Reefs dot com article on triton testing

[JunglePete]

I agree with you and I’d take it a step further and say a healthy level of skepticism is required when interpreting anything new or unsubstantiated. It's incredible how viciously people will hold on to beliefs that they believe are fact, even though they have no proof… Regardless whether it is money driven or not.

That’s why I was so attracted to the "skeptical reefing" method… and why I was so disappointed when I found such a poorly executed and misleading article at:
http://packedhead.net/2015/triton-lab-icp-oes-testing-of-a-certified-artificial-saltwater-standard/
A defamation article, despite no proof.

 

[Rick Mathew]

More on LODs

The above LODs were compared to the average levels of elements in NSW (Pilson 1998).
What about comparing the LODs to the maximum levels found in NSW (Pilson 1998) …. A more comprehensive list can also be found at a site presented by Randy Holmes Farley at:
http://reefkeeping.com/issues/2005-11/rhf/index.php

If one where to run a Triton test on NSW with the maximum concentration of elements found in NSW, Aluminum would enter the detectable range on the Triton ICP Test… Shown in table below.

Also, Triton’s “setpoints” (levels Triton recommends or find acceptable) include Mn, Al, Ni and Zn at levels 12.1x, 1.8x, 7.1x and 6.8x (respectively) higher than the maximums found in NSW. At these setpoint levels these elements are detectable. (Bringing the list of elements that should stay below LOD down to only 12)

So for the 12-16 elements that are below LOD, and desired below LOD, any reading from Triton tests for these 12 to 16 elements would be useful in that it would indicate that there is an excessive metal issue in the Aquarium.


Very useful information IMO.

Very interesting information….Thanks for taking the time to write this up and share it



I actually come at this whole subject with a slightly different view. When I receive a report for an ICP analysis what I would like to know is not so much the LOD but what is the certainty of the measurement. If the reports says my Bromine levels are 26 points to high and I need to take some action to reduce it how certain can I be of that number…is it 26 ± 5 or 26 ± 20. This gets at the question of the variability of the test itself. The deviation number is based on the difference between the recommended set point and the actual measurement which means that the variability of the test for Bromine is included in my number 26. Knowing what part of this “26” is variability in the test would help me to know if action is required or not. I believe this concept is fundamental to any test procedure or measurement where the results would trigger an action. The type and kind of measurement or test should determine the required level of certainty….An weather temperature measurement is less critical than a body temperature measurement. Each of these would require a different level of precision and certainty. I believe we have the same thing in measuring the element in our Reef Tanks….Some elements are more forgiving others are not.

I totally agree with your statement about the value of the usefulness of reporting the 12-16 elements below the LOD. This would be a signal that something could be wrong…but only if there is a high degree of confidence in the reported value.

Every test or measurement has errors both systematic and random, and how large or small these errors are as a percent of the required limits is important. If my upper limit is say 450 and my lower limit is 350 giving me a range of 100, and my error is 50 then I am taking up 50% of my range with error. This might be fine if the measurement is not critical but if it is this would almost like getting random results and the level of certainty would be low and there for any actions to be taken would be uncertain.

If you are interested in more details here is a link to the article I put together…there are 4 parts…this is part 1 https://www.reef2reef.com/ams/getti...count-by-using-a-quality-system-approach.741/

I am a regular user of ICP analysis and see the value in this test methodology. That being said the value would be greatly increased, at least for me, if error statements were provided with each of the measurements.

Example:

Element Value Test Error

Calcium 420 ± 10 or ± 3%

Something like the Hanna Checkers provide…Here is Hanna’s Accuracy Statement for their HI-774 ULR Phosphate Colorimeter

Accuracy @ 25°C/77°F

±0.02 ppm ±5% of reading

This does not represent the total error of the test only that of the meter itself but it gives an idea of what to shoot for when you determine the total testing error….

This brings me to my last point, and then I will shut up…

IMO one of the largest potential errors in the ICP analysis has little to do with the test itself. It has to do with the sampling procedure. When the sample is taken, where the sample is taken from and how long the sample sits before being tested…These are for the most part outside of any Vendors control. The sample has to be shipped which could be several days (variable depending on the vendor). The vendor does have some control over how long the sample sits after it arrives at their facility by my experience is they are fairly quick in their turnaround once the sample has arrive…Not always but most of the time. It is my belief that the sampling procedure has a potentially large variable component. I do not know the full impact of this but there is one area that I have begun to explore. In conjunction with @Dan_P and @taricha I did a limited experiment on the effect of sample storage on test measurement on 4 different parameters with the focus on PO4….Here is a link to the post

https://www.reef2reef.com/threads/s...on-phosphate-measurement.696800/#post-7170140

As you will see from the results of these experiments there is a potential for a large amount of variability in the measurements. I do not know how this translates to ICP test results but there is some indication from many previous posts on PO4 measurements that it could be a factor…here is a link to one of those discussions https://www.reef2reef.com/threads/accuracy-of-phosphate-icp-analysis.381738/



In conclusion again I would like to say I am not in any way against ICP testing or in any way want to disparage or discredit any of the vendors, I just want to point out that I believe we are missing a part of the equation that would be helpful in better utilizing the information they provide which is very valuable.

 

[Randy Holmes-Farley]

I would add to the discussion that ICP is not a foolproof method and I would not assume all companies doing it provide similarly accurate values. Some I have much more confidence in than others based on their level of knowledge of chemistry and analytical methods.

 

[Dan_P]

Very interesting information….Thanks for taking the time to write this up and share it



I actually come at this whole subject with a slightly different view. When I receive a report for an ICP analysis what I would like to know is not so much the LOD but what is the certainty of the measurement. If the reports says my Bromine levels are 26 points to high and I need to take some action to reduce it how certain can I be of that number…is it 26 ± 5 or 26 ± 20. This gets at the question of the variability of the test itself. The deviation number is based on the difference between the recommended set point and the actual measurement which means that the variability of the test for Bromine is included in my number 26. Knowing what part of this “26” is variability in the test would help me to know if action is required or not. I believe this concept is fundamental to any test procedure or measurement where the results would trigger an action. The type and kind of measurement or test should determine the required level of certainty….An weather temperature measurement is less critical than a body temperature measurement. Each of these would require a different level of precision and certainty. I believe we have the same thing in measuring the element in our Reef Tanks….Some elements are more forgiving others are not.

I totally agree with your statement about the value of the usefulness of reporting the 12-16 elements below the LOD. This would be a signal that something could be wrong…but only if there is a high degree of confidence in the reported value.

Every test or measurement has errors both systematic and random, and how large or small these errors are as a percent of the required limits is important. If my upper limit is say 450 and my lower limit is 350 giving me a range of 100, and my error is 50 then I am taking up 50% of my range with error. This might be fine if the measurement is not critical but if it is this would almost like getting random results and the level of certainty would be low and there for any actions to be taken would be uncertain.

If you are interested in more details here is a link to the article I put together…there are 4 parts…this is part 1 https://www.reef2reef.com/ams/getti...count-by-using-a-quality-system-approach.741/

I am a regular user of ICP analysis and see the value in this test methodology. That being said the value would be greatly increased, at least for me, if error statements were provided with each of the measurements.

Example:

Element Value Test Error

Calcium 420 ± 10 or ± 3%

Something like the Hanna Checkers provide…Here is Hanna’s Accuracy Statement for their HI-774 ULR Phosphate Colorimeter

Accuracy @ 25°C/77°F

±0.02 ppm ±5% of reading

This does not represent the total error of the test only that of the meter itself but it gives an idea of what to shoot for when you determine the total testing error….

This brings me to my last point, and then I will shut up…

IMO one of the largest potential errors in the ICP analysis has little to do with the test itself. It has to do with the sampling procedure. When the sample is taken, where the sample is taken from and how long the sample sits before being tested…These are for the most part outside of any Vendors control. The sample has to be shipped which could be several days (variable depending on the vendor). The vendor does have some control over how long the sample sits after it arrives at their facility by my experience is they are fairly quick in their turnaround once the sample has arrive…Not always but most of the time. It is my belief that the sampling procedure has a potentially large variable component. I do not know the full impact of this but there is one area that I have begun to explore. In conjunction with @Dan_P and @taricha I did a limited experiment on the effect of sample storage on test measurement on 4 different parameters with the focus on PO4….Here is a link to the post

https://www.reef2reef.com/threads/s...on-phosphate-measurement.696800/#post-7170140

As you will see from the results of these experiments there is a potential for a large amount of variability in the measurements. I do not know how this translates to ICP test results but there is some indication from many previous posts on PO4 measurements that it could be a factor…here is a link to one of those discussions https://www.reef2reef.com/threads/accuracy-of-phosphate-icp-analysis.381738/



In conclusion again I would like to say I am not in any way against ICP testing or in any way want to disparage or discredit any of the vendors, I just want to point out that I believe we are missing a part of the equation that would be helpful in better utilizing the information they provide which is very valuable.

Nice summary. Your investigations on sample storage were quite thorough. I think you have enough data to present a credible explanation for Triton P measurements being lower than the user’s Hanna Checker measurements. I can’t wait for your next investigation. We need a testing forum.

 

[Rick Mathew]

I would add to the discussion that ICP is not a foolproof method and I would not assume all companies doing it provide similarly accurate values. Some I have much more confidence in than others based on their level of knowledge of chemistry and analytical methods.

I heartily agree!

 

[Rick Mathew]

Te

Nice summary. Your investigations on sample storage were quite thorough. I think you have enough data to present a credible explanation for Triton P measurements being lower than the user’s Hanna Checker measurements. I can’t wait for your next investigation. We need a testing forum.

Thank you!

Testing forum...Good idea...how does that get done?

 

[HotRocks]

Te

Thank you!

Testing forum...Good idea...how does that get done?

We generally do not add sub forums. So testing can be discussed either in the general reef discussion but is probably more fitting for the chemistry section since it’s related.

 

[Thales]

In the final posts, an author, Richard Ross (aka Thalus) claims, regarding his arguments with Triton, “I haven't actually thought much about it”.…

That’s wrong - see post #135 "Some people told me that they were told at MACNA that I had changed my mind about Triton. I haven't actually thought much about it since the response we posted earlier in this thread."
Other than that, I don’t think it will do anyone any good for me to follow up on the same kind of things that were discussed when the thread was current. Well, I will say that I did a triton test a few months ago and just yesterday had a long conversation with my friend that does the triton US stuff.

 

[JunglePete]

I would add to the discussion that ICP is not a foolproof method and I would not assume all companies doing it provide similarly accurate values. Some I have much more confidence in than others based on their level of knowledge of chemistry and analytical methods.

Would this be a fair way to elaborate on what you are saying?

 

[User1]

I would add to the discussion that ICP is not a foolproof method and I would not assume all companies doing it provide similarly accurate values. Some I have much more confidence in than others based on their level of knowledge of chemistry and analytical methods.

Hope ATI is one of them

One thing that always intrigued me with the icp tests is if it matters on the calibration standards and/or processes used to isolate our water samples between them. Granted this is all hobby stuff and not like we are launching a rocket to get out of low earth orbit but it does make me wonder.

I use ATI at least twice a year just to check what I do testing wise and more or less they are pretty close. Even to my trident with what they can both be compared to. Anyway always wondered about the processes and calibration. Maybe it doesn't matter and I'm over thinking this!

Hope all is well!

 

[Randy Holmes-Farley]

Would this be a fair way to elaborate on what you are saying?

A more complete way is to read what those individuals and companies have posted in this forum discussing details and in testing various potential issues that may arise (such as freezing of samples in shipment). One did not even know what alkalinity was. Others seem highly educated in seawater chemistry.

Example:

ICP testing

https://www.icp-analysis.com/ Is this a good thing? Based in Colorado. I've never been into much testing but I would do this. $100 for five tests. Comments please.

www.reef2reef.com

" I know, I did not mention alkalinity. Alkalinity is not an element. It is a term used when we calculate how stable our pH is, i.e. the buffer. The buffer is calculated from compounds containing Ca and a hydroxide compound (OH). Since OH is a compound, ICP-OES will not perform the calculation of alkalinity."

 

[Randy Holmes-Farley]

Hope ATI is one of them

One thing that always intrigued me with the icp tests is if it matters on the calibration standards and/or processes used to isolate our water samples between them. Granted this is all hobby stuff and not like we are launching a rocket to get out of low earth orbit but it does make me wonder.

I use ATI at least twice a year just to check what I do testing wise and more or less they are pretty close. Even to my trident with what they can both be compared to. Anyway always wondered about the processes and calibration. Maybe it doesn't matter and I'm over thinking this!

Hope all is well!

There are lots of issues in getting an ICP test to read accurately on any individual element in seawater. Even ignoring sample prep, storage, and filtration/centrifugation to remove solids before testing, it is surprisingly tricky.

I personally tried testing just calcium myself in 2005, long before it become commercial at labs like Triton. I had access to a state of the art ICP machine (at the time), and here's what I experienced:

http://reefkeeping.com/issues/2005-04/rhf/index.php

"For initial testing I chose to use as the "standard" a sample of artificial seawater that was mixed to an approximate salinity of S=35. I mixed a 44-gallon batch using Instant Ocean artificial salt mix and reverse osmosis/deionized (RO/DI) water to a conductivity of 52.7 mS/cm, and allowed it to settle for three weeks. I then proceeded to measure its calcium concentration by ICP-AES (inductively coupled plasma-atomic emission spectroscopy, an $80,000 analytical instrument. I was somewhat disappointed with my inability to use this sophisticated technique to get a precise answer. Despite taking five different samples and analyzing them at eight different emission wavelengths using two different calibration methods (five standard additions of known calcium concentrations to each sample, as well as comparison to a fixed 1000 ppm commercial calcium standard), I was unable to get consistent values. Some of the samples were acidified or filtered through submicron filter membranes to determine if solid materials were impacting the result (they were not). Overall, I took more than 200 measurements, each involving three replicate observations of the emission intensity. Nevertheless, the result was not very satisfying, with a substantial variation occurring between the different values. The average of every measurement taken was 336 ppm. With the uncertainty involved, however, I'd conclude that the true value was probably 340 ± 40 ppm. I also measured the same sample once with a Salifert brand test kit and got 330 ppm calcium. "

 

[User1]

There are lots of issues in getting an ICP test to read accurately on any individual element in seawater. Even ignoring sample prep, storage, and filtration/centrifugation to remove solids before testing, it is surprisingly tricky.

I personally tried testing just calcium myself in 2005, long before it become commercial at labs like Triton. I had access to a state of the art ICP machine (at the time), and here's what I experienced:

http://reefkeeping.com/issues/2005-04/rhf/index.php

"For initial testing I chose to use as the "standard" a sample of artificial seawater that was mixed to an approximate salinity of S=35. I mixed a 44-gallon batch using Instant Ocean artificial salt mix and reverse osmosis/deionized (RO/DI) water to a conductivity of 52.7 mS/cm, and allowed it to settle for three weeks. I then proceeded to measure its calcium concentration by ICP-AES (inductively coupled plasma-atomic emission spectroscopy, an $80,000 analytical instrument. I was somewhat disappointed with my inability to use this sophisticated technique to get a precise answer. Despite taking five different samples and analyzing them at eight different emission wavelengths using two different calibration methods (five standard additions of known calcium concentrations to each sample, as well as comparison to a fixed 1000 ppm commercial calcium standard), I was unable to get consistent values. Some of the samples were acidified or filtered through submicron filter membranes to determine if solid materials were impacting the result (they were not). Overall, I took more than 200 measurements, each involving three replicate observations of the emission intensity. Nevertheless, the result was not very satisfying, with a substantial variation occurring between the different values. The average of every measurement taken was 336 ppm. With the uncertainty involved, however, I'd conclude that the true value was probably 340 ± 40 ppm. I also measured the same sample once with a Salifert brand test kit and got 330 ppm calcium. "

Wow, thanks. Very interesting. And thanks for the article reference. Going to go read it now. I appreciate the detailed response and information you shared. Have an amazing day!

 

[Randy Holmes-Farley]

The article is actually a review of the Pinpoint Calcium monitor, so the remainder of it isn't ICP related. I just wanted a solution of known calcium content to test it.

 

[User1]

The article is actually a review of the Pinpoint Calcium monitor, so the remainder of it isn't ICP related. I just wanted a solution of known calcium content to test it.

Yup . But it was still a good use of my time to read it. At least I think so. Reefkeeping magazine, articles, are still providing value after all these years. Some hidden gems.

Thank you for clarifying and the answers earlier.