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Unread 02/23/2015, 02:58 AM   #1
Eyore
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critique of the triton critique?

http://www.reefsmagazine.com/mag.php...&articleId=159

Thoughts?

Are the values for manganese, arsenic, and iron near enough to what may be a "typical" /"expected"/"plausable" or "nsw" to give any weight to this?

Or to put another way- is ehsan right to mad as hell!

What is the opinion re zinc, nickel and iodine?


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Unread 02/23/2015, 04:38 AM   #2
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The basic premise of analyzing seawater samples sent in by hobbyists will produce some uncertainties. Scientists don't micro-filter and acidify/stabilize their samples for the fun of it.

During shipping normal unfiltered tank water some or all of the following may occur that will influence the measurement:

- microorganisms will grow or die and take up or release chemicals
- bacteria will grow or die and take up or release chemicals
- chemicals will precipitate onto the container
- chemicals will be dissolved from the container
- gases will diffuse into or out of the solution

So even before Triton gets the sample it will not be a 100% accurate representation of the water in your tank.

If they can't accurately measure a standard reference solution by a third party and claim that it's the standard's fault - what way is there to test their claims?

So either you trust them or the manufacturer of the reference solution that says that the acidification does not interfere with measurements in such a big way as to be noticeable in practice by their equipment.


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Unread 02/23/2015, 09:46 AM   #3
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Asking hobbiests to critique a scientific article seems a fools errand. If Ehsan takes issue with any part of it, he should and likely will speak up. FWIW I think the article actually shows that for the majority of the elements tested, Triton is quite accurate.


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Unread 02/23/2015, 09:58 AM   #4
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I read that article. It's the same issues RHF discussed here: http://www.reefcentral.com/forums/sh...ermedia+blocks

What they really don't mention in the article - which I think is unfortunate - they really don't comment on how ICP is an elemental analysis and doesn't tell you what you really have in your aquarium. It can probably show you Sulfur - but is that hydrogen sulfide or some form of sulfate? ICP can't tell you the difference. Sulfates are fine by the way - but sulfides can be bad.

Quote:
- microorganisms will grow or die and take up or release chemicals
- bacteria will grow or die and take up or release chemicals
- chemicals will precipitate onto the container
- chemicals will be dissolved from the container
- gases will diffuse into or out of the solution
None of these are issues with a triton test. once you take a sample and close the container up - the laws of conservation take hold. Even if bacteria were to "eat" something in the water - the bacteria still have the elements of that thing they ate. If they live or die - again - they still have their elemental composition. Precipitate will be redissolved when it comes time for testing. Off-gassing is also not an issue - as the ICP isn't going to test gases not is it able to.


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Unread 02/23/2015, 10:12 AM   #5
alexander_ktn
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Quote:
Originally Posted by Ted_C View Post
None of these are issues with a triton test. once you take a sample and close the container up - the laws of conservation take hold. Even if bacteria were to "eat" something in the water - the bacteria still have the elements of that thing they ate. If they live or die - again - they still have their elemental composition.
Only true if they use the whole sample.

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Originally Posted by Ted_C View Post
Precipitate will be redissolved when it comes time for testing. Off-gassing is also not an issue - as the ICP isn't going to test gases not is it able to.
They stated in a German online portal that the HNO3 used to acidify the sample would interfere with their testing methods since "they don't test acid, just seawater". So I'm not sure if any potential precipitate gets dissolved or ends up in the ICP-OES device.


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Unread 02/23/2015, 02:16 PM   #6
Eyore
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Is ehsan not a member of this forum?

Imo it would serve him well to publically respond the critisms on a forum instead of the rumblings i heard coming from facebook (which i have no intention of joining)


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Unread 02/23/2015, 02:42 PM   #7
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Quote:
Only true if they use the whole sample.
How? Please explain your thinking to me.

My guess is your assuming:
Bacteria eat metals that will be detected by ICP and The bacteria will not be part of the material injected into the ICP.
The solution has become more concentrated from collection to testing?

If you have 5 mg / 50 ml of Aluminum in the aquarium sample - how do you think this can be any different on testing? The concentration of the sample (as reported by ICP) would be 1 mg/ml. Even if you found a bacteria that are Aluminum - that bacteria is still going to be digested by the ICP and still be 1 mg/ml in the total.

Quote:
They stated in a German online portal that the HNO3 used to acidify the sample would interfere with their testing methods since "they don't test acid, just seawater".
http://www.perkinelmer.com/pdfs/down...wastewater.pdf

Your either reading that wrong or they are stating it wrong. All ICP methodologies I know of require the sample be acidified with HNO3. Of course they aren't testing for nitric acid. That's not what an ICP does.


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Unread 02/23/2015, 02:54 PM   #8
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I work in a lab, in and around ICP-X's of various descrptions and use them myself regularly.

This is pretty shocking to me. Not the high errors as such, but the fact that someone has had to take the time to error check Triton themselves.

If this was really a quality outfit, they would provide precision and accuracy for your results as a matter of course. You should receive accuracy compared to at least 2 or 3 reference materials.

In industry, it's standard practice to provide your own reference materials (disguised as samples) and also make duplicates of your samples to check precision. But triton is geared towards consumers and they should provide such information for you.

In any case, this information will be held by Triton (I would hope they've error checked their technique...), so they should provide it. If any of the elements have consistently high errors, then they shouldn't provide those results to the consumer, as they are meaningless.


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Unread 02/23/2015, 03:00 PM   #9
alexander_ktn
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Quote:
Originally Posted by Ted_C View Post
How? Please explain your thinking to me.
You have a water sample with 0.5µg/l of a trace element which some sedimenting bacteria consume at least partly and thus concentrate in one spot. You don't aspirate the bacteria completely when you get your few µl of fluid you need for the ICP-OES and the measure will be off. Why else would normal scientists do their best to prevent contamination or precipitation in sample shipping? I mean it's so basic a concept it's hard for me to understand why it's necessary to explain my thinking.

I agree everything that gets into the ICP will be heated and analyzed but the question is if a representative part of the sample water is being tested or if a heterogenous sample like the one described will produce different results depending on what part of it was analyzed.



Quote:
Originally Posted by Ted_C View Post
http://www.perkinelmer.com/pdfs/down...wastewater.pdf

Your either reading that wrong or they are stating it wrong. All ICP methodologies I know of require the sample be acidified with HNO3. Of course they aren't testing for nitric acid. That's not what an ICP does.
"Der vermeintlich hochgenaue Standard Meerwasser war gar kein Meerwasser, sondern 2%ige Salpetersäure. TRITON weist deutlich darauf hin, dass nur Meerwasser getestet wird und keine Säure." is what they said. Translated: "The supposedly highly accurate seawater standard wasn't seawater but 2% nitric acid. TRITON stresses that they only test seawater and no acid." Source: http://www.korallenriff.de/artikel/1...s_im_Test.html

What's there to understand wrong?



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Unread 02/23/2015, 03:27 PM   #10
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Quote:
Originally Posted by alexander_ktn View Post
"Der vermeintlich hochgenaue Standard Meerwasser war gar kein Meerwasser, sondern 2%ige Salpetersäure. TRITON weist deutlich darauf hin, dass nur Meerwasser getestet wird und keine Säure." is what they said. Translated: "The supposedly highly accurate seawater standard wasn't seawater but 2% nitric acid. TRITON stresses that they only test seawater and no acid." Source: http://www.korallenriff.de/artikel/1...s_im_Test.html

What's there to understand wrong?
The article addresses this point clearly and directly: "It is important to note that the certified artificial seawater standard has been acidified such that it contains a final composition of 2% HNO3 (nitric acid) by weight. This acidification is standard operating procedure for preparation and storage of natural waters and standards, as it is considered a requirement to prevent loss of analyte from solution (in this case, the 32 elements to be tested) primarily through adsorption to solution container walls. The 2% nitric acid in the certified artificial seawater standard has no meaningful impact on ICP-OES test results (see Figure 2)."

Thus, the acid issue appears to be a non-issue unless, perhaps, if Triton somehow calibrates its instrument to account for the loss of analyte from the test samples. This may be one of the proprietary methods that the authors of the study were unable to consider. Whether it skewed the results in Table 1 at all, for some elements and to what extent, I guess we'll never know without Triton's input.

All in all, I think the article paints a fair and positive picture of the Triton test. I'll continue to use Triton to test my water, keeping in mind the limitations and accuracy issues discussed in the article.

So... anyone know how to remove aluminum from seawater?


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Unread 02/23/2015, 03:31 PM   #11
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The article addresses this point clearly and directly
I understand that but Triton apparently doesn't - that was the issue... It seems they don't acidify their samples and even blamed the acidification for inaccuracies in the reported results.

As for using Triton: of course - there's no alternative for hobbyists at such a price, as long as one is aware of the limitations and doesn't start chasing numbers too much.


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Unread 02/23/2015, 05:13 PM   #12
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Quote:
Originally Posted by alexander_ktn View Post
I understand that but Triton apparently doesn't - that was the issue... It seems they don't acidify their samples and even blamed the acidification for inaccuracies in the reported results.

As for using Triton: of course - there's no alternative for hobbyists at such a price, as long as one is aware of the limitations and doesn't start chasing numbers too much.
I'm not surprised Triton doesn't acidify the samples -- presumably they test them as soon as they get them in and are not concerned about loss of analyte -- any loss already happened by the time they get the sample. I do question the basis for the blame they put on acidification. It may be correct, but if so, an explanation is in order. The bare statement is meaningless without one.

We should also consider whether the failure to acidify renders it impossible for any outside party to verify their testing methods. How can we have a known sample against which to test if the sample degrades in transit?


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Unread 02/23/2015, 08:30 PM   #13
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The Triton accuracy on the trace elements was disappointing, but the major elements do seem to be okay. I guess that's not very surprising given that lower levels are harder to detect.

I suspect Triton just doesn't want to bother with acidification at their price point, but we don't know how they're running their equipment, so it's hard to be very sure about what the effects would be. At least in theory, the acid shouldn't change much of anything since there's very little of it in the sample.


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Unread 02/23/2015, 09:43 PM   #14
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IMO the information that Triton provides for such a low price is perfect for the Hobby. It found a metal problem for me. And I use test kits every day with less precision. It also provides a third party check on my tank chemistry using a different method of testing. We really don't have an alternative for that at this price.


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Unread 02/24/2015, 06:54 AM   #15
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But without quoted accuracy on the trace metals you could find a metal problem that isn't really there.


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Unread 02/24/2015, 07:26 AM   #16
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Quote:
Originally Posted by jimmcwibb View Post
I work in a lab, in and around ICP-X's of various descrptions and use them myself regularly.

This is pretty shocking to me. Not the high errors as such, but the fact that someone has had to take the time to error check Triton themselves.

If this was really a quality outfit, they would provide precision and accuracy for your results as a matter of course. You should receive accuracy compared to at least 2 or 3 reference materials.

In industry, it's standard practice to provide your own reference materials (disguised as samples) and also make duplicates of your samples to check precision. But triton is geared towards consumers and they should provide such information for you.

In any case, this information will be held by Triton (I would hope they've error checked their technique...), so they should provide it. If any of the elements have consistently high errors, then they shouldn't provide those results to the consumer, as they are meaningless.
Exactly! To be accredited in the US as a laboratory you have to do this - spike so many samples, provide calibrations every so many samples, provide accuracy and precision measurements of standards, log everything and be audited for those records and methods.

Triton skirts this by saying they are not accredited because it's not needed to have exact results and it's good enough for aquarium water (i.e. by not accredited I'm assuming that they don't get audited, they don't share their methodology and they don't have a plaque on the wall saying they are a certified testing facility). I say this is B.S.. Without an accreditation - there's no oversight to say their methods are sound and trustworthy from an external party. Your taking a company's word that what they are providing is done according to best methods and is accurate and precise.

Think of it this way: Compare Large Charge Chain restaurants to a vendor on the street selling hotdogs out of a cart. The large chain restaurant has procedures and policies in place to ensure the food they keep and cook and place in front of you wont get you sick and so they wont be fined when the health inspector rolls around. The hot dog vendor has nothing. He is not inspected. Who would you trust?


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Unread 02/24/2015, 07:28 AM   #17
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Quote:
Originally Posted by jimmcwibb View Post
But without quoted accuracy on the trace metals you could find a metal problem that isn't really there.
and without molecular information - it could be the same issue. If Aluminum is detected - is it alumina or aluminum oxide? both behave differently with soft corals - so you may or may not have a problem based on the results.


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Unread 02/24/2015, 07:30 AM   #18
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Quote:
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is it alumina or aluminum oxide? both behave differently with soft corals
Isn't alumina aluminium oxide (Al2O3)?


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Unread 02/24/2015, 09:40 AM   #19
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I'm familiar with ICP (there is one just down the hall), but I'm not following how acidification of the sample would prevent Triton's ability to accurately measure the standard?

Even ignoring the fact that Triton cannot detect many atoms accurately, I think ICP as a technique for reef keeping is next to worthless (I argued this in the alumina thread). Given that ICP cannot discriminate molecular species (e.g., aluminum(III) vs alumina or silicate vs silicon dioxide), I fail to see how any result would give an actionable outcome. If Al is high, what do you do? You don't know whether it's something worth worrying about (and doing something) or something totally benign. And in the case of high Al, I'd argue it will almost always be benign and not worth the trouble and cost of "fixing" the high levels.

And given that we have no idea if they filter the samples (or any of their methods), that complicates things even further. You could have inert metal (aluminum(0)) in nanoparticle form that would give off the charts reading for Al. And panic would ensue.

I'm an academic (chemistry professor) so I love the idea of adding science & new technology to reef keeping. That is why I used NMR to determine what NOPOX is, grew bacteria from several bacteria-in-a-bottle sources, etc. That said, I strongly believe that ICP to measure our water is a forced fit and not worth the money.

I would like to hear from the Triton advocates: what actionable information did you obtain from Triton that you couldn't find from a regular test kit? What action did you take?


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Unread 02/24/2015, 09:49 AM   #20
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I say this is B.S.. Without an accreditation - there's no oversight to say their methods are sound and trustworthy from an external party. Your taking a company's word that what they are providing is done according to best methods and is accurate and precise.
do you trust the company that provides you your salt? and if so why? are they regulated? most anything we dose or add to our tanks is a shot in the dark

with the limited info we have about water chemistry, we have no choice but to trust companies that provide us products and information. look no father than the current test kits we use. they are not very reliable really, yet we use them to give us something because that's all we have. i for one am excited about the possibilities Triton brings to the table. any more information is a step in the right direction that is long overdue!


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Unread 02/24/2015, 09:54 AM   #21
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any more information is a step in the right direction that is long overdue!
This, of course, is not true. Information that isn't a step in the right direction includes:

1) Inaccurate information (the link in the OP is pretty damning)
2) Information that isn't actionable (this includes most metals measured by ICP)


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Unread 02/24/2015, 09:57 AM   #22
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Originally Posted by shermanator View Post


I would like to hear from the Triton advocates: what actionable information did you obtain from Triton that you couldn't find from a regular test kit? What action did you take?
heres a link to someone who has found it somewhat useful

i'm not a chemist, but i find it hard to believe it's "worthless''!

Edit: forgot the link

http://www.*********.com/blog/my-tri...holmes-farley/


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Unread 02/24/2015, 10:04 AM   #23
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Originally Posted by shermanator View Post
This, of course, is not true. Information that isn't a step in the right direction includes:

1) Inaccurate information (the link in the OP is pretty damning)
2) Information that isn't actionable (this includes most metals measured by ICP)
ok then sir, whats the alternative?


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Unread 02/24/2015, 10:10 AM   #24
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ok then sir, whats the alternative?
I'd prefer no information over wrong (or correct but useless, like with Si, Al, ...) information any day.

For the major players in the water chemistry, titration-based testing kits (or spectrophotometers like Hanna) are accurate and easy to use. And cheap.


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Unread 02/24/2015, 10:11 AM   #25
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do you trust the company that provides you your salt? and if so why? are they regulated? most anything we dose or add to our tanks is a shot in the dark
Absolutely. I only use ESV salt. They are not "accredited" or certified to the best of my knowledge - but I believe they provide the absolute best starting materials we can ask for without contaminants or extra non-essential additives.

Do I trust instant ocean or red sea? No I don't. Many do. But not me. I don't trust "amped" salt mixes that give you higher alkalinity and calcium mainly because it's so far outside the parameters of natural sea water. I don't trust the regular salt mixes (one bag for all) because of the non-essential additives like binders, clays, etc (whatever these may be) to allow the ease of mixing with a single bag. I don't want the extra organics that may be present in an evaporated salt product.


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