There Is Phosphate In Aragonite Sand

Dan_P

New member
In a recent post asking about substrate depths, the conversation drifted quite far afield of the initial question. One of the additional topics thrashed out in the thread was whether aragonite sand contains phosphate and whether you can detect it with hobby phosphate test kits. I am reporting that the sample of aragonite sand that I have does show the presence of phosphates with the Salifert phosphate kit. Here is how I tested the sand.

1.052 g of CaribSea Aragonite sand (very fine) was dissolved in 5 ml 5 molar (15%) muriatic acid. A surprisingly stiff foam formed during the dissolution process (see picture below). When the dissolution was complete the solution was diluted and tested for phosphate. A portion of the solution was partially neutralized with sodium bicarbonate to about pH 5. It tested about 2 ppm. A portion of the solution without neutralization did not develop a blue color when tested. Repeating the partial neutralization with sodium bicarbonate on the remaining portion of the dissolution sample and testing, a blue color developed, indicating 2 ppm phosphate (a real scientist would have neutralized the sample that did not develop a blue color and retest it!). This addresses the question about whether the acid used in the dissolving aragonite would interfere with the phosphate test. I propose the answer is yes. So how much phosphate is this?

There was approximately 15 mL of dissolution sample to start with. The phosphate level in this solution was determined to be 2 mg/L. Multiplying the concentration by 0.015 L gives 0.030 mg. This means 1.052 g of aragonite sand contains 0.03 mg of phosphate or approximately 30 ppm. This study does not indicate the chemical form of the phosphate. I wonder whether 30 ppm is a "œnormal" level for aragonite and whether phosphate was placed there during the formation of the aragonite crystals or afterwards by chemical adsorption.

Maybe as interesting as the presence of phosphate is the rigid foam that forms turning the dissolution. This may indicate a small amount of protein mixed in with the aragonite matrix. Not surprising given the biological origin of this aragonite.

The next question that I need to answer is whether there is phosphate in the silica sand bed in my system that is liberated with a brief exposure to acid.

Foam_zpspxahen9q.jpg
 
Interesting! I take it the sand was fresh from the vendor, and not from a tank?

Yes, this was fresh sand taken from the bag. Here is an article reporting similar observations.

http://www.advancedaquarist.com/2003/4/short

The phosphate content is reported to be 1/10 the level I observed. Given that my Salifert test results are "approximate", being off by a factor of ten is not impossible. Using a Hanna checker would provide a better estimate. I was also thinking that it would not be a bad idea to test the muriatic acid and sodium bicarbonate for phosphate content if someone is really interested in an accurate estimate of phosphate content of aragonite. I will be doing both when I look for acid released phosphate in the silica sand substrate in my aquarium.

Dan
 
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Dan, While I can't comment on new sand I can say sand in a tank will harbor phosphate in higher concentrations than the water column.
Heard this from one of the owners of ESV, did the test myself to confirm it.
 
I think all naturally occuring aragonite will contain some inorganic phosphate sunk in the crystal matrix. It doesn't mean it will leach out or affect the aquarium without dissolution of the argonite in acidic conditions . There may also be some bound to surfaces which will equilibrate with the water.
 
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where's the pics of the test? One pic of a spoon being held up with foam isn't sufficient.

what was the result of a blank test? maybe your hcl has phosphate? maybe your bicarbonate has phosphate? maybe your water has phosphate?

Whats your repeatability?
 
where's the pics of the test? One pic of a spoon being held up with foam isn't sufficient.

what was the result of a blank test? maybe your hcl has phosphate? maybe your bicarbonate has phosphate? maybe your water has phosphate?

Whats your repeatability?

A brother skeptic!

This was an N of one test: one sample, one test of the sample.

The phosphate test of the muriatic acid neutralized with sodium bicarbonate in RO water showed no color change. Reagents are innocent of contributing phosphate.

A calibration curve of the Salifert test and Hanna checker confirm the visusl estimation of the 2 ppm phosphate level.

The foam is really interesting because it likely to be caused by an organic substance, maybe not much though. I wonder what else is in aragonite sand and does it lead to issues for new set ups?

Does phosphate in aragonite lead to issues in saltwater aquaria? That seems like a more difficult question to answer. Somebody suggested that a bag of wet sand stored in sunlight that grows algae would answer the question. I am not so sure.

So thst's it. Just a quick and dirty study to address a question. In my case, the answer is yes, my aragonite sand contains phosphate and a foaming agent.
 
Dan, While I can't comment on new sand I can say sand in a tank will harbor phosphate in higher concentrations than the water column.
Heard this from one of the owners of ESV, did the test myself to confirm it.

What did you test, the sand or the pore water?
 
I think all naturally occuring aragonite will contain some inorganic phosphate sunk in the crystal matrix. It doesn't mean it will leach out or affect the aquarium without dissolution of the argonite in acidic conditions . There may also be some bound to surfaces which will equilibrate with the water.

When live rock is "cooked" is it primarily the adsorbed phosphate that is being released rather than the phosphate within the aragonite matrix?

And do we know that the phosphate within the aragonite matrix dissolves as the calcium carbonate disdolves?
 
A brother skeptic!

This was an N of one test: one sample, one test of the sample.

The phosphate test of the muriatic acid neutralized with sodium bicarbonate in RO water showed no color change. Reagents are innocent of contributing phosphate.

A calibration curve of the Salifert test and Hanna checker confirm the visusl estimation of the 2 ppm phosphate level.

The foam is really interesting because it likely to be caused by an organic substance, maybe not much though. I wonder what else is in aragonite sand and does it lead to issues for new set ups?

Does phosphate in aragonite lead to issues in saltwater aquaria? That seems like a more difficult question to answer. Somebody suggested that a bag of wet sand stored in sunlight that grows algae would answer the question. I am not so sure.

So thst's it. Just a quick and dirty study to address a question. In my case, the answer is yes, my aragonite sand contains phosphate and a foaming agent.

Indeed I am a skeptic. Thanks for your follow up.
 
I think all naturally occuring aragonite will contain some inorganic phosphate sunk in the crystal matrix. It doesn't mean it will leach out or affect the aquarium without dissolution of the argonite in acidic conditions . There may also be some bound to surfaces which will equilibrate with the water.

Can you recommend a good post or article or two about how these two processes work?
I think I mostly have my head around the binding action where the phos attaches to the carbon molecule crystal part, because I've read some things about how they use it for kidney dialysis and waste water treatment stuff. But I dont understand the surface adsorption very well.
 
When live rock is "cooked" is it primarily the adsorbed phosphate that is being released rather than the phosphate within the aragonite matrix?

The phosphate bound on (and in) calcium carbonate is always from the water column. As the rock is forming, if phosphate is present it will be incorporated within the rock. Of course in nature it's abnormal to have high phosphate. To get the phosphate out of a rock formed in high phosphate, would be impossible, you would have to dissolve the entire rock.

In the case of rock for our aquaria, phosphate is absorbed onto water-accessible surfaces to make calcium phosphate. So when people "cook" rocks on the timescales used it's to remove the calcium phosphate on the water-accessible surface.

And do we know that the phosphate within the aragonite matrix dissolves as the calcium carbonate disdolves?

The K-sp for calcium carbonate is much higher than the K-sp for calcium phosphate (10^-9 vs 10^-33). But there is much more calcium in solution. You could do the math pretty easily, but it's well known that phsophate leaches from rock that was previously in high PO4 water (when put in low PO4 water).
 
I vacuumed the sand , let the water clear & tested that sample against water in the upper portion of the tank.

OK, this was mostly pore water. I observed the same thing in silica sand when I carefully removed water from the bottom of the bed with a 3/16 in rigid plastic tube, very slowly drawing up water but no sand. The tip of the tube had a small piece of filter floss attached. So this is not necessarily an aragonite phenomenon but what naturally happens in the substrate. I also detected iron and ammonia but nitrate.
 
Just on a biological note: silica sand can offer its own troubles: diatoms use silica.
 
The phosphate bound on (and in) calcium carbonate is always from the water column. As the rock is forming, if phosphate is present it will be incorporated within the rock. Of course in nature it's abnormal to have high phosphate. To get the phosphate out of a rock formed in high phosphate, would be impossible, you would have to dissolve the entire rock.

In the case of rock for our aquaria, phosphate is absorbed onto water-accessible surfaces to make calcium phosphate. So when people "cook" rocks on the timescales used it's to remove the calcium phosphate on the water-accessible surface.



The K-sp for calcium carbonate is much higher than the K-sp for calcium phosphate (10^-9 vs 10^-33). But there is much more calcium in solution. You could do the math pretty easily, but it's well known that phsophate leaches from rock that was previously in high PO4 water (when put in low PO4 water).

How does this sound?

The adsorption mechanism for phosphate onto an aragonite surface is an electrostatic attraction not an ion exchange with carbonate, at least that how I interpret the isotherms. This surface bond phosphate is not in the form of calcium phosphate and is leachable. Diffusion rates are extremely slow. So weeks would be required for the desorption process to be completed in live rock.

The actual incorporation into the aragonite matrix would seem to be ion exchange process that results in calcium phosphate formation which would not be leachable but available to bacteria.

Calcium phosphate has difficulty in precipitating and is supersaturated in seawater but dissolution still behaves in accordance with the Ksp, calcium phospahate needs acid or enzyme to dissolve. I want to obtain calcium phosphate to measure how much dissolves in a couple months in seawater. Stay tuned.

The leachable phosphate notion has not been proven to be strictly a chemical process. Bacterial metabolism of adsorbed organic material or polyphosphates has not been ruled out. Not sure I can test this very well. Heat sterilize a rock and leach under sterile conditions???

Dan
 
The adsorption mechanism for phosphate onto an aragonite surface is an electrostatic attraction not an ion exchange with carbonate, at least that how I interpret the isotherms. This surface bond phosphate is not in the form of calcium phosphate and is leachable.

It's an ionic interaction, just like aragonite formation is an ionic process. On the surfaces of aragonite crystal lattice, there will be calcium ions available to react with phosphate. Live rock has a lot of surface area and anywhere water can go, phosphate can go.

Diffusion rates are extremely slow. So weeks would be required for the desorption process to be completed in live rock.

It's an equilibrium. The rate depends on the concentration of phosphate in the water column and the amount of phosphate bound to rock.

The actual incorporation into the aragonite matrix would seem to be ion exchange process that results in calcium phosphate formation which would not be leachable but available to bacteria.

Anything available to bacteria or algae will be leachable. The non-water-accessible matrix won't be accessible to bacteria.

Calcium phosphate has difficulty in precipitating and is supersaturated in seawater but dissolution still behaves in accordance with the Ksp, calcium phospahate needs acid or enzyme to dissolve. I want to obtain calcium phosphate to measure how much dissolves in a couple months in seawater. Stay tuned.

This experiment is where the K-sp value comes from. I'm not sure what you will learn by doing the experiment you suggest.

The leachable phosphate notion has not been proven to be strictly a chemical process. Bacterial metabolism of adsorbed organic material or polyphosphates has not been ruled out.

I'm not following any of this. It's a chemical process. I have no idea where polyphosphates fit into this.
 
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There is no connection that I can find. This seems to be a hobby myth. Silica sand is not a source of silicate.

Silicate is Si(OH)4 and is what diatoms use. Diatoms have specific transporters for silicate and use it to build their cell walls. There might be finite silicate in silica sand, but diatoms cannot uptake and directly utilize SiO2. There is debate among reef scientists about whether SiO2 can dissolve over time to make Si(OH)4. I've not looked into it, but I know Randy has suggested that silica sand does increase diatom growth. Whether that is from contaminating silicate is unclear.
 
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It's an ionic interaction, just like aragonite formation is an ionic process. On the surfaces of aragonite crystal lattice, there will be calcium ions available to react with phosphate. Live rock has a lot of surface area and anywhere water can go, phosphate can go.

Yes, this makes sense. Just to broaden the topic a bit, the aragonite surface also binds amino acids and proteins. It does a super job on methylene blue too. The point here is that aragonite has a very reactive surface. It is not just sand and a decoration but a chemical adsorbsant. it may not be a stretch to say it is like have a GAC substrate.

It's an equilibrium. The rate depends on the concentration of phosphate in the water column and the amount of phosphate bound to rock.

The ratio of phosphate on the surface to the bulk water is determined by the equilibrium constant but is mediate through chemical diffusion. It takes time to equilibrate because of diffusion. Even an exposed surface has a boundary layer that slows the migration of the phosphate from surface to bulk water. When that surface is buried in a pore, it takes a very long time.

This experiment is where the K-sp value comes from. I'm not sure what you will learn by doing the experiment you suggest.

Yeah, maybe not a good experiment but something I will do anyway.

Given the Ksp, I don't think cakcium phosphate dissolves to a detectable amount in saltwater. Lower pH or bacterial action will dissolve it but given the small amount of calcium phosphate in aragonite, this release in aquariums is not a detectable amount. The leachable phosphate observed in "cooking" live rocks is from some other source. Is it surface adsorbed phosphate? Could be. Is it bacterial digestion of organophosphates and polyphosphates adsorbed onto the surface? Could be.

The point is the phosphates are from surface bond phosphates or bacterial digestion of surface bond polyphosphates and organophosphates not calcium phosphate in the aragonite matrix. Do we agree on this? But how do I prove this?
 
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