing it for quite a while actually. Next time I add it, I'll cut it in half (either half cup or even potentially less).

This stuff is absolutely amazing.

[tajaba]

sorry to stir up an old thread again, but anyone have more long term info on this product? I am very limited in choice of GFO since I am in Thailand.

Actually I only have 2 choices, keep rinsing Rowaphos or use this instead.

any info would be appreciated, thanks!

[xtlosx]

sorry to stir up an old thread again, but anyone have more long term info on this product? I am very limited in choice of GFO since I am in Thailand.

Actually I only have 2 choices, keep rinsing Rowaphos or use this instead.

any info would be appreciated, thanks!

So I have been using this product continuously, and LOVE it... Last couple months, they had some production problems and wasn't available. I had to use Rowa, and or BRS stuff and noticed a large difference. I'm back on PO4x4, and I love it.. so glad it's back.

[imagex]

how long does it last?? and how much of this stuff do you use?

[bertoni]

Well, it's basically GFO, so I'd expect a fairy similar amounts whichever you're using, although the polymer coating might reduce adsorption. It should last about as long as GFO, as well.