Another Triton ICP "High Tin" Case

[Dr. Jim]

August 13 UPDATE....(New Info Resumes here)....

From GROUP B it appears that there are 2 unrelated sources of the tin (B-3 and B-4).
Next, I set up Group "C" (C-1 and C-2 will narrow down B-3; and, C-3 and C-4 will narrow down B-4; all items soaked for at least 4 days.)

C-1 Skimmer (minus the pump; a similar DC pump was previously ruled out) (soaked in 10 gal glass tank with newly mixed TMPro salt).....Sn=7.14 (slightly elev)
C-2 Plumbing from Red Sea Reefer (Sched 80 pipes and green plastic hose)...Sn=56.87

C-3 Kalkwasser (newly mixed kalk in RO/DI)....Sn=11.81
C-4 Kalk reactor. (Reactor was flushed with garden hose, towel dried, rinsed with RO/DI, dried; then filled with RO/DI and allowed to sit for 5 days. .....Sn=11.79

DISCUSSION

It is certainly frustrating and disappointing that tin was found in all 4 samples when I was expecting, and hoping, that only 1 item from each group would be elevated. The highest level (56.87) was the Red Sea "Plumbing." However, because previous levels of the two combined were 201 and 199, I expected higher levels. But still, 56.87 is very high compared to all values I've gotten over 19 ICP tests. The slightly elevated level from the skimmer could have been tin that it had adsorbed then released.

The Kalk and Kalk Reactor showed very similar results (11.81 and 11.79). This might make one wonder if the RO/DI is contaminated, but the RO/DI has been shown numerous times, directly and indirectly to be Nn. (Indirectly, because ALL samples were either soaked in RO/DI or in new saltwater made with the same RO/DI and several of these results showed Nn.) Another disturbing finding is that previous tests with the two combined showed levels of 125 and 150. Perhaps this can be explained by the fact that those elevated samples were from water that had been sitting for many weeks (in the reactor); whereas, the newly tested samples were only sitting for 4-5 days.

Today, I call Red Sea and ordered new piping for the tank. This may not turn out to be fruitful, but if I follow the ICP results....and that's all I have to go on....at this point, the "Red Sea Plumbing" seems to be the most likely candidate. Once I get these parts, I will soak and test them before changing them on my system.

Regarding the Kalk and Kalk reactor, I discontinued use of them long ago, after the first "elevated" tin result. I will work on them later. For now, I just want to get the tin out of my tank so will concentrate on the Red Sea Plumbing theory.

Today, I sent out two more samples, one of my MT (which I haven't checked in a while) and another repeat test of my RO/DI water.

Be thankful if you never have a tin issue!!

 

[esther]

UPDATE ON MY TIN PROBLEM:

-The suspicious plastic pump guard mentioned in my last post turned out to NOT be the problem.

-Most of this post was copied and pasted from another thread (where someone asked me a question) so if you've seen it, skip to the next post titled "Aug 13 update"

Warning: This is lengthy, so if you aren't interested in "TIN" you may want to skip it!

AUGUST 6, 2020 POST (from another thread):

In Summary
5/11/20--Triton ICP: Sn = 18 (set pt is 0.1) I then performed 4 water changes over the next 5 days: 25%, 30%, 30%, 30% which should have brought the level to about 4.8.
I then used TLF Metasorb for 5 days (placed in sump mesh sock so had good water flow on/thru it). I then performed another 20% water change, so even if the Metasorb did nothing, the level should have been around 3.9.
On 6/1, I sent water to Triton and ATI. Triton showed 22 and ATI showed 45.84 (set point is 0.47 for ATI) (when I was expecting < 3.9).
Next......After 8 days of a combination of Polyfilters, Seachem Cuprisorb, MetaSorb, carbon and Power Cleanse (3 days)…..and enough water changes to lower the tin from 22 (Triton) to about 8.5 (even if other products didn’t work)….the ICP showed the tin at 18 (Triton) on 6/22. (This doesn't necessarily mean these products didn't work, the leaching may have been occurring faster than it could be removed).

RO/DI, RODI holding tank, and salt mixing tank were all confirmed, more than once, to be free of tin.

----------------------------------

MISC COMMENTS:
1) I seriously doubt that there is metal causing the problem, being that no other metal was elevated on the ICP tests, everything was brand new 7 months ago, and since I "broke down" the system, it was easy to look for metal. Also, the results tend to suggest otherwise.
2) I know a lot of people say "don't worry about tin" and/or "take ICP results with a grain of salt". I agree that one should not jump to conclusions from just one elevated element from a single test. But with all the "positive" values I have gotten, it has to be significant. And, yes, I do believe that my SPS are being affected.
3) I think glass as a source can be ruled out given the results above. (The slight level of Sn in A-5 could be from leftover water I didn't get out when I cleaned the tank, or possibly from Sn that was adsorbed and released by the plastic overflow box. In any case the relative low value of 7.6 compared to the 150-200 values makes me put the "glass idea" on the back-burner for now.)
4) I'm fairly convinced that rock can adsorb AND release tin. This would make sense and may explain A-1 and A-2. (We know rock can do that with phosphates and copper, so why not with tin?)
5) -From a lengthy discussion regarding metal-binding products with Jack Kent (CEO of Continuum and owner of Brightwell) I learned:
-Nobody to his knowledge has studied the ability of any of these products to remove tin, but he felt there is a very good chance that they should. (You will notice that none of these products lists tin as a metal it will remove).
-There is a "pecking order" as to which metal/element is removed first, second, etc but nobody knows what this order is.
-His product, Power Cleanse, is similar, if not the same, as Cuprisorb. (It looks identical to me). It consists of 2 resins that bind metals without affecting pH. I would recommend his product over the Cuprisorb: you get a whole lot more of it and he recommends using a much larger volume than what you get with Cuprisorb. He feels that, if it is going to work, it should "work" in just 24 hours. (Remember that any of these problems will throw off most of the trace elements so it might be prudent to perform huge water changes after finsishing with any of these products).
- He has no idea what is in MetaSorb. (I opened it and found a white powder which can also be a resin (according to Randy Holmes-Farley). Polyfilter is a resin-like material sprayed on the "sponge".

-----------------------------------

Now it was time to disassemble my tank and I started testing "components" individually or in groups, in separate tanks. (ATI was used for all tests to follow since they run 2 samples per kit). These "trials" included:

-GROUP "A" (first set of "trials"; "soaked" for 5 days before sampling):
Aug 7, 2020

A-1. Live Rock Tank. 25 lbs of live rock and all livestock (fish), including 30+ SPS frags were moved to a 29 gal tank for the duration of "trials". Sn = 13.73
A-2. Artificial Rock. 40 lbs soaked in new saltwater; aerated). Sn=30.55
A-3. Hang-on Algae filter. Run on 10 gal tank. Sn=N.n.
A-4. Sump (of Red Sea Reefer 170; also contained GHL probes, magnets and ATO apparatus) after thorough cleaning with RO/DI and filled with new saltwater. Sn= N.n.
A-5. Main tank (after similar cleaning as sump) Sn=7.61
A-6. Misc Tank "A": In a plastic storage container, I ran the protein skimmer and soaked the main pump, Echotech pumps, pvc pipes and misc pvc items, magnets, etc. Sn=201.3
A-7. Kalk water (from reactor) and ATO water run thru GHL doser (50:50 mix): Sn=125.1
A-8 New Saltwater (80% TM + 20% IO); Sn=25.53

The A-8 value is very disturbing because this is the water that was used in all the tests above (except A-7) so how can Sn in A-3 and A-4 be "undetectable"? I'm forced to temporarily ignore this value and look at the extremely elevated values in A-6 and A-7.

Next batch of tests, GROUP "B" (to further explore A-6 and A-7):
B-1-New salt mix (used in these Group B trials; TM only)...... Sn=N.n
B-2 Main pump (I took the pump from A-6 above so I could see if I can use it when I start up main system again):..... Sn=N.n
B-3 Misc Tank "B"- I took only the skimmer (minus its pump) and Red Sea pipes/tube from Group A and tested them alone, this time in the 10 gal glass tank from A-3 (shown to be N.n.). I was concerned that the high Sn in A-6 may have come from the plastic tub, (but apparently this was not the case)...... Sn=199.0
B-4 Kalk water (this time I eliminated the ATO water and all tubing from A-7 and just sampled water directly out of the Kalk reactor...... Sn=150.3

Super thorough. Great info, but man you must be frustrated. lol

 

[Dr. Jim]

Super thorough. Great info, but man you must be frustrated. lol

LOL !!! That's an understatement!! ....my wife wonders why she never sees me anymore!

 

[esther]

LOL !!! That's an understatement!! ....my wife wonders why she never sees me anymore!

I just got my ICP back from Triton and it came back at 5.6. It’s come down from 15, but I can’t seem to get rid of it. I’ve done a 30% water change weekly for the last 5 months.

 

[Dr. Jim]

I just got my ICP back from Triton and it came back at 5.6. It’s come down from 15, but I can’t seem to get rid of it. I’ve done a 30% water change weekly for the last 5 months.

If you only had two tests, 15 and 5.6, I don't think you need to panic over it, (yet).
If it was me, I'd send a sample to ATI (along with an RO/DI sample; you probably know they run 2 tests per kit). I'd be happy if I got a reading of 5.6.....but granted, I would still want to see it get to zero. But as long as corals aren't hurting, I'd wait it out a bit.

 

[esther]

If you only had two tests, 15 and 5.6, I don't think you need to panic over it, (yet).
If it was me, I'd send a sample to ATI (along with an RO/DI sample; you probably know they run 2 tests per kit). I'd be happy if I got a reading of 5.6.....but granted, I would still want to see it get to zero. But as long as corals aren't hurting, I'd wait it out a bit.

Ive done about 5 tests over the last 6 months. It kind of jumps around. Everything else is good though.

 

[Dr. Jim]

CONCLUSION TO MY TIN PROBLEM --- Finally!!

In short, the problem was traced to the green tubing that came with the Red Sea Reefer 170. A recent ICP test (ATI) showed a tin level of 1438. The green tubing was soaked, and aerated, in 1.5 gal of RO/DI water in a bucket for about 11 days. This number should be extrapolated for my 60 gal tank which holds 40 gal of water. So, we might conclude that if this green tube was in use on my tank for 11 days, the tin level would rise by 53.9 (calculated by: 1438 div by 40/1.5). Actually, it would probably be higher if the tube was in use because of the abundant flow of water through it. In the testing bucket, I only had an air tube inserted inside the green tube to agitate the water.

Going back a few steps, a previous test of the Red Sea sched. 80 pipes plus the green tubing plus my Octopus skimmer soaked together in a tank with 10 gal of saltwater came back at 199. Not knowing if it was the Octo skimmer or the Red Sea plumbing, I bought a new Red Sea Skimmer and soon came to discover that it, too, was leaching tin. (ICP = 43.84 after short soak of the RS Skimmer for 3 days in 4 gal RO/DI which extrapolates to 4.38 for a 40gal tank volume). At the same time, I bought a new green tube and sched. 80 plumbing from Red Sea. I soaked all these parts for about 5 days in 8 gal RO/DI and the ICP came back at 764.5 (which extrapolates to 152.9 for a 40 gal tank volume). I did not test them individually.

The Octopus skimmer tested 7.14, (soaked in 4 gal so negligible after extrapolating to 40 gal value: 0.71

The original Red Sea sched 80 pipes came back at 18.46 (soaked in 8 gal, so extrapolated to my 40 gal: 3.69.

I wrote a long letter to Red Sea today describing all I've been through and to request return of the recent plumbing and skimmer purchase. I also requested that they consider reimbursing me for the nearly $3000 this ordeal has cost me (dead corals; ICP tests; Misc). I'm hoping they will do the "right thing".

After investigating plastic tubing, I ordered some TYGON tubing which is supposed to be very inert and will be used to replace the original green tubing.

Hope somebody may find this helpful.

 

[Cory]

CONCLUSION TO MY TIN PROBLEM --- Finally!!

In short, the problem was traced to the green tubing that came with the Red Sea Reefer 170. A recent ICP test (ATI) showed a tin level of 1438. The green tubing was soaked, and aerated, in 1.5 gal of RO/DI water in a bucket for about 11 days. This number should be extrapolated for my 60 gal tank which holds 40 gal of water. So, we might conclude that if this green tube was in use on my tank for 11 days, the tin level would rise by 53.9 (calculated by: 1438 div by 40/1.5). Actually, it would probably be higher if the tube was in use because of the abundant flow of water through it. In the testing bucket, I only had an air tube inserted inside the green tube to agitate the water.

Going back a few steps, a previous test of the Red Sea sched. 80 pipes plus the green tubing plus my Octopus skimmer soaked together in a tank with 10 gal of saltwater came back at 199. Not knowing if it was the Octo skimmer or the Red Sea plumbing, I bought a new Red Sea Skimmer and soon came to discover that it, too, was leaching tin. (ICP = 43.84 after short soak of the RS Skimmer for 3 days in 4 gal RO/DI which extrapolates to 4.38 for a 40gal tank volume). At the same time, I bought a new green tube and sched. 80 plumbing from Red Sea. I soaked all these parts for about 5 days in 8 gal RO/DI and the ICP came back at 764.5 (which extrapolates to 152.9 for a 40 gal tank volume). I did not test them individually.

The Octopus skimmer tested 7.14, (soaked in 4 gal so negligible after extrapolating to 40 gal value: 0.71

The original Red Sea sched 80 pipes came back at 18.46 (soaked in 8 gal, so extrapolated to my 40 gal: 3.69.

I wrote a long letter to Red Sea today describing all I've been through and to request return of the recent plumbing and skimmer purchase. I also requested that they consider reimbursing me for the nearly $3000 this ordeal has cost me (dead corals; ICP tests; Misc). I'm hoping they will do the "right thing".

After investigating plastic tubing, I ordered some TYGON tubing which is supposed to be very inert and will be used to replace the original green tubing.

Hope somebody may find this helpful.

Thats some excellent investigative work there! Got a pic of the offending tubing?

 

[esther]

CONCLUSION TO MY TIN PROBLEM --- Finally!!

In short, the problem was traced to the green tubing that came with the Red Sea Reefer 170. A recent ICP test (ATI) showed a tin level of 1438. The green tubing was soaked, and aerated, in 1.5 gal of RO/DI water in a bucket for about 11 days. This number should be extrapolated for my 60 gal tank which holds 40 gal of water. So, we might conclude that if this green tube was in use on my tank for 11 days, the tin level would rise by 53.9 (calculated by: 1438 div by 40/1.5). Actually, it would probably be higher if the tube was in use because of the abundant flow of water through it. In the testing bucket, I only had an air tube inserted inside the green tube to agitate the water.

Going back a few steps, a previous test of the Red Sea sched. 80 pipes plus the green tubing plus my Octopus skimmer soaked together in a tank with 10 gal of saltwater came back at 199. Not knowing if it was the Octo skimmer or the Red Sea plumbing, I bought a new Red Sea Skimmer and soon came to discover that it, too, was leaching tin. (ICP = 43.84 after short soak of the RS Skimmer for 3 days in 4 gal RO/DI which extrapolates to 4.38 for a 40gal tank volume). At the same time, I bought a new green tube and sched. 80 plumbing from Red Sea. I soaked all these parts for about 5 days in 8 gal RO/DI and the ICP came back at 764.5 (which extrapolates to 152.9 for a 40 gal tank volume). I did not test them individually.

The Octopus skimmer tested 7.14, (soaked in 4 gal so negligible after extrapolating to 40 gal value: 0.71

The original Red Sea sched 80 pipes came back at 18.46 (soaked in 8 gal, so extrapolated to my 40 gal: 3.69.

I wrote a long letter to Red Sea today describing all I've been through and to request return of the recent plumbing and skimmer purchase. I also requested that they consider reimbursing me for the nearly $3000 this ordeal has cost me (dead corals; ICP tests; Misc). I'm hoping they will do the "right thing".

After investigating plastic tubing, I ordered some TYGON tubing which is supposed to be very inert and will be used to replace the original green tubing.

Hope somebody may find this helpful.

This is insane! So glad you finally figured it out. It's crazy to me than tin can be leached from tubing. I would have never guessed that. Hoping that Red Sea does the right thing.

 

[Dr. Jim]

Thats some excellent investigative work there! Got a pic of the offending tubing?

Nothing fancy....just a green tube from return pump to bottom of overflow within the cabinet.

 

[lkc]

THAT is Eheim tubing.......

 

[Dr. Jim]

THAT is Eheim tubing.......

It is green like Eheim tubing, but how can we be sure it is the same?
The replacement green tubing that Red Sea sent to me is different from the orginal green tubing. The wall thickness is thinner on the new one.
I'd guess that more than one company makes green tubing. And I would guess Eheim and Red Sea don't actually make the tubing but buy it from somebody else....and that "somebody else" may not even be the same source.

 

[Randy Holmes-Farley]

It is green like Eheim tubing, but how can we be sure it is the same?
The replacement green tubing that Red Sea sent to me is different from the orginal green tubing. The wall thickness is thinner on the new one.
I'd guess that more than one company makes green tubing. And I would guess Eheim and Red Sea don't actually make the tubing but buy it from somebody else....and that "somebody else" may not even be the same source.

Google green flexible tubing under images. Hundreds of types.

 

[Randy Holmes-Farley]

This is insane! So glad you finally figured it out. It's crazy to me than tin can be leached from tubing. I would have never guessed that. Hoping that Red Sea does the right thing.

https://pharosproject.net/files/case-studies/Example-Final-Report-Tin-Stabilizers-in-Drinking-Water.pdf

" Though there are other forms of PVC stabilizers, tin stabilizers are the most widely used stabilizers in North America. PVC stabilizers are used due to their ability to absorb HCl and prevent degradation of PVC. The leaching of organotins into drinking water is a concern due to the health impacts that they potentially pose for humans. "

 

[ReefLab]

https://pharosproject.net/files/case-studies/Example-Final-Report-Tin-Stabilizers-in-Drinking-Water.pdf

" Though there are other forms of PVC stabilizers, tin stabilizers are the most widely used stabilizers in North America. PVC stabilizers are used due to their ability to absorb HCl and prevent degradation of PVC. The leaching of organotins into drinking water is a concern due to the health impacts that they potentially pose for humans. "

There are so many thousands of tanks using PVC it seems almost an impossibility that PVC could have a negative effect on our tanks..
Is there maybe a company that coats their PVC or does some proprietary process that would mean some of us have different kinds of PVC?

 

[Randy Holmes-Farley]

There are so many thousands of tanks using PVC it seems almost an impossibility that PVC could have a negative effect on our tanks..
Is there maybe a company that coats their PVC or does some proprietary process that would mean some of us have different kinds of PVC?

So many tanks have elevated tin...

 

[Topreefer92]

I am having the same problem currently, whenever there are elevated tin levels from my icp my corals are going south. Never experienced this in other tanks. I am systematically replacing things to try and get rid of the problem. Metasorb is not a permanent option to get rid of all toxic metal levels. This thread has helped immensely. Thank you!!

 

[ReefLab]

So many tanks have elevated tin...

IIRC there are a few ICP threads that were concerned about tin levels as high as 15ug/l but had healthy coral. at what level would it be considered significant?

If PVC were an issue, there would be so few successful tanks

 

[ReefLab]

So many tanks have elevated tin...

https://onlinelibrary.wiley.com/doi/abs/10.1002/aoc.590050210

"Results showed that inorganic tin, MBT and DBT compound were released from the material tested under experimental static leaching conditions. The total amount of inorganic tin and organotin compounds observed upon leaching varied considerably from one PVC material to another."

 

[spsick]

I struggled with Tin a lot in the early life of my new tank and went crazy but it eventually subsided. I think this is only seen on smaller systems where the dilution is much lower. Hard lesson learned for new systems:
RUN ALL EQUIPMENT AND NEW SYSTEMS IN HEATED RODI WATER FOR A WEEK+ AND TOTALLY DRAIN BEFORE SETUP.

I think this is the only way to be sure.