Another Triton ICP "High Tin" Case

[ScottB]

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.

Hmm. I've never had troubles before, but that is certainly a minor inconvenience relative to the OPs situation.

 

[Christoph]

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.

Dr Jim,

excellent work, thanks for conducting and financing this study on your own to find out the source of tin in your reef tank. Your corals will thank you, any many other reefers will benefit from your work that are searching for mysterious tin sources.

If youll ever find yourself in such a "hunt" again: Let me know, we will analyze those samples free of charge due to the huge benefit for the hobby of such experiments.

Best regards,
Christoph

 

[Dr. Jim]

Dr Jim,

excellent work, thanks for conducting and financing this study on your own to find out the source of tin in your reef tank. Your corals will thank you, any many other reefers will benefit from your work that are searching for mysterious tin sources.

If youll ever find yourself in such a "hunt" again: Let me know, we will analyze those samples free of charge due to the huge benefit for the hobby of such experiments.

Best regards,
Christoph

Thank you, Dr. Denk, for your generous offer!

For those that do not know about Dr. Denk’s ICP Lab (OCEAMO) you can read about it here:

OCEAMO ICP TESTING COMING TO U.S. SOON !!

Recently, Dr. Christoph Denk, a chemist, research engineer, and founder of OCEAMO contacted me after reading about my “tin problem” on a R2R thread. He generously offered to run 10 ICP tests for me for free for which I am most grateful. (I posted new comments on my “tin thread” here...

www.reef2reef.com

I recently received 10 ICP test results from OCEAMO that Dr. Denk ran for free for me to help me further solve my tin problem. Controls were submitted for each of the samples where water that was used for the “soaks” was tested before the soak was initiated. Of interest are the following results:

• I repeated the “soak test” with the “green tube” but this time in 2 gal saltwater, without circulation, for 7 days. The ICP result was 111.6 which is only 7.7% of the original test value, but certainly still significant. I suspect the difference is due to the fact that saltwater was used this time….(RO/DI water is more “reactive” and IMO would be more likely to “draw out” the tin); and, no circulation through the tube was used this time.
• I tested a white PVC pipe (intended for Home Central Vacuum System) that I used temporarily as a drain to my sump when I found elevated tin from the Red Sea Sched. 80 drain pipe. 4 gal of RO/DI was used for 1 month and the Tin came back at 360.8. This appeared worse than the original Red Sea drain pipe so I put that one back on!
• Since Jack Kent (CEO of Continuum) sent me a free bottle of POWER CLEANSE, I decided to perform a “crude” experiment to see if this product can remove tin, thinking he would be interested. I placed 4 ml of Power Cleanse in 946 ml of the water from #1 above (i.e. the sample that the “green tube” was soaked in). This would extrapolate to twice the recommended dosage. I simply shook the bottle several times a day for 2 days, then took a sample. Although running water through a media bag would have been a better option, I would have expected some decrease in the tin from what I did. But unfortunately, the tin came back at 107.6; the original sample before adding the Power Cleanse was 111.6 so the decrease was probably not statistically significant. (Jack told me that if a product was to be successful removing tin, it should be apparent after just 24 hrs; I allowed 48 hours).

These tests will conclude my tin saga. My level is now down to 14 which suggests I am going in the right direction now that I eliminated the green tubing. (I am still awaiting a response from Red Sea).

The following are some of my “gut” feelings about my thoughts regarding tin, (after 45+ ICP tests), presented in two categories:

A. Comments for which I have a STRONG suspicion:
1. Most plastics (PVC pipes; tubing; skimmers; reactors) very likely leach tin, especially when new.
2. Tin problems are probably less common in large-volume tanks (> about 100 gal).
3. Rock adsorbs tin and can release it (which may lead to faulty conclusions when trouble-shooting a tin problem).
4. Different corals probably have varying degrees of susceptibility to elevated tin levels.
5. If tin is the only heavy metal elevated on the ICP test, then the tin is probably coming from plastic rather than a corroding piece of metal.

B. Comments for which I have suspicion but with less evidence:
1. For many corals, tin levels up to 20-30 may not be especially harmful although obviously not desirable. The tin level at which a coral suffers is probably related to other concurrent negative factors, (i.e. the more stable the system and the healthier the coral to begin with, the greater the level of tin it may be able to tolerate).
2. Popular media used for removing Cu and other heavy metals may not be very effective for tin. This seems to be the case for Power Cleanse, and if so, then probably also SeaChem’s Cuprisorb which is probably the same product (according to Jack Kent). (Note that none of the products being used for attempted tin removal are labeled for this use).
3. Release of tin from plastics probably gradually subsides but may take more than a year to reduce to negligible levels.
4. If an ICP test reveals tin, it is probably a true value; however, it may be prudent to retest with the same or a different company before panicking and taking drastic measures.
5. It may be prudent to soak or run any new reactors or plastic items in a bucket of RO/DI for a day or two when possible. However, IMO, probably only a small, perhaps negligible, amount of tin will be removed in such a short time. (RO/DI probably “draws” out more tin than saltwater would).

Just hope that you never have a tin problem!

 

[Topreefer92]

I have had a tin problem for the last year. This effort and write up has been tremendous and very insightful. Thank you for taking the time out of your day to go the extra mile!! Back to systematically replacing things in my tank .

 

[Dr. Jim]

I have had a tin problem for the last year. This effort and write up has been tremendous and very insightful. Thank you for taking the time out of your day to go the extra mile!! Back to systematically replacing things in my tank .

Just out of curiosity, would you mind indicating the values you have gotten and the size of your tank?
Thanks.
Jim

 

[spsick]

Dr. Jim THANK YOU for your efforts on this!

I am in the process of a new build and after being through a Tin event myself I will be completely assembling system and running for a few weeks in heated RO water. At the end of that time I’ll send in an ICP test and see what good it did. I’ll report back here if it was of any use. I guess I’ll quantify that by if Tin is 0. And if it’s high I guess I’ll wait longer and retest.

 

[Topreefer92]

Just out of curiosity, would you mind indicating the values you have gotten and the size of your tank?
Thanks.
Jim

Hey Dr. Jim,

So I usually only do the ICP tests when I am seeing a decline in corals and die off. Total system volume is 100 US Gallons.

4/8/20 - 6.001 µg/l of Tin

9/20/20 - 5.067 µg/l of Tin

It has been a roller coaster, Corals do really well and than a few months later boom this happens. I have done everything besides a new tank, I am starting to think it might be my water source (just started using a brand new Spectrapure MegamaxCap) or the glass itself.

Thanks Dr. Jim

 

[Dr. Jim]

Hey Dr. Jim,

So I usually only do the ICP tests when I am seeing a decline in corals and die off. Total system volume is 100 US Gallons.

4/8/20 - 6.001 µg/l of Tin

9/20/20 - 5.067 µg/l of Tin

It has been a roller coaster, Corals do really well and than a few months later boom this happens. I have done everything besides a new tank, I am starting to think it might be my water source (just started using a brand new Spectrapure MegamaxCap) or the glass itself.

Thanks Dr. Jim

When you say "roller coaster" are you actually testing tin at zero when all is well and 5 to 6 when the corals die? If so, that would tend to disprove my idea that levels that low aren't harmful. Actually, I'd be happy if my tin got down to that level! I've been thinking my corals are looking better now (with tin around 14).

In retrospect, I'm wondering if some of my early problems from 6 months ago may have been due to the fact that my tank was only 4 months "old". (This is the reason I mentioned above that I think how a coral "reacts" to tin depends partly on other factors, like, how established and "healthy" the corals and tank are in the first place).

 

[Topreefer92]

When you say "roller coaster" are you actually testing tin at zero when all is well and 5 to 6 when the corals die? If so, that would tend to disprove my idea that levels that low aren't harmful. Actually, I'd be happy if my tin got down to that level! I've been thinking my corals are looking better now (with tin around 14).

In retrospect, I'm wondering if some of my early problems from 6 months ago may have been due to the fact that my tank was only 4 months "old". (This is the reason I mentioned above that I think how a coral "reacts" to tin depends partly on other factors, like, how established and "healthy" the corals and tank are in the first place).

Sadly no, during the times I had great growth and coloration I did not test the water for tin only when I noticed a problem. My tank is a mature mixed reef (uln) and I am having those issue with such a low number I think your research is still very valid. I ordered a number of triton icp kits tonight so when the tank is on the rise I will let you know what the results are.

 

[Dr. Jim]

Sadly no, during the times I had great growth and coloration I did not test the water for tin only when I noticed a problem. My tank is a mature mixed reef (uln) and I am having those issue with such a low number I think your research is still very valid. I ordered a number of triton icp kits tonight so when the tank is on the rise I will let you know what the results are.

In that case, since you don't know if the tin level was zero when everything looked good, I'd be very skeptical that tin is the problem with levels at that low level (5 to 6). I'd guess that there is a good chance that the levels have been around 5 to 6 all along.
In any case, hope you can solve your problem.

 

[Randy Holmes-Farley Verified Community Expert]

Hey Dr. Jim,

So I usually only do the ICP tests when I am seeing a decline in corals and die off. Total system volume is 100 US Gallons.

4/8/20 - 6.001 µg/l of Tin

9/20/20 - 5.067 µg/l of Tin

It has been a roller coaster, Corals do really well and than a few months later boom this happens. I have done everything besides a new tank, I am starting to think it might be my water source (just started using a brand new Spectrapure MegamaxCap) or the glass itself.

Thanks Dr. Jim

FWIW, I do not think those values are an apparent problem, at least judging by reefers who have had those and higher levels.

 

[Topreefer92]

FWIW, I do not think those values are an apparent problem, at least judging by reefers who have had those and higher levels.

I would Completely agree with you and others here have said. I test alk daily and other items weekly with weekly water changes. So I guess I just had those test done and assumed it was the tin based off the rapid decline I was seeing in corals.

 

[Petesreef]

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. "

Ok, I don't want to seem like an alarmist here but after reading this thread and the articles that Randy and ReefLab posted all I can say is Holy Crap! Why isn't this a much bigger concern and why isn't it being discussed more in this hobby more than the 50 thousand videos on PAR from Led's?

Organotins in PVC that probably leach into our water systems to various degrees seems like a really big deal to me? How much is in all our other plastic equipment that sits in our sumps? Obviously not everyone is having a problem with this but from reading the article Randy posted it certainly sounds like it could be (will be?) an increasing problem since tin stabilizers are now used in all (99%) PVC applications in North America (Europe doesn't allow this, shocking).

Wow, Thanks Dr Jim for all your time and expense that you put into this - I wish more mfg & distributors in this hobby spent more time & money in "Quality Control" of the products they sell and weren't so consumed with pushing out the next latest and greatest thing!

 

[spsick]

Ok, I don't want to seem like an alarmist here but after reading this thread and the articles that Randy and ReefLab posted all I can say is Holy Crap! Why isn't this a much bigger concern and why isn't it being discussed more in this hobby more than the 50 thousand videos on PAR from Led's?

Organotins in PVC that probably leach into our water systems to various degrees seems like a really big deal to me? How much is in all our other plastic equipment that sits in our sumps? Obviously not everyone is having a problem with this but from reading the article Randy posted it certainly sounds like it could be (will be?) an increasing problem since tin stabilizers are now used in all (99%) PVC applications in North America (Europe doesn't allow this, shocking).

Wow, Thanks Dr Jim for all your time and expense that you put into this - I wish more mfg & distributors in this hobby spent more time & money in "Quality Control" of the products they sell and weren't so consumed with pushing out the next latest and greatest thing!

Could this be why German reef tanks are so amazing?! Is it possible tin stabilizers in plastics are used more now than in years past? So many questions. We need someone who runs a PVC factory to chime in here. Somebody has to know somebody!

 

[Petesreef]

"So many questions" - this issue of Tin in our water systems has sent me down a serious rabbit hole, thanks Dr Jim

First, why should there be ANY tin in our controlled aquarium water environments? As I understand it this is a heavy metal pollutant (primarily the organotins) that is usually toxic to most aquatic life and shouldn't be there at any level (seems completely arbitrary to me that these labs set a level that is "OK").

Second, the source for aquariums seems pretty obvious - plastics/PVC that specifically use organotins as a stabilizer which we know leaches out of the plastics (that's why we don't use PVC for our potable water supply)! The problem is that it's pretty unavoidable in this hobby and we have no idea how much is going to end up leaching into our systems- not to mention that it is also adsorbed into our rock and sand only to be leached from there later.

Finally, it just really troubles me that I might be now knowingly putting these living creatures into a potentially toxic environment and saying "good luck" and that we as a community aren't doing enough to try and figure out how serious and significant this problem might be (just search Tin on R2R).

Sorry for hijacking your thread Dr Jim

 

[Dr. Jim]

..... (seems completely arbitrary to me that these labs set a level that is "OK").

Sorry for hijacking your thread Dr Jim

You're not hijacking.....the more the merrier!

I'm not sure how the labs arrive at their set values but there may be some evidence that an "ultra low" level of Sn is beneficial or essential. KZ puts Sn in their MACRO ELEMENTS additive, so they must have a reason for doing that.

I'd be very content if the highest my Sn ever got was the 0.1 to 0.49 values that Triton and ATI use as their setpoints! (I doubt those levels would have any deleterious effects).

---------------------------
(I may have some interesting things to report soon, depending on how Red Sea handles my case.)

 

[Randy Holmes-Farley Verified Community Expert]

Why isn't this a much bigger concern and why isn't it being discussed more in this hobby more than the 50 thousand videos on PAR from Led's?

Well, the fact that lots of folks have detectable tin without detectable issues compared to folks without tin means maybe it isn't a big problem at the levels often detected.

Granted it is very hard to assess since not everyone will have the same forms of tin, but it is clearly not a death sentence for a reef tank to detect tin.

 

[Petesreef]

It seems a lot of these elevated Tin issues are on newer systems (<1yr) - could it be that this potential "leaching" effect from plastics/PVC diminishes (bacterial & photo degradation) over time and eventually stabilizes? Some of the variability factors would then be amount & type of plastic/PVC used and when it was introduced into the system, size of the system, bacteria/light, etc...

 

[esther]

It seems a lot of these elevated Tin issues are on newer systems (<1yr) - could it be that this potential "leaching" effect from plastics/PVC diminishes (bacterial & photo degradation) over time and eventually stabilizes? Some of the variability factors would then be amount & type of plastic/PVC used and when it was introduced into the system, size of the system, bacteria/light, etc...

I definitely think that this may be the case. We started up our tank in February of this year. It was a new @Waterbox Aquariums 220.6. We started doing ICP tests through Triton starting in February because I wanted to make sure we documented regularly and with the same company. We have basically been doing a 32g water change weekly. Here are our Tin values over this past year. One thing to note... Our corals and fish are doing great and we haven't really seen any adverse effects (that we know of) so far.

2/2020	3/2020	5/2020	6/2020	8/2020	9/2020	10/2020	11/2020
5.259	15	7.098	5.512	5.624	5.476	9.555	8.407

 

[Randy Holmes-Farley Verified Community Expert]

It seems a lot of these elevated Tin issues are on newer systems (<1yr) - could it be that this potential "leaching" effect from plastics/PVC diminishes (bacterial & photo degradation) over time and eventually stabilizes? Some of the variability factors would then be amount & type of plastic/PVC used and when it was introduced into the system, size of the system, bacteria/light, etc...

I think that is likely. Certainly, if the source is tin leaching from plastic or the aquarium glass, it will have limited ability to keep adding to the water over time.

i had plenty of PVC and other types of plastic (especially Brute cans) and saw no detectable tin by ICP by Triton, but no part of the system was less than a few years old at the time.