ICP results - extremely high barium?

[TheBiochemist]

Hello reefers,

today, I received my first ICP-OES data. Before commenting on the obtained results, I would like to say that my livestock (including several acroporas) is doing great, and I dont observe any problems. Thus, my decision to perform ICP-OES (AF Labs) test was more curiosity-driven then done to search for causes of some issues. I also prefer to know about slowly developing issues before they cause obvious troubles. I use RO-DI unit with in-line TDS meter and the output is always 0-1 ppm. Now, I use Microbe-Lift Premium Reef salt, which is not so common; however, in following weeks, I will slowly transfer to RS Coral Pro as it better matches my desired parameters.

And now to the results. I dont copy the whole record as in most cases there are no significant issues. However:
My Ba is 0.2230 mg/L, which seems to be incredibly high. Actualy, I suspect a kind of analysis error, improper sample handling or similar deviation (I work in a lab so I can imagine it).
Im quite confident that higher amounts of Ba should not have detrimental effects on livestock, but I find this concentration really to high too not cause any effect in long-term perspective.
This data was associated with:
Higher Al (0.0600 mg/L), and higher Zn (0.0377 mg/L). I actually dont consider these values too problematic, but I can imagine that long-term accumulation of these ions in organism could cause undesired effects. I have no idea what is the reason behind the high Ba/Al/Zn values. I didnt find any corrosion (I initally suspected the Radion XR15 G5 Pro mount, but it looks absolutely OK and it is not in contact with water at all), the tank room is free of deodorants, air freshener or whatever could contain Zn or Al...

Is there anybody with such experience? Any hints or discussion that could lead me to a solution of this issue might be helpful. Of course, I know that I can solve this by water change, etc., but I would rather prefer to find a culprit. Or do you think that I should forget it and let it be? Im not a fan of this idea.

Many thanks!

Zbynek

 

[DrZoidburg]

I consider maybe that these impurities in the actual salt mix, or additives. Some of the 3 you mention are commonly found together in sources for certain elements.

 

[725196]

Welcome to R2R and congratulations on getting into the habit of testing and keeping yourself in the know for your water parameters. This is so important as we keep water not fish and corals.

Although I highly recommend doing icp testing. I do one on the 1 at of every month. I have 2 years of data (3 months on my current tank) and it can be very helpful. The few suggestions I will make are; 1. don’t get caught up on numbers, 2. don’t over react to a very minor trace element that seems off and 3. DO regular icp tests.


1. Do not shoot for exact numbers. Look for a range. For example I like my Alkalinity to be about 9.5 but I am good with it anywhere be 9-10 dkh. I like my pH to be 8.3 but as long as it stays above 8 and below 8.35 I am good with it. Your tank inhabitants will tell you if there is a problem but you need to observe daily and if you will keep up on it write a short journal of what you see and do to/in yourevery day


2 & 3. You want to use the icp for following trends and not react to every result that seems off. If you get a result that is off but NOTHING looks bad it is likely an error in the test. Do some water changes and in a couple weeks send another test out. I will venture to say it will be normal next time.

I hope this helps. Enjoy the hobby!

remember the most expensive part of this hobby is impatience.

 

[Randy Holmes-Farley]

Most people have elevated barium, though not as high as yours. Typically, I do not consider barium an issue.

If the tank is not apparently suffering, I wouldn't worry about it.

 

[TheBiochemist]

Welcome to R2R and congratulations on getting into the habit of testing and keeping yourself in the know for your water parameters. This is so important as we keep water not fish and corals.

Although I highly recommend doing icp testing. I do one on the 1 at of every month. I have 2 years of data (3 months on my current tank) and it can be very helpful. The few suggestions I will make are; 1. don’t get caught up on numbers, 2. don’t over react to a very minor trace element that seems off and 3. DO regular icp tests.


1. Do not shoot for exact numbers. Look for a range. For example I like my Alkalinity to be about 9.5 but I am good with it anywhere be 9-10 dkh. I like my pH to be 8.3 but as long as it stays above 8 and below 8.35 I am good with it. Your tank inhabitants will tell you if there is a problem but you need to observe daily and if you will keep up on it write a short journal of what you see and do to/in yourevery day


2 & 3. You want to use the icp for following trends and not react to every result that seems off. If you get a result that is off but NOTHING looks bad it is likely an error in the test. Do some water changes and in a couple weeks send another test out. I will venture to say it will be normal next time.

I hope this helps. Enjoy the hobby!

remember the most expensive part of this hobby is impatience.

Many thanks for kind words and insights! Actually, the data came with a suggested range, which is (according to the AF Labs) 0.001-0.04 mg/L. Thus my value is more than 5-fold higher than the higher cut-off. I dont know how they propose the range. Its most likely a common NSW level. Now my plan is to start my regular WCs with RS salt and wait one-to-two months to send a new sample to exclude or confirm that salt contamination was a culprit.

 

[TheBiochemist]

Most people have elevated barium, though not as high as yours. Typically, I do not consider barium an issue.

If the tank is not apparently suffering, I wouldn't worry about it.

Agree. The interesting thing is that as Ba is highly reactive it is not likely to be present as free Ba and should be there in a carbonate or sulfate forms. But these might IMHO not be water soluble, so I should observe precipipation, which I dont. In contrast, water soluble Ba compounds (that might be there as anthropogenic pollutants?) are known to be quite poisonous, so I should see some toxicity symptoms or at least their onset. Ba 2+ ions are competitive to K and block potassium transport channels, so there might be some CNS functionality alterations. But still (as I cant evaluate this with corals..), my fish are doing great.

 

[DrZoidburg]

There can be barium double salts, nitrated, and halogenated barium. Those are all soluble. Some of the "insoluble salt" are to a degree soluble in alkaline conditions.

 

[TheBiochemist]

There can be barium double salts, nitrated, and halogenated barium. Those are all soluble. Some of the "insoluble salt" are to a degree soluble in alkaline conditions.

Ok, so this brings another level of complexicity! Many thanks for info.

 

[Randy Holmes-Farley]

Agree. The interesting thing is that as Ba is highly reactive it is not likely to be present as free Ba and should be there in a carbonate or sulfate forms. But these might IMHO not be water soluble, so I should observe precipipation, which I dont. In contrast, water soluble Ba compounds (that might be there as anthropogenic pollutants?) are known to be quite poisonous, so I should see some toxicity symptoms or at least their onset. Ba 2+ ions are competitive to K and block potassium transport channels, so there might be some CNS functionality alterations. But still (as I cant evaluate this with corals..), my fish are doing great.

Highly reactive? What reaction?

 

[TheBiochemist]

Highly reactive? What reaction?

It's properties are very similar to calcium, and it has quite low toxicity relative to the concentrations reefers see.

Reactive with alcohols, water, air. At least from what I know BaO is toxic for aquatic organisms. But it is clear that without further speciation or more insightful analysis, its impossible to say in which form Ba occurrs in the tank.

 

[Randy Holmes-Farley]

Developmental effects of barium exposure in a marine bivalve (Mytilus californianus)

Previous reports indicated that barium (Ba) and/or strontium (Sr) were primarily responsible for the toxicity of a southern California produced water to developing marine embryos. To further investig...

setac.onlinelibrary.wiley.com

"Although Ba is a known potassium membrane channel inhibitor at high concentrations [11], potential toxic effects on marine organisms at lower, more environmentally relevant concentrations have not received research attention"


They tested in what is generally believed to be the most sensitive type of organisms, larvae, and found:

"Adverse effects occurred between 200 and 900 mg/L"

Whether that means there's any effect in a reef at 200 ug/L, where it may be bound to organics, is a different issue.

 

[Randy Holmes-Farley]

Reactive with alcohols, water, air. At least from what I know BaO is toxic for aquatic organisms. But it is clear that without further speciation or more insightful analysis, its impossible to say in which form Ba occurrs in the tank.

You must have looked at barium metal, not barium salts. There's no barium metal in seawater. It's all Ba++, just like calcium, and that is unreactive toward those things.

 

[TheBiochemist]

Developmental effects of barium exposure in a marine bivalve (Mytilus californianus)

Previous reports indicated that barium (Ba) and/or strontium (Sr) were primarily responsible for the toxicity of a southern California produced water to developing marine embryos. To further investig...

setac.onlinelibrary.wiley.com

"Although Ba is a known potassium membrane channel inhibitor at high concentrations [11], potential toxic effects on marine organisms at lower, more environmentally relevant concentrations have not received research attention"


They tested in what is generally believed to be the most sensitive type of organisms, larvae, and found:

"Adverse effects occurred between 200 and 900 mg/L"

Whether that means there's any effect in a reef at 200 ug/L, where it may be bound to organics, is a different issue.

Randy, many thanks for your time and the attached paper. I will definitely take a look at it. I absolutely agree with you that binding with organics can affect Ba bioavailability/toxicity.

 

[Marc Pardon]

Zeolite can release barium. I have used a while zeolite stones in the sump to make some mulm for feeding the corals. Using GFO based on aluminium will lower the value ..... You can see clearly in my icp the moment of starting with zeolite and the moment I have started to use GFO based on aluminium ..... the disadvantage is that Al raised I don't think you use the zeolite stones but in case of trouble this might work .... My corals had no problems with the high barium but the LPS didn't like the high aluminium .... but that is removalble with GFO iron based ....

 

[TheBiochemist]

Zeolite can release barium. I have used a while zeolite stones in the sump to make some mulm for feeding the corals. Using GFO based on aluminium will lower the value ..... You can see clearly in my icp the moment of starting with zeolite and the moment I have started to use GFO based on aluminium ..... the disadvantage is that Al raised I don't think you use the zeolite stones but in case of trouble this might work .... My corals had no problems with the high barium but the LPS didn't like the high aluminium .... but that is removalble with GFO iron based ....

You are right. I dont have zeolite. Use of GFO sounds definitely worth to try. The problem is my phosphates being quite low and this will likely erase them. But this is another story and something that can be solved. I will see what my next ICP will show and if the problem will remain or will look progressive, I will absolutely give it a try! Thanks.

 

[Marc Pardon]

Is it possible that the rock you used causes the high barium level? What kind of rock do you use?

 

[TheBiochemist]

Is it possible that the rock you used causes the high barium level? What kind of rock do you use?

I dont think so (however I am not able to exclude it for 100 %). These are live rocks provided by my LFS and they were picked up from his larger tanks. They are covered by coralline algae quite a lot so I suppose they originate from a stable well-established system.

 

[DrZoidburg]

It is also found in carbonate rocks. Origin of rock unknown. That is possible too.

 

[TheBiochemist]

So for anybody interested, here is an update on my high Al, Zn and Ba issues. Last week, I decided to clean my powerheads including the one I use for prep of fresh saltwater. I found out that this powehead (cheap Aqua Nova NWM 2000) had a rusted propeller and the plastic around it crumbled and very small pieces were released to the water.

Thus, I performed a small experiment and prepared fresh RO/DI, fresh RO/DI with salt mixed with Aqua Nova powerhead and fresh RO/DI with salt mixed with one of my DT poweheads (Koralia Nano 900), and asked colleagues at our department to analyze the samples using atomic absorption spectrometry.

It turned out that the only sample containing high Zn and Al was the one prepared with the rusting Aqua Nova powerhead. Unfortunately, they dont have a Ba cathode lamp, hence the high Ba issue remains unresolved. However, Im quite sure that also in this case, the powerhead is the culprit.

As I still dont observe any detrimental effects on inhabitants, Im not going to do any radical measures. Just bought new, better powerhead for saltwater prep, switched on my GAC fluid filter (not sure if it will adsorb the metals, but I feel its worth to try - any experiences?), and will continue with regular 10% WC each week. In two months, I will submit my water for ICP analysis and will see what will be the output.

Important thing to note - regular control and maintenance of our equipment is of utmost importance. Fortunately, I didnt lose any fish or coral, but nobody knows what would follow in close future if I will not identify and start to solve the problem.

Thanks all of you involved in the discussion and I wish you happy reefing!

 

[DrZoidburg]

@TheBiochemist Cool glad you found this. I'm thinking now it might of started its life out as BaSO4. Your .2230mg/L almost matches its solubility in plain water. Gives it more chemical resistance and a filler in plastics to dampen vibration. In presence of other anions it can be more soluble. How many liters is your tank? If from metal maybe a oxide to hydroxide form. The Al and zn from the metal parts. I try to get ceramic impeller shafts. Some of the metal ones I replace with grade 2 titanium rods. It galls up at first but usually smooths itself out. Guess not much one can do about the plastic parts in that case.