HOBBY GRADE TEST KITS CAN OUTPERFORM ICP MEASUREMENTS…REALLY??

[Reefahholic]

Depending on what you're diluting with and how accurate your dilution measurements are, you can induce mechanical error, or, in some cases, you can change the bias levels in terms of analyte response, which affects the reported analyte value.

Just for the record, from what I understand Christoph doesn’t dilute the samples himself. All dilution is happening “on-line” in the ICP-MS by addition of internal standard and further argon gas dilution which would reduce possible contamination issues from a lab technician or chemist.

There are also other potential factors affecting precision and accuracy, things like non-linear detector response above or below the range of analyte levels

This is why I have transitioned to ICP-MS. When you’re getting too close to the LLOD error becomes especially significant, since noise is already a big portion of the total signal. Many times I was noticing elements like Cobalt being detected on OES. Even though a few of these elements do have better sensitivity than something like Selenium, it’s still at the LLOD, and not fully trusted.

What I started to notice and understand is that just because it’s showing up doesn’t necessarily mean it’s accurate. That element was showing up, but the trending was all over the place which told me all I needed to know, and validated what Andre had been telling me.

 

[hunterallen40]

I’d say under 5% is still pretty acceptable wouldn’t you?

I think this is a completely acceptable margin of error.

Considering that most of us cannot state our water volume to within 5% of the actual value, I think 5% here is within tolerance (at least it seems to be -- my corals have been very happy).

 

[ingchr1]

...It just makes life easier and reefing more enjoyable for everybody...

I'm not convinced that sending in monthly ICP samples, entering the data into an assessment tool and dosing several various individual elements on a daily basis is going to be easier and more enjoyable than what I currently do for my 40-gallon mixed reef. It would also be significantly more expensive. I simply use A- elements in soda ash, K+ elements in CaCl and balling part C. Every two weeks I do a 16% water change (5 gallons).

Is my dose of A- and K+ proper for my tank? To me my corals have good color, good PE and are growing. So, if the dose is off, it's probably not too far off. If off, could it lead to an issue down the road? Possibly.

I do send out ICP samples (two a year) and think it is a beneficial tool to have.

 

[Reefahholic]

I'm not convinced that sending in monthly ICP samples, entering the data into an assessment tool and dosing several various individual elements on a daily basis is going to be easier and more enjoyable than what I currently do for my 40-gallon mixed reef. It would also be significantly more expensive. I simply use A- elements in soda ash, K+ elements in CaCl and balling part C. Every two weeks I do a 16% water change (5 gallons).

Is my dose of A- and K+ proper for my tank? To me my corals have good color, good PE and are growing. So, if the dose is off, it's probably not too far off. If off, could it lead to an issue down the road? Possibly.

I do send out ICP samples (two a year) and think it is a beneficial tool to have.

It really depends what you’re trying to accomplish. I keep mostly Acro’s so for me it’s very beneficial, and the more frequent I send ICP, the tighter the chemistry. If the reefer is keeping more LPS or Softie’s, sending a analysis every 3-4 weeks might be overkill.

Let me address your comment about some of these products that contain multiple elements in one bottle. Specifically let’s just discuss K+ elements for a moment which contains 10 elements (Ba, B, Cr, Co, Fe, Cu, Mn, Ni, Sr, and Zn).

I’d like to illustrate why this doesn’t work well from a control/precision standpoint.

Here’s the reason why. If any one of those 10 elements (let’s use Cu for this example) starts to become elevated beyond a safe range (which you may never know before it’s too late, especially if you’re not receiving consistent data to see it). That one element has the potential to slow growth, cause RTN/STN, color loss, or even crash your entire system.

Now you might say…no, it’s all based off Alk or Cal consumption. The problem with that is every single tank consumes each element differently. That’s not debatable. Some elements will be consumed more, and some less depending on multiple different variables. In fast growing acro systems I’ve observed that these elements in one bottle cannot keep up. In a slow growing or new system some of these elements are “very likely” to drift out of target range or become overdosed. I’ve seen it over and over again. I’m not picking on a specific product, but in general this is what happens when you start putting multiple elements into one bottle.

Furthermore, if you need to stop that one element like Copper, you also stop your 9 other elements in the same bottle with it, and let’s say Cal or Alk is in that bottle, you have now stopped those main elements, but If you don’t stop everything you risk overdosing or decelerated growth rates. Or let’s say Cr, Co, Fe, Mn, Zn, and Ni can’t keep up (which for sure they would get let behind in most fast growing acro tanks), you’d need to supplement a different product to keep up with your bottle.

For me it makes more sense to do away with all of that which is why I dose them all individually so that I gain complete control over every single element, but also the precision needed to hit the target ranges consistently. If one element starts elevating, I have the ability to stop it. If one element is too low I have the ability to increase it.

I’m not saying you have to do any of this, but this is what I’ve experienced as well as many others, and why we choose to reef the way we do. I do the same in the hospital. A patient comes in, we draw labs and start correcting their chemistry. We don’t mix all the supplements into one bag and say…here you go…we made you a nice cocktail! We dose them individually, and we make corrections as needed. Nothing more. When they hit the targets we stop or titrate the doses to say within the target range’s. Any smart Physician would laugh at me if I told him he could only pick magnesium, sodium, and potassium for corrections. He would look at me and say what about the rest of the patients chemistry that’s out of wack? I guess for me this is more logical, because I’ve been doing this in the hospital for 15 years. Maybe to others it’s not as straightforward.

 

[BeanAnimal]

I think that is a very smart choice. I’m definitely a huge fan of ICP-MS if you haven’t noticed. HaHa.

I’ve seen enough in my own system and others to know that the compass isn’t broken. Maybe not for every lab, but for the labs I’ve been using personally. There was one time where I did see ATI come back with high copper for several of us (5-10 people). It was like 10-12 ug/L. Normal would be below 1-2 ug/L. I target about 0.7. We all knew that it was most likely inaccurate, because none of us had done anything different. Another time I had Zinc come back around 20 ug/L and I target about 5. I sent a Triton off the next day (fast turnaround) to verify, and it was actually accurate. So I stopped Zinc for a while. Zinc can have a very negative effect at higher levels just like Copper. These are the only two incidents I can remember where something was “significantly” off, and only the Copper incident turned out to be inaccurate, because the next analysis came back normal. I’ve seen some low salinity readings, but I believe ICP has the more accurate data. It comes out pretty close to my Tropic Marin Hydrometer. Recently I had a incident with elevated Vanadium, and Christoph reached out to me asking if I adding a lot of ceramic frag plugs. I said…actually, I did add quite a few over the last 2-3 months. I put them in the sump to soak, but after he mention that could be the problem, I removed all of them. Oops! I’ll be able to see the results of that on this next analysis.

In some of these cases (which are very few) if you know your system you’ll likely already have a good idea how accurate the anomaly is (if there even is one). At that point you can make a educated decision to act or do nothing. Or maybe get a second conformation from a different lab, and most will retest the sample water if you call or email them.

The point I’m trying to make is that this is fairly rare, and there are ways around it. What if you didn’t have the data at all? You can’t make any decisions. Keep in mind, You DON’T Have to ACT unless YOU want to. I find the majority of the time I’m getting very accurate results, and I haven’t got any crazy data from OCEAMO yet.

I’ve helped countless people recover their systems, and that wouldn’t have been possible without having good ICP data. I’m not saying it can’t be off by 10-15ppm. Sure it can, but most reefers know to question critical elements and not to dose them if it could potentially crash their system. For main elements ICP has been very accurate for me, and for trace elements, MS has been fantastic. Typical detection limits are 0.05 ug/L or better for most elements. That is really impressive. We’re taking 10,000X more sensitivity. Most of my trace metal targets are 0.3 ug/L or higher, and the MS has no problem getting down there. With Uranium it’s able to get down to 0.001 ug/L which is mind blowing. That is 1 ng/L (Nanogram) I believe!

For me it’s just as much about the pollution in a tank as it is for the actual elements being dosed. We can’t maintain a thriving reef tank with pollutants. I’ve seen so many tanks with problems that stem from pollution. Being able to see their RO water has been a game changer in many cases. I’ve seen zinc and other crap coming through their filters at very high levels a number of times which turned out to be the primary problem. I’ve seen heaters, wavemakers, and frag racks breaking down. I’ve seen Tin flaking off cabinet hinges. If you were not sending ICP, none of these issue would have been known or addressed. For pollutants accuracy doesn’t matter as much, because we’re not dosing them. We just need to know if they’re present. Having the ability to see Tungsten, Neodymium, Copper, Antimony, Zinc, Vanadium, etc…is a huge help in diagnosing some serious or tank crashes.

Look, I only continue to write to you guys, because having more data to act on is super important. I get it, the data needs to be accurate, but from what I’ve seen it’s good enough, and better than not having data at all. We have tools that take all this data, and do these calculations for you, or give you guidance about what to do which is extremely helpful for newer reefers, and honestly even season veterans. It makes it easy for everybody. Even the mathematicians avoid using their brian’s. You can see your exact daily dose, daily elemental dose, your resulting multiplier (how many times you’ve increased each ultra trace element). It just makes life much easier, and quite frankly reefing becomes more enjoyable for everybody.

The tool may tell you to add 1X your “daily standard dose” which may be something like .01 - 1 ug/L starting out depending on your system volume. The precision we have with ICP-MS is really amazing, and I want all you guys to experience that. I’ve mentioned before that you can literally see the elements coming up/down by 0.1-0.2 ug/L as you’d expect to see (even less, but that is just an example), and colors becoming more intense reflecting the changes. This is verification that the corals are responding accordingly to dose corrections, and good data was received which is echoed on subsequent analysis. I’ve been playing with ICP for like maybe 3-4 years, and I’ve never crashed a tank behind it. Most labs are becoming competitive with one another, and before you know it they will all be filtering samples, using nutrient stabilizer’s.

I believe most labs will be using MS in the future once they see the value. I believe they already see it now, but the machines are expensive, and maybe they don’t have the money to upgrade so they continue to market and push their OES machines. I don’t want to knock OES too much, because for the majority of elements I do find they are accurate depending on the lab.

I’m not trying to convince you to adopt my method, although you’re more than welcome to join in, and I’ll help you to get started with as much as I can, but I do want to persuade you to get a quality ICP and start looking at the data. Continue to compare with your home test kits, and if you see it’s trustworthy over time, start making corrections on some of the elements like Strontium, Potassium, & Boron that maybe you haven’t corrected before. Then maybe start correcting some of the Halogens like Iodine, Bromide, Fluoride, etc. to see what you observe. At the same time keep an eye out for corroding equipment and source water. It’s just smart reefing.

Your entire response is predicated on the precision of ICP-MS

Again, I don’t think the test results presented here or elsewhere support that the results are that precise or accurate.

 

[ingchr1]

It really depends what you’re trying to accomplish...

Exactly, my reefing goals and the needs of my tank are significantly different than yours.

I think we've drifted off topic a bit. To bring it back, what I've gotten out of this thread is:

1. Which ICP labs to use and which ICP labs to avoid at this moment in time.
2. Our "hobby grade" test kits are not the highly inaccurate inconsistent analytical methods or toys that they are made out to be.

 

[taricha]

I’d say under 5% is still pretty acceptable wouldn’t you?

Thanks for tee-ing up the question like this.
This is something we ramble about a bit occasionally: the idea of "fit for purpose."

Let me present it this way: there are some things that I might like to know that even the worst-performing ICP vendor is capable of answering confidently.
"I have livestock dying and I want to know if I have toxic levels of zinc or copper (etc) contamination"

There are other things I'd really like to know that even the best ICP vendor can't confidently answer for me.
"does polyfilter lower the amount of metals in my tank water?"
I think I'd need like 6 ICP tests to feel good about the answer to that, and even then - only for a few metals.

Other relevant questions that ICP major element performance of "better than 5%" doesn't answer for you...
"which Ca titration test kit is better?"

"I am dialing in my dosing. Are Ca and Mg higher or lower than a week ago?"
etc.
The ICP data we receive is probably not "fit for the purpose" of answering those questions.

 

[Randy Holmes-Farley]

Thanks for tee-ing up the question like this.
This is something we ramble about a bit occasionally: the idea of "fit for purpose."

Let me present it this way: there are some things that I might like to know that even the worst-performing ICP vendor is capable of answering confidently.
"I have livestock dying and I want to know if I have toxic levels of zinc or copper (etc) contamination"

There are other things I'd really like to know that even the best ICP vendor can't confidently answer for me.
"does polyfilter lower the amount of metals in my tank water?"
I think I'd need like 6 ICP tests to feel good about the answer to that, and even then - only for a few metals.

Other relevant questions that ICP major element performance of "better than 5%" doesn't answer for you...
"which Ca titration test kit is better?"

"I am dialing in my dosing. Are Ca and Mg higher or lower than a week ago?"
etc.
The ICP data we receive is probably not "fit for the purpose" of answering those questions.

This is what I was driving at in asking about the 3% error mentioned. IMO, this is a serious problem in the hobby, both for kit testing and ICP testing. Companies providing errors in device specs is just not enough, and most do not even do that.

Whatever the error limits are for ICP and test kits, normal reefing consumers just do not get it. ICP companies and various digital devices sometimes make that false perception worse by producing answers with more digits than are justified (say, magnesium of 1343.2) implying an error far lower than reality.

This has big real world consequences.

How many threads do we see where someone claims their magnesium consumption is 10 ppm per day, while they use almost no alk or calcium?

Of course they have no such demand.

If their kit or ICP test provided an answer such as

1254 -1386 ppm (which is 1320 +/-5%)

rather than just saying 1320 ppm, folks would have a far better understanding of the reality of the result and the implications in it changing from

1320 to 1310 ppm in one day
vs

1254 - 1386 to 1244 - 1376 ppm in one day

 

[Thales]

Thanks for tee-ing up the question like this.
This is something we ramble about a bit occasionally: the idea of "fit for purpose."

Let me present it this way: there are some things that I might like to know that even the worst-performing ICP vendor is capable of answering confidently.
"I have livestock dying and I want to know if I have toxic levels of zinc or copper (etc) contamination"

There are other things I'd really like to know that even the best ICP vendor can't confidently answer for me.
"does polyfilter lower the amount of metals in my tank water?"
I think I'd need like 6 ICP tests to feel good about the answer to that, and even then - only for a few metals.

Other relevant questions that ICP major element performance of "better than 5%" doesn't answer for you...
"which Ca titration test kit is better?"

"I am dialing in my dosing. Are Ca and Mg higher or lower than a week ago?"
etc.
The ICP data we receive is probably not "fit for the purpose" of answering those questions.

I wonder if the hobby will ever be able to really accept this, or if the marketing and misunderstanding will always be with us.

 

[taricha]

How many threads do we see where someone claims their magnesium consumption is 10 ppm per day, while they use almost no alk or calcium?

"But Mg has gone down by 10 ppm 3 days in a row. So I'm pretty sure it's real!"

( as someone who is personally guilty of hunting for trends inside of error bars, just don't do it. It's finding faces in the clouds. Your brain is good at patterns and you will always find some. But they mean nothing.)

 

[Pod_01]

If their kit or ICP test provided an answer such as

1254 -1386 ppm (which is 1320 +/-5%)

rather than just saying 1320 ppm, folks would have a far better understanding of the reality of the result

Randy you expressed it well.

I think it is just human nature to become push button operators. Hanna told me PO4 is 0.02ppm so it must be true. The machine is always right!!!!!

Yet many don’t realize the sensitivity / accuracy of the egg is:

So if I get 0.02ppm what am I really measuring and what should I do?

I also think the other part of the puzzle is one needs to look at the corals. If all looks well and test claims my Alk is at 5, hmmm…. don’t add Alk double check the test.
But this is easier said, when I started I had no idea what is happy coral vs. not happy and I chased those numbers up and down…..

 

[taricha]

I wonder if the hobby will ever be able to really accept this, or if the marketing and misunderstanding will always be with us.

"Our data isn't good enough to answer that question."
"Okay, then I need better data!"
"Sorry, this is the best data you can get. So either change your question, or just live with the uncertainty."

 

[rtparty]

I wonder if the hobby will ever be able to really accept this, or if the marketing and misunderstanding will always be with us.

It’s the latter, unfortunately.

 

[BeanAnimal]

I think the previous 5 posts sum up my (likely poorly expressed) responses to @Reefahholic and in general.

If we can't get 8 parameters nailed down with a testing method, why in the world would we trust the same methodology to nail down 48?

 

[areefer01]

If we can't get 8 parameters nailed down with a testing method, why in the world would we trust the same methodology to nail down 48?

Better yet do we even care about those other 20 or 8 parameters? We are successful today without ICP or eDNA tests. Furthermore the delay between sample and what could happen in flight makes them questionable if triaging a system is warranted. The immediate need vs travel, queue, and processing times. And let us not even talk about the presentation for user consumption.

We've been successful keeping reefs in our homes without these services. Why now? Small businesses making a living growing corals to sale is not home aquaria and the needs are different.

 

[Rick Mathew]

I wonder if the hobby will ever be able to really accept this, or if the marketing and misunderstanding will always be with us.

I fear the latter

 

[lpramos]

This thread is amazing. Thank you to the innovators... the OP (Rick Mathew), taricha, Dan_P, RHF, Reefaholic, Christoph, many others. You know who you are.

Question 1: I'm testing Iodine with the HI-707. Thank you for your hard work. Wasn't there another parameter you guys were working on repurposing a Hanna egg to test? Any updates?

Question 2: I've been using Fauna Marin for ICP-OES bimonthly. FM is inexpensive, but also one of the most accurate and has an adequate turnaround time. FM is an incredible value. This thread convinced me on ICP-MS, but I'm price constrained. I get that Oceamo is the new darling of ICP-MS, and well deserved, but I can't afford it. Who is the value proposition for ICP-MS?

 

[Rick Mathew]

Randy you expressed it well.

I think it is just human nature to become push button operators. Hanna told me PO4 is 0.02ppm so it must be true. The machine is always right!!!!!

Yet many don’t realize the sensitivity / accuracy of the egg is:

So if I get 0.02ppm what am I really measuring and what should I do?

I also think the other part of the puzzle is one needs to look at the corals. If all looks well and test claims my Alk is at 5, hmmm…. don’t add Alk double check the test.
But this is easier said, when I started I had no idea what is happy coral vs. not happy and I chased those numbers up and down…..

"I think it is just human nature to become push button operators. Hanna told me PO4 is 0.02ppm so it must be true. The machine is always right!!!!!"
Excellent point!

There is so much in this statement!!! I have been fighting this battle for many many years...Not just in this hobby but in my professional life...There seems to be this belief that if the "instrument" says it it must be true!!! Forgetting that a measurement is not just the "instrument" but every element of the test protocol...from sampling to final results...The instrument is only one part of many!, with a key component being the tester themself and their understanding and skills in performing the test...

I use the analogy in my training classes "You could buy me the very best cookware available but that does not make me a chef"

Rick

 

[Rick Mathew]

This thread is amazing. Thank you to the innovators... the OP (Rick Mathew), taricha, Dan_P, RHF, Reefaholic, Christoph, many others. You know who you are.

Question 1: I'm testing Iodine with the HI-707. Thank you for your hard work. Wasn't there another parameter you guys were working on repurposing a Hanna egg to test? Any updates?

Question 2: I've been using Fauna Marin for ICP-OES bimonthly. FM is inexpensive, but also one of the most accurate and has an adequate turnaround time. FM is an incredible value. This thread convinced me on ICP-MS, but I'm price constrained. I get that Oceamo is the new darling of ICP-MS, and well deserved, but I can't afford it. Who is the value proposition for ICP-MS?

Thank you for your kind compliment!

Question #1
I am not sure which parameter you might be referring to, we are not currently doing any work on repurposing any Hanna Checkers, but looking at Potassium test kits.

On question # 2....It is not clear to me what you are asking.

 

[rtparty]

Thank you for your kind compliment!

Question #1
I am not sure which parameter you might be referring to, we are not currently doing any work on repurposing any Hanna Checkers, but looking at Potassium test kits.

On question # 2....It is not clear to me what you are asking.

Do you think Hanna could make an accurate enough and reliable Potassium checker? I am not a huge fan of the Salifert kit but I also don't have much experience with it so it is still a daunting test IMO