Tin in Icp test

[Chip]

My SPS frags weren't doing well. I know there could be a million reasons, but 3 ICP tests showed Sn levels of 18, 22, then 45 and I am fairly convinced that it is causing a problem. I started a thread about this a couple of months ago and will add comments soon. I've tore down my tank and set up temporary "make-shift" tanks to soak various items separately, like: live rock, artificial rock, pvc piping and pvc products, protein skimmer, kalk reactor, RO/DI filter, Salt and salt mixing tank, RO/DI mixing tank, hang-on algae filter, etc. I cleaned and rinsed the tank and sump with RODI, filled them with new saltwater and tested each separately. Those tests from the tank and sump ruled out tin coming from the glass.

Note that many believe that when Sn is elevated without any other metal being elevated, then it isn't likely that the Sn is coming from corroding metal, but rather, from plastic or glass (and I'm not sure if acrylic is included with "plastic.")

I've run 19 ICP tests so far (awaiting for 4 to come back next week). This will sound crazy, but at the moment I've narrowed it down to two completely unrelated sources:

A. Protein skimmer and/or Sched 80 piping that came with Red Sea Reefer. (These were soaked in a 10 gal tank, known to be "free" of tin. (Of course, out of all the variables, one needs to be being able to believe the results). Sn came back around 150!
AND
B. Kalkwasser and/or Kalk reactor. Sn came back also around 150!
(Everything was brand new 7 months ago).

I've separated each of the above 4 items, soaked them for 4 days, and sent out samples recently. (These are the ones I am waiting for). So, I will receive separate results for:
1) Kalkwasser (in RODI)
2) Kalk Reactor (soaked with RODI)
3) Sched 80 PVC and green tubing that came with Red Sea Reefer
4) Protein skimmer (minus the pump; a similar DC pump was previously ruled out)

Some things I found along the way:
-I have strong reason to believe that rock can adsorb the tin (and release it) similar to how rock adsorbs phosphates or copper, probably. (This has added a small degree of confusion to interpreting results).
-I used Cuprisorb, Continuum Power Cleanse, Polyfilter, MetaSorb and carbon, not all at the same time, but many overlapped, for 7-8 days. During that time I performed major water changes. The Sn should have decreased from 22 to about 7, just from the water changes, (even if these products did nothing) but it came back higher, around
45. (This doesn't necessarily mean these products didn't work, the leaching may have been occurring faster than it could be removed).

-From a lengthy discussion 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; definitely not a resin). Polyfilter is a resin-like material sprayed on the "sponge".

I'll post again after I get the results.

Good thing I've got a lot of free time these days!! :) This has definitely been a frustrating challenge....but I'm determined to figure this out!

Did you ever find the source of your tin? I've been battling this for quite a while now.

You're like a tin Sherlock Holmes, it's inspiring! I look forward to reading your conclusions.

 

[Randy Holmes-Farley]

Did you ever find the source of your tin? I've been battling this for quite a while now.

It appears that plastics are a common source. It is used as a stabilizer in many.

 

[Chip]

It appears that plastics are a common source. It is used as a stabilizer in many.

Do you think it's in the PVC itself?

 

[lpramos]

I think I have a different source of tin.

I used to buy adult brine shrimp from my LFS. Tin went up.

I stopped. Tin went down.

I wasn't good at raising copepods for my dragonet. I bought a Ziss Brine Shrimp Hatchery around June. That thing is awesome. Tin is back up.

Fauna Marin Total ICPs:
11-23-2023 Tin 10.8
02-23-2024 Tin 10.3
04-24-2024 Tin 8.2
07-15-2024 Tin 15.3
09-06-2024 Tin 32.3

Questions:
1. Do brine shrimp result in the good tin or the bad/poison tin?
2. I know we're not agreeing on what level of tin becomes a concern. But, given the source, is it time to be concerned?

 

[Randy Holmes-Farley]

Do you think it's in the PVC itself?

I do not know. It is used in PVC, but also certain types of flexible tubing.

Regardless of the source, how high is yours?

 

[lpramos]

If anyone is wondering what I mean by bad tin, see here:

What would cause elevated tin levels? Is this level dangerous to coral?

My icp shows a crazy spike in tin. not sure whats causing it. to be safe yesterday i replaced my Chaeto reactor tubing and the pump that powers it. but it was a brand new pump so i dont think thats the cause. the only other thing i can think of is my main red sea pump, but its only 6 months...

www.reef2reef.com

 

[Randy Holmes-Farley]

The brine shrimp source, if real, is likely from them using plastics or metals I. Raising them.

None of the values seem high enough to be a sure problem.

 

[Chip]

I think I have a different source of tin.

I used to buy adult brine shrimp from my LFS. Tin went up.

I stopped. Tin went down.

I wasn't good at raising copepods for my dragonet. I bought a Ziss Brine Shrimp Hatchery around June. That thing is awesome. Tin is back up.

Fauna Marin Total ICPs:
11-23-2023 Tin 10.8
02-23-2024 Tin 10.3
04-24-2024 Tin 8.2
07-15-2024 Tin 15.3
09-06-2024 Tin 32.3

Questions:
1. Do brine shrimp result in the good tin or the bad/poison tin?
2. I know we're not agreeing on what level of tin becomes a concern. But, given the source, is it time to be concerned?

I was wondering about PE Mysis shrimp. I feed a lot of it. Any insight on it.

 

[Randy Holmes-Farley]

I was wondering about PE Mysis shrimp. I feed a lot of it. Any insight on it.

I see no reason to think any type of food can be associated with tin. It is the specific batch process details that would lead to contaminants. If PE mysis was a big source, far more people would report elevated tin.

 

[Chip]

What are the odds that a RO booster pump could be the problem? i have a Aquatec 8800 Booster pump it is quite old. lol 8 or so years?

 

[Randy Holmes-Farley]

What are the odds that a RO booster pump could be the problem? i have a Aquatec 8800 Booster pump it is quite old. lol 8 or so years?

Almost none. Anything upstream of the RO/DI is not going to be a problem for tin. It doesn't get through if the RO/DI is working.

 

[Dr. Jim]

Did you ever find the source of your tin? I've been battling this for quite a while now.

I'm convinced the culprit in my case was the green tubing that came with my tank. But other plastics were involved as well.
Recently, I've got tin leaching from either Florida Keys and/or Gulf live rock. Been trouble-shooting this for a while but haven't been in any big hurry because it is leftover rock I'm not using at the present time. I'm gradually separating small portions and testing. Might be easier just to discard it all!! :rolleyes:

 

[cybermeez]

I realize I'm late to the game here, but I had tin from solder in the building's plumbing wipe out an entire tank. I documented it in my local reef club's forum, maybe it will save someone else the heartache: https://reefs.com/forum/general-discussion/223365-what the heck-happened.htmlpost-1857987

 

[Randy Holmes-Farley]

I realize I'm late to the game here, but I had tin from solder in the building's plumbing wipe out an entire tank. I documented it in my local reef club's forum, maybe it will save someone else the heartache: https://reefs.com/forum/general-discussion/223365-what the heck-happened.htmlpost-1857987

Tin in building plumbing will be taken out by an ro/di. Were you not using one?

 

[cybermeez]

Tin in building plumbing will be taken out by an ro/di. Were you not using one?

Hi Randy,

I was using RO/DI with a mixed bed resin cartridge. It was fine in my old building (built in the early 90s), but that was not enough for the newly built one I'd just moved into. Here's the full story.

A Tank Wipeout
In June 2019 I moved to an apartment in a brand new building. It took me about a month to get the proper adapters to hook up my 6 stage RO/DI unit to my kitchen faucet. During that time I was using seawater in a box (Nature's Ocean Nutri-SeaWater) to fill the tank and do water changes, and everything was fine for that month.

When I finally got the proper adapters for my RO/DI, I replaced the sediment and carbon media (the DI resin was relatively new and still properly colored), slipped in a new RO membrane and made my own RO/DI water for the first time in the new apartment, and mixed up some saltwater. From there things went downhill really fast.

Within 24 hours the stony corals (SPS and LPS) had lost color and died, and all the soft corals completely closed. All the tank's water parameters were within normal limits. Still, thinking something went wrong with the water change I did another to try and rectify it and remove all the pollution caused by the coral die-off. "The solution to pollution is dilution," right?

During the next 24 hours every living thing in the tank except one fish, one cleaner shrimp and the zoanthids I could pull out of the tank died. When I say every living thing, I'm not kidding. All amphipods, copepods, aiptasia anemones, mysis shrimp and bristle worms, everything was wiped out.

The Hunt for a Cause
The few survivors lived in buckets of Nature's Ocean Nutri-SeaWater for the next 4 weeks while I tried to figure out what went wrong. I sent a sample of my RO/DI water to Triton Labs for testing and waited.

During that time a heater in one of the buckets malfunctioned and killed the cleaner shrimp. The water got so warm it felt like bath water and the only remaining fish (an Aiptasia Eating Filefish) barely survived.

A week later I got the results back from Triton which showed levels of tin in the RO/DI filtered water were through the roof at 53 ppm. I did not test the pre-filtered tap water since all I really needed to know was if there was something wrong with my RO/DI water, and there was.

The Search for a Solution
I searched extensively for info on how to deal with this from others reefers who'd had the same problem. As it turns out, nobody did. All accounts of tin in reef tanks at the time were caused by equipment corrosion and easily remedied with water changes once the offending piece of equipment was found. Those aquarists who tried additives on the market designed to remove heavy metals like lead, copper and iron met with mixed results. I had to figure out how to remove the tin from the RO/DI water before it ever made it into the tank.

A Potential Solution...With a Twist
After a couple weeks of discussions with the staff at Triton, PolyFilter and BRS, I thought I finally had a way to get the tin out of my RO/DI water.

I had been using one canister of DI resin (mixed bed cation/anion resin) in my RO/DI. It may have worked for the water at my old apartment, but wasn't enough to remove the excessive positively charged tin ions leaching from the solder in building's brand new plumbing.

What I needed to do was expand my RO/DI so it had 3 resin canisters; the first with cation resin, the second with anion resin and the third with a mixed bed resin. The first would remove any positively charged ions like tin and lead. The second negatively charged ions like phosphate, chlorine etc. And the third would catch any stragglers that may make it through the first 2 DI stages.

I expanded my RO/DI filtration unit to include separate stages of cation, anion and 50/50 mixed bed DI resins. I flushed the unit for about 45 minutes then took another sample of the filtered product water (not mixed with salt) and shipped it off to Triton Labs.

The results indicated tin that the level actually increased, and there were also new toxic levels of zinc and manganese too. At this point I should have had the purest dang water in NYC, but the test said otherwise.

Help from the Experts
Since I dropped several Benjamins at BRS on the additions to the RO/DI system, I reached out to them about the situation and what to do to fix it.

BRS thought that the Triton results were not accurate because it was done on RO/DI water vs. my saltwater mix, but I wan't sure.

At the time, ATI would test your RO water for free when you sent in a sample of your saltwater. So, I took them up on that offer. I mixed up some saltwater using the RO/DI water and also sent a plain sample of RO/DI in with it.

The results of both came back still positive for tin, zinc and manganese. Even more confusing, the sample of saltwater I sent them had lower contamination than the RO/DI sample, despite the fact that I used the very same RO/DI to make the saltwater.

After numerous email exchanges with Triton and BRS (where the I got the DI expansion), the conclusion was that the tests had to be wrong. Still not totally convinced I decided to add one more canister to the RO/DI unit filled with PolyFilter pads. They absorb all sorts of contaminants and if there really was any metal still in my RO/DI water the PolyFilter should absorb it.

One Last Test...
With the Triton and ATI analysis in doubt, there was one final test to do before using the water in my tank, and it meant someone might have to die.

I mixed up a couple gallons of saltwater in a bucket and bought a "cheap" green Seiatapora frag to serve as the sacrificial lamb. I put it in the bucket of saltwater made with my RO/DI and, since all the SPS that had previously been wiped out died within 24 hours of the water change that killed them, if the frag was still alive and well the next day, the water should be safe for my tank.

In the end the little seriatapora frag survived, meaning my RO/DI water was finally safe to use. I don't know if the water test results from ATI were wrong or if the final canister in the RO filter filled with PolyFilter pads removed any residual metal, but after more than 3 months I was finally able to do a water change without using boxed water.

I haven't had a problem with my RO/DI water since. It's probably excessive at this point, but the tank wipe out was so traumatically complete that 5 years later I still run a canister stacked with PolyFilter rounds as a 9th stage on my RO/DI.

 

[Randy Holmes-Farley]

Thanks.

Do you really mean 53 ppm tin ( unlikely) or 53 ug/L (= ppb)?

I suspect that if 53 ppb tin got through it, that the DI may have been depleted without you knowing it, and tin escaped. That said, tin often also comes from new plastics where it is used as a heat stabilizer. Hopefully it was not used in the manufacture of your actual RO/DI plastics. Places like BRS may not even know what heat stabilizers were used.

I think that if tin getting through a DI was common, there would be far more reports of tin in folks RO/DI water, but that is not common at all despite many folks testing it. That said, maybe the folks constructing your building left a lot of exposed solder in the pipes.

 

[Huskereef]

FWIW i have had high tin, 4-5 ugl. zinc, nickel, and aluminum slightly elevated also. Dissected a 2 year old mp40 Wetside and found rust buildup on the magnet. Hoping that’s the only culprit. the older wetside I have looks absolutely fine. Weird.