Lanthanum chloride

[Scej12]

I would start w/ a 1% dilution with RO/DI and go with something closer to 1.1ml per HOUR! to start. Then gradually increase based on the progress of your results. On my particular system, the dosing pump turns on for 3 minutes every 2.5 hours; approx 1% dilution; 1000g total system volume. I don't remember exactly what the output of my dosing pump is per minute, but 1.6ml sounds familiar. So that works out to about 4.8ml per 2.5 hrs.

Bottom line is that this chemical is extremely potent. Start at a point that you're sure is too low, then work your way up based on regular testing. If you see cloudy water, back down right away.

Regards,

Sheldon

 

[tmz]

I disagree.
Whatever is going on lanthanum phospahte doesn't dissolve at ph levels in the tank, imo. If it doesn't dissolve there is no addition of PO4 to the water. Lathanum phospahte is highly insoluble. It might dissolve in the acid of the test vial if the sample is polluted with fine undissolved precipitant thus giving a false high measure for the water in the tank.

 

[Dustin1300]

I would start w/ a 1% dilution with RO/DI and go with something closer to 1.1ml per HOUR! to start. Then gradually increase based on the progress of your results. On my particular system, the dosing pump turns on for 3 minutes every 2.5 hours; approx 1% dilution; 1000g total system volume. I don't remember exactly what the output of my dosing pump is per minute, but 1.6ml sounds familiar. So that works out to about 4.8ml per 2.5 hrs.

Bottom line is that this chemical is extremely potent. Start at a point that you're sure is too low, then work your way up based on regular testing. If you see cloudy water, back down right away.

Regards,

Sheldon

I disagree with this. You need to dilute the chemical but your talking a much different technique than what Spotter is trying to achieve. If I understand your expectation Steve you want to drop phosphates from time to time using filter sock? Or are you looking to achieve what Sheldon is doing by constantly feeding the LaCl and feeding to a skimmer? To my knowledge Sheldon is only one testing this technique out thus far so dosing would be different.

 

[SPotter]

I disagree with this. You need to dilute the chemical but your talking a much different technique than what Spotter is trying to achieve. If I understand your expectation Steve you want to drop phosphates from time to time using filter sock? Or are you looking to achieve what Sheldon is doing by constantly feeding the LaCl and feeding to a skimmer? To my knowledge Sheldon is only one testing this technique out thus far so dosing would be different.

Correct Dustin....I just want to do it with the filter sock method on an as needed basis.

 

[Dustin1300]

Someone can correct me if I'm wrong but believe Gary/Tom both do the sock method. I have been using about 3 mL of LaCl, drip in at about 1 drop a second via IV line and now am dripping it into my overflow pipe which dumps into a 10 micron sock. I let it run overnight or during the day and change out once the filter sock is overflowing. I try not to feed during this period due to the sock quickly clogging! Gary/Tom can correct me if I'm wrong

 

[Scej12]

Not claiming to know why it works, only that it works under the circumstances cited..

Not claiming to know why it works, only that it works under the circumstances cited..

I disagree.
Whatever is going on lanthanum phospahte doesn't dissolve at ph levels in the tank, imo. If it doesn't dissolve there is no addition of PO4 to the water. Lathanum phospahte is highly insoluble. It might dissolve in the acid of the test vial if the sample is polluted with fine undissolved precipitant thus giving a false high measure for the water in the tank.

Unfortunately, I don't have the chemistry credentials to argue the nuances of which reactions are taking place, and under which [chemical] conditions. I can only go from an empirical standpoint, and note observations made. From that perspective, I can say that there is a very clear time frame between when the reactor system works as hoped - i.e. drops PO4 definitively; and when the system slows; stalls; then eventually becomes noticeably inefficient; even ineffective at removing PO4.

Based on observations made, I also very strongly believe that the effectiveness of the system was (again in my opinion) 'obviously related' to the population of precipitates left within the system or otherwise unexported.

With regard to the exact reasons why.... as mentioned prior, I'm not a chemist, but I can speak to the pattern-consistency and repeat-ability of the findings I've been reporting. I'll leave the actual mechanics to those trained to tackle that monster. Even if you disagree with the reasons as to why; I'm convinced that the results I've found, as well as the accounts others have mentioned suggest some degree of consistency.

Could it be possible that the overall drop in PO4 levels slows not because Lanthanum Phosphate is redissolving, but for some other reason (among numerous possiblities...); could it be something related to a maximum capacity; threshold; saturation point - similar to how kalkwasser works toward a certain saturation point...? <-- just throwing that one out there--

A Chemist as you've mentioned could dig much deeper and uncover exactly why the process worked in my case the way it did; but that still doesn't change the results found; and based on the repeat-ability; I don't think it comes down to a vile tainted with undissolved precipitant. My focus is not so much why it works (on a chemical level) but rather on the circumstances under which the system worked... if you can repeat the circumstances, I'm pretty confident that the results most certainly can also be repeated.

I disagree with this. You need to dilute the chemical but your talking a much different technique than what Spotter is trying to achieve. If I understand your expectation Steve you want to drop phosphates from time to time using filter sock? Or are you looking to achieve what Sheldon is doing by constantly feeding the LaCl and feeding to a skimmer? To my knowledge Sheldon is only one testing this technique out thus far so dosing would be different.

Correct you are Dustin - I heard dosing pump; 1.1ml per minute; and thought 'constant-run setup'. If the objective is periodic treatment, then for sure the dosage would be different.

I should add that I'm not the only one tampering with this approach as my inspiration came from Mike Cao's Tank of the Month Article in August 2011. This is where I was first introduced to the concept of settling out lanthanum Phosphate (as opposed to straining it out via filter socks). The only thing I've done differently was use larger canisters; and tried a couple post-canister options/experiments. There were also a couple diy setups posted by H2OENG and thebanker on pg 18 which I think are similar in concept to what I was experimenting with.

Correct Dustin....I just want to do it with the filter sock method on an as needed basis.

I agree with Dustin in that case; and one of the many using that method should comment on your original question on feed rate.

Regards,

Sheldon

 

[Dustin1300]

Appreciate the link Sheldon. I hope to have my 600 gallon DT in place soon and I'd like to plan to have a reactor/reservoir of some sort which feeds to the skimmer input and was inspired by yours I'm continually trying to think of different ways to inject it but will have to see what works best. In the systems you maintain, do they also use GFO or are you using LaCl as the sole phosphate export?

 

[Scej12]

No Problem Dustin.

Because I'm a heavy-handed feeder; I can blow through about $100 per month or two using gfo. For that reason alone I'm a LC guy exclusively where possible. I know there was talk about LC being most effective at higher PO4 levels and GFO taking over the low end, but I've been able to get away with using LC alone. SeaKlear's my new best friend... (especially since I practically have a lifetime supply in my basement .

Regards,

Sheldon

 

[tmz]

Sheldon ,

I am not a chemist but a longtime student of reef chemistry and a reef keeper.

The method you are trying and sharing is interesting. Removing precipitant is a good thing too because it can clog the respiratory apparatuses of fish and filter feeders.

However,the conclusion and extrapolation that precipitated lanthanum phosphate contributes to PO4 in the water is erroneous and just not possible at reef tank ph.

Lanthanum phospahte is a highly insoluble solid, much more so than calcium carbonate( aragonite) for example . So your rock ,sand and corals would dissolve long before the precipitant lanthanum phosphate in acidic water and the dissolving calcium carbonate would add carbonate alkalinity carbonate boosting the ph back up.

A possible explanation for your observation is that when you use that hanah checker ,the powder you put in the vial is acid and the low ph in the vial could dissolve some precipitant polluting the sample water leading you to think PO4,free inorganic phosphate in the tank water is high when it only may be so in the testing vial. Once you clean out the precipitant the odds are your not picking up the precipitant or at lest not as much in the sample used for retest , thus a lower reading. Other testing errors or noise could be in play too.

Knowing the properties of the elements we are using is an important part of developing the right techniques to use them and they need to be accounted for before claims of a proven technique or interaction are made or accepted.
Lanthanum phosphate will not dissolve at reef tank ph. This precipitant is a solid as such it will not add PO4 to the water. The hypothesis that when lanthanum phosphate solids are in the water PO4 is raised not sustainable because of that simple fact.

Here is the process in a nutshell:
Lanthanum chloride which is very soluble disassociates when it goes into the water. The chloride joins all the other free chloride in the tank water . The lanthanum cruises around and binds to free inorganic phosphate,PO4, hanging out in the water, forming a solid,lanthanum phosphate. Thus the free inorganic phosphate (PO4) is sunk in a solid lanthanum phosphate crystal and stays there. It no longer plays in the water or does anything else inorganic phosphate does. If lanthanum runs out of phosphate to bind to it will grab some carbonate.
Saturation refers to how much of certain elements can be held in solution,ie ,in the water , like: calcium and carbonate; or phosphate and lanthanum; or phosphate and carbonate.
When their saturation levels are exceeded they fall out of the water as solids as they bind to other elements. When this binding occurs they become solids, like sand. You can't over saturate with solids. Solids are a consequence of over saturation.

These solids redissolve at variable ph levels depending on the nature and strength of the bond which varies depending on the elements involved.
Calcium carbonate for example begins to dissolve at about 7.7,which is why letting ph in a reef tank go below that is harmful as coral skeletons,coraline, and other calcareous organisms and aragonite(live rock and coral sand) begin to dissolve at 7.7 ph.
Lanthanum when it binds to phosphate becomes the soid lanthanum phosphate which won't just unbind because there is more of lanthanum phosphate precipitant ;just like coral sand(calcium carbonate) won't dissolve just because there is more of it.
For lanthanum phosaphte to raise PO4 in the water the ph needs to be low enough to break lanthanum phosphate into PO4 and lanthanum and that's very low given the insolubility of lanthanum phosaphte relative to a reef tank; low enough to make it through the human digestive tract which is at least as low as 6.8( probably lower). which if reached in a reef tank would likely kill everything in it.

 

[tmz]

Someone can correct me if I'm wrong but believe Gary/Tom both do the sock method. I have been using about 3 mL of LaCl, drip in at about 1 drop a second via IV line and now am dripping it into my overflow pipe which dumps into a 10 micron sock. I let it run overnight or during the day and change out once the filter sock is overflowing. I try not to feed during this period due to the sock quickly clogging! Gary/Tom can correct me if I'm wrong

That sounds like a better method than I used and use.

To start , I have not needed lanthanum chloride on the main system for about 3yrs. I rely on vodka and vinegar dosing.
When I used lanthanum chloride on the main system I dribbled small amounts at a time into a drain from a frag tank that runs into the bottom of brute garbage can full of live rock and out the top. From there ,the water goes over another 3 foot course of sand and live rock before hitting the sump near the skimmer intake. Most times I used filter floss along the way but not always. Any way I think a good deal of precipitant lanthanum phosphate settled in the cryptic refugium, ie brute can, and elsewhere along the roughly 12 foot run before it hit the sump. Never had cloudy water in the tanks. Never worried much about the precipitant away from livestock.

I still use lanthanum chloride in curing bins for rock leaching PO4 and then I just dose it directly and swish off the rock before adding it to the system.

I also use it in for an off system 65 gallon tank with leathers and such that runs with a canister filter. I dose about 1.5 ml of seaklear mixed in a liter of ro water . I just dribble it in to a high flow area in small increments over a couple of days every two weeks or so.PO4 stays under .08ppm in this tank .There is no effect I can discern from any accumulated setlled precipitant.

I think the socks and drip are a fine method. I just never used them and don't have a way to do that neatly for the off system tank.

 

[Scej12]

Sheldon ,

I am not a chemist but a longtime student of reef chemistry and a reef keeper.

The method you are trying and sharing is interesting. Removing precipitant is a good thing too because it can clog the respiratory apparatuses of fish and filter feeders.

However,the conclusion and extrapolation that precipitated lanthanum phosphate contributes to PO4 in the water is erroneous and just not possible at reef tank ph.

Lanthanum phospahte is a highly insoluble solid, much more so than calcium carbonate( aragonite) for example . So your rock ,sand and corals would dissolve long before the precipitant lanthanum phosphate in acidic water and the dissolving calcium carbonate would add carbonate alkalinity carbonate boosting the ph back up.

A possible explanation for your observation is that when you use that hanah checker ,the powder you put in the vial is acid and the low ph in the vial could dissolve some precipitant polluting the sample water leading you to think PO4,free inorganic phosphate in the tank water is high when it only may be so in the testing vial. Once you clean out the precipitant the odds are your not picking up the precipitant or at lest not as much in the sample used for retest , thus a lower reading. Other testing errors or noise could be in play too.

Knowing the properties of the elements we are using is an important part of developing the right techniques to use them and they need to be accounted for before claims of a proven technique or interaction are made or accepted.
Lanthanum phosphate will not dissolve at reef tank ph. This precipitant is a solid as such it will not add PO4 to the water. The hypothesis that when lanthanum phosphate solids are in the water PO4 is raised not sustainable because of that simple fact.

Here is the process in a nutshell:
Lanthanum chloride which is very soluble disassociates when it goes into the water. The chloride joins all the other free chloride in the tank water . The lanthanum cruises around and binds to free inorganic phosphate,PO4, hanging out in the water, forming a solid,lanthanum phosphate. Thus the free inorganic phosphate (PO4) is sunk in a solid lanthanum phosphate crystal and stays there. It no longer plays in the water or does anything else inorganic phosphate does. If lanthanum runs out of phosphate to bind to it will grab some carbonate.
Saturation refers to how much of certain elements can be held in solution,ie ,in the water , like: calcium and carbonate; or phosphate and lanthanum; or phosphate and carbonate.
When their saturation levels are exceeded they fall out of the water as solids as they bind to other elements. When this binding occurs they become solids, like sand. You can't over saturate with solids. Solids are a consequence of over saturation.

These solids redissolve at variable ph levels depending on the nature and strength of the bond which varies depending on the elements involved.
Calcium carbonate for example begins to dissolve at about 7.7,which is why letting ph in a reef tank go below that is harmful as coral skeletons,coraline, and other calcareous organisms and aragonite(live rock and coral sand) begin to dissolve at 7.7 ph.
Lanthanum when it binds to phosphate becomes the soid lanthanum phosphate which won't just unbind because there is more of lanthanum phosphate precipitant ;just like coral sand(calcium carbonate) won't dissolve just because there is more of it.
For lanthanum phosaphte to raise PO4 in the water the ph needs to be low enough to break lanthanum phosphate into PO4 and lanthanum and that's very low given the insolubility of lanthanum phosaphte relative to a reef tank; low enough to make it through the human digestive tract which is at least as low as 6.8( probably lower). which if reached in a reef tank would likely kill everything in it.

Hi Tom,

I can't argue any of what you state. I have to run out now but will spend a little time detailing how my samples were taken; and perhaps in the future see if I can be certain that precipitants aren't polluting the test samples (which I really don't think is the case to be honest based how the samples have been taken). Will follow up some more later.

Regards,

Sheldon

 

[Elliott]

Sheldon ,

I am not a chemist but a longtime student of reef chemistry and a reef keeper.

The method you are trying and sharing is interesting. Removing precipitant is a good thing too because it can clog the respiratory apparatuses of fish and filter feeders.

However,the conclusion and extrapolation that precipitated lanthanum phosphate contributes to PO4 in the water is erroneous and just not possible at reef tank ph.

Lanthanum phospahte is a highly insoluble solid, much more so than calcium carbonate( aragonite) for example . So your rock ,sand and corals would dissolve long before the precipitant lanthanum phosphate in acidic water and the dissolving calcium carbonate would add carbonate alkalinity carbonate boosting the ph back up.

A possible explanation for your observation is that when you use that hanah checker ,the powder you put in the vial is acid and the low ph in the vial could dissolve some precipitant polluting the sample water leading you to think PO4,free inorganic phosphate in the tank water is high when it only may be so in the testing vial. Once you clean out the precipitant the odds are your not picking up the precipitant or at lest not as much in the sample used for retest , thus a lower reading. Other testing errors or noise could be in play too.

Knowing the properties of the elements we are using is an important part of developing the right techniques to use them and they need to be accounted for before claims of a proven technique or interaction are made or accepted.
Lanthanum phosphate will not dissolve at reef tank ph. This precipitant is a solid as such it will not add PO4 to the water. The hypothesis that when lanthanum phosphate solids are in the water PO4 is raised not sustainable because of that simple fact.

Here is the process in a nutshell:
Lanthanum chloride which is very soluble disassociates when it goes into the water. The chloride joins all the other free chloride in the tank water . The lanthanum cruises around and binds to free inorganic phosphate,PO4, hanging out in the water, forming a solid,lanthanum phosphate. Thus the free inorganic phosphate (PO4) is sunk in a solid lanthanum phosphate crystal and stays there. It no longer plays in the water or does anything else inorganic phosphate does. If lanthanum runs out of phosphate to bind to it will grab some carbonate.
Saturation refers to how much of certain elements can be held in solution,ie ,in the water , like: calcium and carbonate; or phosphate and lanthanum; or phosphate and carbonate.
When their saturation levels are exceeded they fall out of the water as solids as they bind to other elements. When this binding occurs they become solids, like sand. You can't over saturate with solids. Solids are a consequence of over saturation.

These solids redissolve at variable ph levels depending on the nature and strength of the bond which varies depending on the elements involved.
Calcium carbonate for example begins to dissolve at about 7.7,which is why letting ph in a reef tank go below that is harmful as coral skeletons,coraline, and other calcareous organisms and aragonite(live rock and coral sand) begin to dissolve at 7.7 ph.
Lanthanum when it binds to phosphate becomes the soid lanthanum phosphate which won't just unbind because there is more of lanthanum phosphate precipitant ;just like coral sand(calcium carbonate) won't dissolve just because there is more of it.
For lanthanum phosaphte to raise PO4 in the water the ph needs to be low enough to break lanthanum phosphate into PO4 and lanthanum and that's very low given the insolubility of lanthanum phosaphte relative to a reef tank; low enough to make it through the human digestive tract which is at least as low as 6.8( probably lower). which if reached in a reef tank would likely kill everything in it.

very good explanation Tom

I ran LC into a pool DE filter that traps debris down to 2 microns, that was off line when not in use and backwashed with tank water before each weekly run. I found that if I didn't backwash it before each use it did not lower P04 much if any, even while dosing LC into it. I tested P04 with a Hanna meter from the DT water column.

Maybe your explanation of dissolved precipitate in the test vial is possible however the precipitates would need to get through a DE filter and sump, then DT and into a very small sample test tube, which would mean there would have to be widespread precipitates in the water column.

 

[Scej12]

Sorry dble post..

 

[Scej12]

Hi Elliott & Tom - that last paragraph represents my immediate hesitation re the polluted vile possibility; however I do realize that it's just a single possibility of probably several others.

I didn't have much time yesterday to get online, but I did pop into my subject system early in the morning. I found that the PO4 started to creep back up it was at 0.11 again. My next move is to clean out the canisters (which I neglected to do on Wednesday night); and clean out the skimmer head(s). I suspect the measurement will drop again, but will be sure to report back after the various phases of maintenance.

Alternatively, I was also hoping for an opportunity to test Tom's vile theory, so I might just do nothing for a period, see how far the levels rise up over a week or so, while I try to find a 10 micron filter sock kicking around (or something equivalent) so that I can collect a mechanically filtered vile sample.

The other thing I should note is that I noticed [yesterday morning] a fair amount of particulate floating/in suspended animation as the lights came on in the display tank (and immediately thought maybe Tom's onto something:fun5. I don't often look that closely, but this could be a result of the scooter goby and mandarin goby kicking up detritus as they scour the liverock and sand for crustaceans.... or perhaps as Tom suggested it could be precipitates floating around. Now any reef tank with decent flow has a fair bit of detritus in suspension, but I'll have to pay closer attention to see if there are any notable differences between times of higher PO4 test results and Lower test results.

If there are any other angles y'all can think of that I should be experimenting with, please feel free to let me know and I'll be happy to attempt a scenario to validate it.

I think I'll let the reactor system run without cleaning out the particulates for a while; and try to test Tom's theory next. I might have an extra RO/DI prefilter canister kicking around that I can stick a 10 micron cartridge into for collecting test samples.

Oh and finally (almost forgot), the other change I made between the 0.04ppm reading of Wednesday night; and 0.11ppm reading of Friday morning was put the Calcium reactor back on line after topping up the media, and rinsing the the existing media (remember it was collecting precipitates for several weeks prior); and the single feed pump serves both the PO4 reactor system and the CaCO3 reactor independently (i.e. not in series this time); sooo - one of the consequences of this latest change is that the flow through the PO4 reactor system has been cut down by at least 50 - 70%. Quite possibly the PO4 could be leaching out or the liverock at a faster rate than the PO4 reactor can process it; or perhaps (just perhaps.. in light of all the argument against) if my original theory had a modicum of truth to it there is also the possibility (fully appreciative of Tom's objections) that weakly bonded PO4 precipitates stored up in that old CaCO3 media could in some way be contributing to the rise of total system PO4 among other factors... even though the CaCO3 reactor is no longer inline with the PO4 reactor system!

I'm aware of the objections, but just laying all of the thoughts on the table to be rolled into some kind/kinds of experiment(s) to see if they can be put to rest, no matter what side of reality they reside on...

Will let you know how it all goes in about a week or so.

Regards,

Sheldon

 

[tmz]

I am not suggesting one should leave the precipitants in the tank, or filters which they can clog. ; just that lanthanum chloride won't redissolve at reef tank ph. A simpler test for that might be to precipitate some in a gallon of tank water and test PO4 after everything is settled ;then test it again several hours later. Running the sample through a small micron filter in both cases to eliminate precipitant particles.

 

[Scej12]

Thanks Tom - Yes I do understand your position as stated. You also raise a good test idea. I'll see if I can set something up accordingly when I have the opportunity; or if anyone else can get to it first, or even in tandem so that we can collect multiple independent results that would also be of value.

I'll be at my site tomorrow morning and will therefore be able to take another test snapshot to see where the PO4 has gone to now (another couple days without cleaning out the effective elements).. will let y'all know how it measures up.

Regards,

Sheldon

 

[SPotter]

I started my LC treatment today with a 3ml LC to 2L of rodi water. I started dripping at a rate of 1.1ml per minute at 10 am today. Last night my po4 was .0767 and I just tested after dripping for 10 hrs. I am excited to report that my po4 is down to .0399. I am not seeing any problems with the filter sock clogging or any precipitate in the tank. I was concerned that the drip rate would be too slow and not have an impact on it but thats not the case. I will continue to drip and test again tomorrow evening.

 

[Greg 45]

It does work steve just go slow

 

[tmz]

Good report Steve. It can drop it quickly ;be careful not to move it down too fast.I run my system at PO4 .03 fwiw. Ran it for a long time at .05ppm. Most recommend ,>.03 to limit nuisance algae. Precipitous drops can be hard on corals though.

 

[SPotter]

Good report Steve. It can drop it quickly ;be careful not to move it down too fast.I run my system at PO4 .03 fwiw. Ran it for a long time at .05ppm. Most recommend ,>.03 to limit nuisance algae. Precipitous drops can be hard on corals though.

Thanks for the feed back tom. I just tested it this morning and its down .0307 now with about 1/3 of a liter left to dose. I think I will shut the pump off for now and do another treatment in a few days.

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