Marine Pure does release some form of Al into tank

zack801

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What makes these marine pure blocks leach aluminum. I've been using the brightwell aquatics version but I don't know if they have the same problems?
 

A4goulet

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If you remove them can you let us know if the aluminum concentration gets lower over time?
I am also very curious of this, especially since the OP is implementing the Triton Method (minimal/no water changes).

Edit: Assuming the OP is doing Triton Method*.
 

Scott Campbell

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What would be a better solution if MP leaches.

It's not all that clear that Marine Pure blocks are indeed leaching aluminum. At least not in significant amounts.

As noted, increased amounts of aluminum will usually show up on an ICP test if you place Marine Pure blocks in your aquarium. But ICP tests break everything down into the most basic elements. What the blocks are likely releasing is relatively inert ceramic dust (alumina silicate dust).

Reasons to suspect alumina silicate dust rather than aluminum:

BRS studies showed the amount of aluminum showing up on an ICP test was several times greater relative to the total volume of Marine Pure material for the "dustier" blocks. Namely, the very thin blocks. For the same amount of material, the thin blocks released something like 4 times as much aluminum. If the blocks were actually leaching aluminum, the amount of aluminum released would be roughly proportional to the amount of ceramic material added to the tank. Which is not the case. The spheres released much less aluminum than either block shape. The blocks are extruded shapes which are then cut to size. The cutting process clearly degrades the integrity of the block. The spheres are molded shapes and are much more stable.

Ceramic flower pots will release aluminum at very low and at very high pH levels. Plants in ceramic flower pots will experience obvious aluminum toxicity at low and high pH levels. Plants in ceramic flower pots do not however exhibit symptoms of aluminum toxicity at pH values in the 7.6 to 8.3 ranges. Ceramic materials (alumina silicates) are rather inert and non-reactive at pH values normally seen in a reef aquarium. Bacteria growing on flower pots also does not appear to slow the release of aluminum at low and high pH values. At a pH of 8.0 or so, a Marine Pure block would at worse leach aluminum very, very slowly.

Aluminum toxicity is not something an organism will usually recover from. Plants exposed to high levels of aluminum will continue to decline as long as the source of aluminum remains in place. The plants do not respond poorly at first and then regain health. And most organisms find high levels of aluminum to be toxic. So the fact that just select organisms (like mushroom corals and sponges) react negatively and then recover is not something that would probably happen if the Marine Pure blocks were leaching aluminum. The leaching would continue, the effects would get worse over time and quite a broad range of organisms would likely eventually suffer. Suddenly releasing a bunch of ceramic dust into the aquarium could however temporarily irritate certain corals - which could then recover as the dust slowly settles out. Ceramic dust can be a powerful irritant and is considered a hazard even for humans.

You can visibly see dust fall off of the Marine Pure blocks.

BRS studies also showed a spike of silica on ICP tests when aluminum levels jumped. Which would also be consistent with a sudden cloud of alumina silicate dust.

Many, many people use Marine Pure blocks without seeing any long-term elevated levels of aluminum. I personally use the spheres and have no detectable aluminum. Many folks using the thin blocks (and to a lesser extent the thick blocks) do, however, experience short-term elevated levels of aluminum on an ICP test soon after placing the blocks. And many also notice short-term coral irritation.

I believe largely inert dust is mostly what is showing up on ICP tests. The effect of dumping a bunch of dust into the aquarium is consistent with what most people experience when they place a Marine Pure block in their sump.
 

Randy Holmes-Farley

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A couple quick questions for Doctor.Farley
Will cuprazorb remove Al3+ from water?
Are any other soft corals affected by Al3+
What compound did you dose to cause that close up response?

I dosed aluminum chloride.

Triton says GFO may absorb aluminum. I’m not certain how well the polymer metal binders bind aluminum. In seawater it actually is neutral Al(OH)3 or anionic Al(OH)4-, which is different than most metals. That said, the OH-can come off if it is displaced by something that binds more strongly.

Mushrooms responded in my tests as well.
 

40B Knasty

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ICP test got back today. I have seen reports of people saying Marine Pure block releases some form of Al. It does based on ICP tests before and after placement of marine pure block in sump of my 700 gallon tank. Below is 11-14-2017 test and have several tests before this without reported Al
icp test 11-14-2017.jpg
ICP test today after running marine pure block for 6 weeks.
icp test 1-30-208.jpg
Is that with no water change in 6 weeks?
 

Randy Holmes-Farley

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It's not all that clear that Marine Pure blocks are indeed leaching aluminum. At least not in significant amounts.

As noted, increased amounts of aluminum will usually show up on an ICP test if you place Marine Pure blocks in your aquarium. But ICP tests break everything down into the most basic elements. What the blocks are likely releasing is relatively inert ceramic dust (alumina silicate dust).

Reasons to suspect alumina silicate dust rather than aluminum:

BRS studies showed the amount of aluminum showing up on an ICP test was several times greater relative to the total volume of Marine Pure material for the "dustier" blocks. Namely, the very thin blocks. For the same amount of material, the thin blocks released something like 4 times as much aluminum. If the blocks were actually leaching aluminum, the amount of aluminum released would be roughly proportional to the amount of ceramic material added to the tank. Which is not the case. The spheres released much less aluminum than either block shape. The blocks are extruded shapes which are then cut to size. The cutting process clearly degrades the integrity of the block. The spheres are molded shapes and are much more stable.

Ceramic flower pots will release aluminum at very low and at very high pH levels. Plants in ceramic flower pots will experience obvious aluminum toxicity at low and high pH levels. Plants in ceramic flower pots do not however exhibit symptoms of aluminum toxicity at pH values in the 7.6 to 8.3 ranges. Ceramic materials (alumina silicates) are rather inert and non-reactive at pH values normally seen in a reef aquarium. Bacteria growing on flower pots also does not appear to slow the release of aluminum at low and high pH values. At a pH of 8.0 or so, a Marine Pure block would at worse leach aluminum very, very slowly.

Aluminum toxicity is not something an organism will usually recover from. Plants exposed to high levels of aluminum will continue to decline as long as the source of aluminum remains in place. The plants do not respond poorly at first and then regain health. And most organisms find high levels of aluminum to be toxic. So the fact that just select organisms (like mushroom corals and sponges) react negatively and then recover is not something that would probably happen if the Marine Pure blocks were leaching aluminum. The leaching would continue, the effects would get worse over time and quite a broad range of organisms would likely eventually suffer. Suddenly releasing a bunch of ceramic dust into the aquarium could however temporarily irritate certain corals - which could then recover as the dust slowly settles out. Ceramic dust can be a powerful irritant and is considered a hazard even for humans.

You can visibly see dust fall off of the Marine Pure blocks.

BRS studies also showed a spike of silica on ICP tests when aluminum levels jumped. Which would also be consistent with a sudden cloud of alumina silicate dust.

Many, many people use Marine Pure blocks without seeing any long-term elevated levels of aluminum. I personally use the spheres and have no detectable aluminum. Many folks using the thin blocks (and to a lesser extent the thick blocks) do, however, experience short-term elevated levels of aluminum on an ICP test soon after placing the blocks. And many also notice short-term coral irritation.

I believe largely inert dust is mostly what is showing up on ICP tests. The effect of dumping a bunch of dust into the aquarium is consistent with what most people experience when they place a Marine Pure block in their sump.

There certainly may be some particulate aluminum materials released. In some cases that could be most or all of it, but I’ve seen no evidence to suggest that is the case in normal reef usage. The fact that Triton thinks GFO binds it would suggest at least some is soluble. I’m also not sure that it ultimately makes a difference what form it takes if it is irritating corals.

I don’t buy the assertion that the aluminum released would be unrelated to the physical shape if it was dissolved. For a kineticaly slow dissolution, one would expect that it is related to surface area, and the thicker a piece, the less surface area is near the outer edge of the block, and hence readily diffusable out of it. That is, after all, what is supposed to make these blocks good at denitrification: the pores are deep enough to make diffusion of O2 into them slow. Aluminum diffusion would also be slow.

That said Seachem tried to play the dust card when I studied Phosguard for aluminum release, but even very fine particulate filters left most of the aluminum in solution.

Finally, the comments on organisms not recovering if it was soluble aluminum seems to be at odds with my tests on corals using soluble aluminum. They did recover.

While I have not looked for it, particulate icp results should show a relatively fixed silicon to aluminum ratio, while separate release of individual soluble ions that are then subject to potentially rapid consumption of silicate by diatoms might well show quite divergent ratios. So perhaps we have the data already at hand to answer this. [emoji3]
 

Scott Campbell

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Finally, the comments on organisms not recovering if it was soluble aluminum seems to be at odds with my tests on corals using soluble aluminum. They did recover.

This is from your article. It doesn't sound like the corals are recovering. At least not as long as the corals remain exposed to aluminum.

After 48 hours, the leather no longer opened at all. It then stayed closed for the next 3 days until the termination of the experiment. I’ve since moved it to my main tank in the hope that it will recover.


5 hours after the last aluminum addition, the mushroom corals appeared less expanded than before the aluminum additions, but not nearly as dramatically as the leather. They stayed that way until the termination of the experiment.


The green star polyps seemed unchanged for the first 48 hours. After that, they expanded significantly less than they had previously. The polyps were about half of the size that they were before dosing aluminum. They were still that way at the termination of the experiment.


I’m also not sure that it ultimately makes a difference what form it takes if it is irritating corals.

If Marine Pure blocks are leaching aluminum, then it is a long-term exposure issue. If it is ceramic dust, then it is a short-term exposure issue. A short-term problem is better than a long-term problem.


For a kineticaly slow dissolution, one would expect that it is related to surface area, and the thicker a piece, the less surface area is near the outer edge of the block, and hence readily diffusable out of it.

The spheres have a lot of surface area relative to the volume of ceramic material (maybe the most) yet release the least amount of alumina / aluminum. And again - you can just look at the thin blocks and see that they are *much* dustier and much more fragile than the spheres.


(W)hen I studied Phosguard for aluminum release, ... even very fine particulate filters left most of the aluminum in solution.

Kiln-fired alumina-silicate material is very different from Phosguard. Phosguard is meant to be reactive in order to bind with phosphate. I honestly don't see the value in comparing the two materials.
 

Forsaken77

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MP suggests thoroughly rinsing the media before use to rid it of dust. Are people just dropping that dusty block right into the tank?

Also, can't carbon absorb any aluminum?

I wonder if placing a block in a bucket of rodi with a powerhead blasting through it would help to clean it out?
 

Randy Holmes-Farley

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So Scott, I will address the points you just made shortly, but lets look at some actual silicon and aluminum data from Triton where people are testing marine Pure. I think it provides evidence that the material released is not a particulate containing both Si and Al.

In this thread relating to the BRS test:

https://www.reef2reef.com/threads/i...brstv-investigates.307515/page-7#post-3820366

You stated:

"If you just look at the spheres it would appear the ceramic material is roughly 90% silica and 10% alumina. Which is unlikely. The block gives you a ratio of 80% silica to 20% alumina. Possible. And the plate is something like 55% alumina and 45% silica. Also possible. But I feel certain Marine Pure is using a single formula - at least for the square shapes. If you average the 3 shapes you get a ratio of roughly 70% silica and 30% alumina - which is a very common ratio for ceramic materials."

Here's the raw data:

Aluminum
Control with no marine pure 1.64 ug/l
Large marine pure block 51.00 ug/l
Marine pure plate 174 ug/l
Marine pure sphears 32.00 ug/l

Silicon
Control Si - 174 ug/l
Block Si - 380 ug/l
Plate - 313 ug/l
Spheres - 544 ug/l

As you note, there's a lot of silicon released.

You have some handwaving arguments about why the Al/Si ratios are not the same for the different shapes, but you ignore an obvious possibility: that the are not actually particulates but dissolved materials, and after release they are prone to different processes that remove them from the water.

Nevertheless, let's assume all the aluminum and silicate rise in those tanks is particulat, and accept your 70% silica number.

Now lets look at other people with similar tests.

Jason does some testing here, where he observed his leather to cycle just like mine with soluble aluminum dosing:
https://www.reef2reef.com/threads/how-much-aluminum-will-it-leach-lets-guess.247034/

His starting water
https://www.reef2reef.com/threads/how-much-aluminum-will-it-leach-lets-guess.247034/page-7
Al 0 ug/L
Si 88 ug/L

After a few weeks, he found:
https://www.reef2reef.com/threads/how-much-aluminum-will-it-leach-lets-guess.247034/page-9

Si 43.7 ug/L
Al 19 ug/L

So if the aluminum is from particulates in the water, one would have expected Si to rise. It did not. It declined. The only explanation that can save the particulate hypothesis with 70% silica is that the the background soluble Si in the water declined to almost nothing during the test and the particulate Si is what is left. While I cannot prove that didn't happen, it seems to require one to look for unusual explanations to try to preserve the particulate hypothesis.

FWIW, none of these values are close to the limit of detection and accurate quantitation published by Triton:
https://www.triton-lab.de/fileadmin/user_upload/triton-lab/TRITON_LOD.pdf
 

Randy Holmes-Farley

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This is from your article. It doesn't sound like the corals are recovering. At least not as long as the corals remain exposed to aluminum.
.

I thought we were talking about "recovery" after removal to clean water. They recovered in my main tank where there was no substantial aluminum. Maintaining corals in a high aluminum environment by adding soluble aluminum for long term tests would be quite labor and test intensive, and not something that I pursued. I thought the article mentioned the recovery, but I guess it did not. I only said in it that I moved it to the main tank in the hope that it would recover. They all did.

If Marine Pure blocks are leaching aluminum, then it is a long-term exposure issue. If it is ceramic dust, then it is a short-term exposure issue.

I'm not sure why one would make the assumption that dissolution will not slow down considerably over time as the material becomes coated with organics and such.

Also, any inorganic material may have surfaces with crystal edges, points, and even different phases or even different minerals that may more readily dissolve, quickly leaving more insoluble materials exposed (e.g., I showed that silica (quartz) sand releases a lot of soluble silicate, and I think exposed inclusions of different minerals than quartz may be the most likely explanation).

For these reasons, both soluble and particulate releases may be worse in the short term (days to weeks) than the long term (months to years).

Kiln-fired alumina-silicate material is very different from Phosguard. Phosguard is meant to be reactive in order to bind with phosphate. I honestly don't see the value in comparing the two materials.

They are obviously different and release from one does not imply release from the other. But both were widely touted by the hobby reseller as leaching no aluminum. Then when data began to suggest otherwise, both companies did their own tests to try to buttress those claims after the fact. IMO, both company tests were inadequate tests for different reasons (MarinePure started with a salt mix having aluminum already unusually high (above the published solubility limit of aluminum in seawater) and Seachem used a machine with a stated limit of detection that, by its own specs, could not detect the levels of aluminum that I found, so finding none didn't dispute my findings, but still allowed them to claim none was released. lol).
 

Randy Holmes-Farley

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MP suggests thoroughly rinsing the media before use to rid it of dust. Are people just dropping that dusty block right into the tank?

Also, can't carbon absorb any aluminum?

I wonder if placing a block in a bucket of rodi with a powerhead blasting through it would help to clean it out?

Some people may be, but certainly many people getting an aluminum rise are rinsing them.

This is from the guy doing the test I showed data from:
https://www.reef2reef.com/threads/how-much-aluminum-will-it-leach-lets-guess.247034/#post-2902503

"I gently rinsed the block in rodi several times before gently placing it in the sump. There have been reports of these falling apart or erroding away which regardless of Al content or type does concern me."
 

Randy Holmes-Farley

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My nitrates are 30~ hard to judge between 20 and 40 on my Red Sea test.

If you are not seeing issues with leathers or other corals, I'd probably leave it in unless nitrate drops below 1 ppm. There certainly are alternatives, but most methods have pros and cons. I prefer organic carbon dosing to these sorts of media.
 

Scott Campbell

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So Scott, I will address the points you just made shortly, but lets look at some actual silicon and aluminum data from Triton where people are testing marine Pure. I think it provides evidence that the material released is not a particulate containing both Si and Al.

In this thread relating to the BRS test:

https://www.reef2reef.com/threads/i...brstv-investigates.307515/page-7#post-3820366

You stated:

"If you just look at the spheres it would appear the ceramic material is roughly 90% silica and 10% alumina. Which is unlikely. The block gives you a ratio of 80% silica to 20% alumina. Possible. And the plate is something like 55% alumina and 45% silica. Also possible. But I feel certain Marine Pure is using a single formula - at least for the square shapes. If you average the 3 shapes you get a ratio of roughly 70% silica and 30% alumina - which is a very common ratio for ceramic materials."

Here's the raw data:

Aluminum
Control with no marine pure 1.64 ug/l
Large marine pure block 51.00 ug/l
Marine pure plate 174 ug/l
Marine pure sphears 32.00 ug/l

Silicon
Control Si - 174 ug/l
Block Si - 380 ug/l
Plate - 313 ug/l
Spheres - 544 ug/l

As you note, there's a lot of silicon released.

You have some handwaving arguments about why the Al/Si ratios are not the same for the different shapes, but you ignore an obvious possibility: that the are not actually particulates but dissolved materials, and after release they are prone to different processes that remove them from the water.

Nevertheless, let's assume all the aluminum and silicate rise in those tanks is particulat, and accept your 70% silica number.

Now lets look at other people with similar tests.

Jason does some testing here, where he observed his leather to cycle just like mine with soluble aluminum dosing:
https://www.reef2reef.com/threads/how-much-aluminum-will-it-leach-lets-guess.247034/

His starting water
https://www.reef2reef.com/threads/how-much-aluminum-will-it-leach-lets-guess.247034/page-7
Al 0 ug/L
Si 88 ug/L

After a few weeks, he found:
https://www.reef2reef.com/threads/how-much-aluminum-will-it-leach-lets-guess.247034/page-9

Si 43.7 ug/L
Al 19 ug/L

So if the aluminum is from particulates in the water, one would have expected Si to rise. It did not. It declined. The only explanation that can save the particulate hypothesis with 70% silica is that the the background soluble Si in the water declined to almost nothing during the test and the particulate Si is what is left. While I cannot prove that didn't happen, it seems to require one to look for unusual explanations to try to preserve the particulate hypothesis.

FWIW, none of these values are close to the limit of detection and accurate quantitation published by Triton:
https://www.triton-lab.de/fileadmin/user_upload/triton-lab/TRITON_LOD.pdf


Randy

I think BRS did a good job with their Marine Pure tests. Their results showed a significant increase in silica across all the tests. It would have been nifty if the silica / aluminum ratios were the same for each test but ICP testing may not allow for that level of precision. Most people take a "on average across multiple tests" view of ICP results. Your theory that this is dissolved silica rather than particulate silicate doesn't explain why the silica increased beyond expectations in some samples any more than my theory explains why it is less than expected in some samples. On average across all the samples in the BRS tests, the results showed silica increased in relation to aluminum in a normal ceramic material ratio.

After placing a Marine Pure block in their aquarium, most people notice a rather immediate negative reaction by some corals followed by a slow and complete recovery. This is consistent with a large amount of particulate matter being released into the aquarium. Your own studies show that corals exposed to aluminum in significant amounts to cause a negative reaction do *not* recover as long as the corals remain exposed to aluminum. You are arguing that there is perhaps organic matter that somehow shields the corals from continued aluminum exposure over time or that the pointy nature of the ceramic shape degrades and less aluminum is released over time. These seem implausible arguments in my opinion. Plants in ceramic flower pots should see the same mitigating effects over time, but don't. If a ceramic material is leaching aluminum, odds are good it is going to continue leaching aluminum. Particularly a ceramic material as porous as a Marine Pure block. Short-term exposure to dust is the most reasonable theory to explain why a select few organisms respond negatively and then recover. Especially since the Marine Pure blocks often appear to be little more than a pile of dust waiting to happen.

And my "hand waving" away the differences in silica / aluminum ratios across multiple BRS tests isn't much different from you hand-waving away the BRS results about the shape of the block affecting the release of aluminum. The spheres, despite a very high level of surface area relative to volume, release the least amount of aluminum. The thin blocks, with perhaps less surface area relative to volume than the spheres, release several times more aluminum for the same amount of material. Like 5-6 times more aluminum. Again, particulate matter is the simplest explanation for these results.

I absolutely believe you were correct to sound the alarm about Phosguard releasing toxic aluminum. But I'm not sure Marine Pure blocks represent the same type or level of hazard.

Scott
 
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Question - can't we just ask the manufacture if aluminum is somehow in the marine pure product or what could be leaching / releasing it? Show them the test results. I do not use any of the dosing methods (triton, etc) but was considering the use of marine pure blocks in the sump to set my heater on or to place between chambers. I have a mature and old golden leather. After reading this thread this morning tells me I won't be following through with that idea...

Just wondering what their response is or was.
 

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Question - can't we just ask the manufacture if aluminum is somehow in the marine pure product or what could be leaching / releasing it? Show them the test results. I do not use any of the dosing methods (triton, etc) but was considering the use of marine pure blocks in the sump to set my heater on or to place between chambers. I have a mature and old golden leather. After reading this thread this morning tells me I won't be following through with that idea...

Just wondering what their response is or was.

There is aluminum - which is a base element, rather toxic and rather reactive. And there is alumina - which is the second most common material on the planet (behind silica), not particularly toxic and not particularly reactive. Basically a component of dirt. Alumina contains the element aluminum. And then there are ceramic materials which contain alumina-silicates which are kiln fired to a high temperature to harden the dirt into something slightly glass-like. Ceramic materials are generally even less toxic and less reactive. Vortech powerheads, for example, use some ceramic parts. The Marine Pure blocks are a ceramic material of some sort. So they will contain alumina-silicates by default. They are also kiln fired to some temperature. All 3 materials - base aluminum, alumina and ceramic alumina-silicates will show up as simply aluminum in an ICP / Triton test.

As nearly everyone has noticed, the Marine Pure blocks clearly release a lot of something into the tank. But it is difficult to determine if that something is toxic aluminum or just ceramic alumina-silicate dust. Ceramic materials can certainly leech a lot of things. Run of the mill ceramic containers will leech a lot of aluminum at low and high pH values. On flower pots you can see the white aluminum scum forming all over the pot. My brother has spent a decent amount of time trying to formulate a low alumina flower pot material so that orchids are not harmed at extreme pH values. Porous dust will be more likely to leech than a vitrified and glass-like solid. So it is certainly possible that toxic aluminum is being released from any and all ceramic material used in a reef tank (including decorative skulls, Vortech parts, magnets, etc.) At normal reef pH ranges, however, most ceramic materials are rather safe and inert. Which is why you don't see a lot of threads about ceramic pump parts killing corals. What makes Marine Pure blocks problematic is how degraded and fragile some of the shapes are. Plus, the company seems rather clueless about their own product line.
 
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