ICP testing

[cigarshark]

I would like to introduce myself. My name is Dr. Ben Funk, I have my Ph.D. in biology and I am the leader of the lab and the R&D department of ATI.

I have many challenging tasks at ATI. Beside R and D I also ensure, with the help of my team, that our machines do a proper job.

You can not only put somebody in front of such a machine who is able to push the buttons. You need passion, knowledge and technical understanding to reach and keep 98-99% accuracy with an ICP-OES machine.
If you have a team like mine, it is no problem to get ICP results of natural seawater that fit to the principle of constant proportions (Check).

So Ben, are you the one operating the instruments for all testing as you co-worker inferred or are you overseeing the process? There is a big difference saying a PhD is running the tests or saying the testing is overseen by a PhD. I would never have a PhD hired to just run the instruments, I would have them oversee and create protocols for the testing because that is sound business practice.

 

[DSC reef]

So Ben, are you the one operating the instruments for all testing as you co-worker inferred or are you overseeing the process? There is a big difference saying a PhD is running the tests or saying the testing is overseen by a PhD.

You already argued with one chemist and got shut down. So are you saying that you personally do all your testing yourself?

 

[DSC reef]

Would you mind sharing what those degrees are? Since the strength of ICP-OES testing lies in the expertise of the person running and analyzing the tests, it is important to know what the qualifications of that person are.

I was almost ready to place an order for water testing through "ICP-Analysis.com" and then decided to do some basic internet digging. Turns out the owner of ICP-Analysis, and their sistem company, Stone Aquatics, is Steve Visser (is that you @cigarshark ?). Steve Visser also owns another company "Great White Bottling" (that shares the same address), whose primary product is third-party insurance on furniture you buy at Furniture Row. I have dealt with similar furniture insurance once before and I know what type of scam they are. Looks like Great White Bottling is no better. Read the reviews on Google and judge for yourself: https://www.google.com/search?q=gre...8#lrd=0x876b86a8fba9d54b:0x87496c369a261c26,1, . Here's more: https://www.pissedconsumer.com/great-white-bottling/RT-F.html

I wouldn't trust any water testing results from a company that has so many upset customers. Better to spend the extra $20 and send it to Triton.

@cigarshark This says what we need to know

 

[cigarshark]

@cigarshark This says what we need to know

If you look up any aftermarket accidental damage company you find negative reviews being the majority of the posts. The reason for this is customers always think they are right. Our program we offer is sold by sales people that often oversell the program and the consumer chooses not to read the first page on the brochure that tells the consumer what we cover and do not cover, and when consumer files a claim on something we state in bold clear print that we do not cover they get ticked and rant on the web. When you sell thousands of warranty programs a year there are always going to be unhappy customers. Examples of things we denied on a regular basis are children taking knives and scissors stabbing their furniture, manufacturing defects, such as leather bursting because it is too thin and pulled so tight that it can not handle the pressure of someone sitting on it, stiching coming undone. These are all happening within the first 2 years of furniture being in use. These examples make up 99% of upset people and these items are beyond an accidental coverage program. When people are happy with a program like ours they rarely take the time to post a positive review. When they are not happy with a denial reply from us they feel cheated and have a lot of negative emotions and they post negative things. If you look at any service company on the net you will find a majority of reviews to be negative for these reasons. Look at the average person and ask yourself how often do they go on line to post a reply about a good job the plumber, electrician, cable tech did when they fixed a problem? When people are happy they continue on with their life because we expect a proper job to be done and no further action is required.
The small percentage of unhappy customers we have is a result of people believing that we should cover something we tell them up front we do not cover and that the customer is always right. News flash, the customer is not always right.

 

[cigarshark]

You already argued with one chemist and got shut down. So are you saying that you personally do all your testing yourself?

I set up all the protocols and the testing procedures for each element and I review the results before they are sent out. Our system is automatic, we load the protocol for the testing, enter the customers into the system and hit run. We then come back and review the data and send it out. The actual running of the machine is not a complicated process. The complication is figuring out which wavelength you want to analyze an element at that will not interfere with another element and knowing the sensitivity of the machine. It is not as simple to tell the machine to test these 40 elements because you will get interference from other elements if they are not chosen at a proper wavelength and intensity. When choosing 5-10 elements it is pretty easy to set it up but when you want to test 40 elements the setup is like an intricate dance where every additional element creates a potential problem with the previous elements you have selected.

 

[DSC reef]

I don't know @cigarshark. My customers post all kinds of good comments and reviews in my field. To me it sounds like your trying to convince others why you have so many bad reviews and excuses why people don't leave good reviews. Typical company I'd never do buisness with and I'll leave it at that. I trust the chemist on this site and i trust ATI.

 

[cigarshark]

I don't know @cigarshark. My customers post all kinds of good comments and reviews in my field. To me it sounds like your trying to convince others why you have so many bad reviews and excuses why people don't leave good reviews. Typical company I'd never do buisness with and I'll leave it at that. I trust the chemist on this site and i trust ATI.

That is your choice and you are free to do business with who you wish to. The reputation of my fish store and working with CoralVue to distribute our and sell our testing will speak for itself. You will be hard pressed to find any vendor in the fish world that will say anything negative of my fish store or the ICP testing.

 

[Randy Holmes-Farley Verified Community Expert]

You will be hard pressed to find any vendor in the fish world that will say anything negative of my fish store or the ICP testing.

In other threads, we have discussed apparent issues with the natural seawater results that you provide along with results. I applaud the idea of presenting natural data, but the values are concerning.

https://www.reef2reef.com/threads/did-i-pick-the-wrong-icp-testing-company.339369/#post-4233542

"The natural seawater samples do not follow the expected ratios of the major ions in normal seawater. That is probably due to testing errors on them, but might also be due to electing locations for testing that are unusual (that is, near surface run off)."

Can you shed any light on this issue?

 

[cigarshark]

In other threads, we have discussed apparent issues with the natural seawater results that you provide along with results. I applaud the idea of presenting natural data, but the values are concerning.

https://www.reef2reef.com/threads/did-i-pick-the-wrong-icp-testing-company.339369/#post-4233542

"The natural seawater samples do not follow the expected ratios of the major ions in normal seawater. That is probably due to testing errors on them, but might also be due to electing locations for testing that are unusual (that is, near surface run off)."

Can you shed any light on this issue?[/


Our oceans circulate the world because of changes in temperature and salinity. I will refer you to NOAA, http://oceanexplorer.noaa.gov/facts/currents.html
This is also what I was taught at Colorado School of Mines in their environmental chemistry class too. So if this wrong I would like to see the proof of it.

 

[JimWelsh]

Millero, Chemical Oceanography, Chapter 2 the first three paragraphs.

EDIT: Changes in temperature and/or salinity do not affect the ratios of the major, conservative ions in seawater. Your answer does not address the question Randy is asking.

 

[DSC reef]

anyone else do any tests recently? I think I am going to give ICP-anaylsis a try

I'd stick with ATI or triton. The other is to shady IMO

 

[cigarshark]

Millero, Chemical Oceanography, Chapter 2 the first three paragraphs.

EDIT: Changes in temperature and/or salinity do not affect the ratios of the major, conservative ions in seawater. Your answer does not address the question Randy is asking.

To say the ratios are the same all over the world is crazy. The real World does not operate like laboratory environments, if it did approximation theory would never had been invented. Just look at the Great Salt Lake in Utah, which goes back to when the Ocean covered the western part of North America. It is heavily concentrated in sodium chloride and lacking calcium chloride. Geology changes all over the world and as the water makes it's circulation around the world it will pick up additional elements. If you think that volcanoes do not emit additional minerals into the ocean to change a regions concentration of elements then I want to see the studies that have been taken and show me the results of the water samples collected from locations all over the world. If ATI wants to challenge the water samples we have tested on our ICP from locations we have sampled from around the world then tell them to put their money where their mouth is and go get the water samples themselves and test it and provide the results. It is pretty easy to attack another business from 5000 miles away with theories but I want to see hard data. Our testing of water from around the world is to provide our customers a baseline of what the water looks like around the world so they can compare their results with NSW. If anyone disputes the results I challenge them to go get a sample of water and have it tested. There is one other aspect that has to be remembered about instruments, and Agilent even publishes this on their equipment information, it is possible to have a 5% margin of error, so take Na (sodium) with a level of 10,000 ppm and put a 5% error on it and you have a + or - of 500 ppm.

I have to say that I started the ICP testing to provide a good service in America so customers did not have to send their samples to Europe and wait 2-3 weeks for results. I have found this forum to be filled with attack after attack on myself and my service. I had decided to be a sponsor of this site but if these attacks are what I am going to pay thousands of dollars a year to hear then I say this forum is filled with too many negative people and uncalled for rudeness that ATI started and I will not support any forum that has nothing positive to say. These are my final words, this is America and the Land of the Free and the land where people can choose where the do their business, and I am not a politically correct person and will not tolerate anyone calling myself or my businesses shady.

 

[JimWelsh]

You do understand that we are talking about the ratios of the major components of seawater (Na+, K+, Ca++, Mg++, Sr++, Cl-, SO4--, HCO3-/CO3--, Br-, F-, B(OH)3), and in the oceans, not landlocked seas/lakes, yes?

To say the ratios are the same all over the world is crazy.

No, to dispute that they are is crazy. This well-established fact has been referred to by renowned oceanographers as "the first law of chemical oceanography".

I want to see the studies that have been taken and show me the results of the water samples collected from locations all over the world.

Well, if you were to simply refer to the citation you asked for and I provided above, you would see references to a myriad of studies involving many thousands of samples from literally all over the globe at varying depths beginning in the early 19th century to present.

What you are being asked to address is how widely the values you publish here vary from the findings of oceanographers worldwide, which are also clearly described in standard textbooks such as Millero's. Not only do your numbers show ratios wildly different from the well-established ratios, e.g., your "Florida Water" has a S:Cl ratio that is 1.3 times the NSW ratio, but your numbers are also nonsensical in terms of charge balance. For example, for your "Hawaii Water", the sum of the millimoles of each cation times the charge of each cation is 580, but for your anions, the same calculation gives 653. That is not a small error, and is clearly impossible. And, that's even leaving out corrections for alkalinity and fluoride, which would just make the error larger.

To back off of the mathematical pedantry and put it in simple layman's terms, just looking at the numbers between your baseline samples, the ratios of the major elements Na, Mg, Ca, K, Sr, Cl, S, Br, & B, vary among themselves and also stray from well-known NSW levels too widely to conform with this "first law of chemical oceanography". To quote Marcet, who said in 1819: "All the species of seawater contain the same ingredients all over the world, these bearing very nearly the same proportion to each other, so that they differ only as to the total amount of their saline contents." This has been shown to be true over and over again over time. Since you cited NOAA earlier, I refer you to this link explaining Forchhammer's Principle.

 

[Gareth elliott]

Just look at the Great Salt Lake in Utah, which goes back to when the Ocean covered the western part of North America. It is heavily concentrated in sodium chloride and lacking calcium chloride.

The Great Salt Lake is a remnant of a larger inland lake not the ocean. The larger Bonneville lake formed ~30,000BCE. Towards the end of the Upper Paleolithic, the larger lake flooded over its upper limit and never regained its prior size. This being well into the Quaternary period. The Western Inland Sea on the other hand had ceased to exist by the Thanetian age ~60m BCE

 

[cigarshark]

You do understand that we are talking about the ratios of the major components of seawater (Na+, K+, Ca++, Mg++, Sr++, Cl-, SO4--, HCO3-/CO3--, Br-, F-, B(OH)3), and in the oceans, not landlocked seas/lakes, yes?



No, to dispute that they are is crazy. This well-established fact has been referred to by renowned oceanographers as "the first law of chemical oceanography".



Well, if you were to simply refer to the citation you asked for and I provided above, you would see references to a myriad of studies involving many thousands of samples from literally all over the globe at varying depths beginning in the early 19th century to present

What you are being asked to address is how widely the values you publish here vary from the findings of oceanographers worldwide, which are also clearly described in standard textbooks such as Millero's. Not only do your numbers show ratios wildly different from the well-established ratios, e.g., your "Florida Water" has a S:Cl ratio that is 1.3 times the NSW ratio, but your numbers are also nonsensical in terms of charge balance. For example, for your "Hawaii Water", the sum of the millimoles of each cation times the charge of each cation is 580, but for your anions, the same calculation gives 653. That is not a small error, and is clearly impossible. And, that's even leaving out corrections for alkalinity and fluoride, which would just make the error larger.

To back off of the mathematical pedantry and put it in simple layman's terms, just looking at the numbers between your baseline samples, the ratios of the major elements Na, Mg, Ca, K, Sr, Cl, S, Br, & B, vary among themselves and also stray from well-known NSW levels too widely to conform with this "first law of chemical oceanography". To quote Marcet, who said in 1819: "All the species of seawater contain the same ingredients all over the world, these bearing very nearly the same proportion to each other, so that they differ only as to the total amount of their saline contents." This has been shown to be true over and over again over time. Since you cited NOAA earlier, I refer you to this link explaining Forchhammer's Principle.

Do you own an ICP? Have you calibrated an ICP-OES to analyze salt water? Have you tested the water yourself and looked at the intensities of each element at the various wavelengths?
If not then come use ours and show us what we are doing wrong because a senior ICP chemist with Agilent found our results and procedure to be accurate and our standards, spikes and check standards always come out right in the number. Our process is sound and the standards, spikes and our check standard always come out correct.
Our sulfur levels 6 months ago were off because of operater error and not forcing more argon gas through to read a lower wavelength of sulfur but not anymore.

If anyone who wants to pipe in and is a qualified ICP analyst I will fly you out and put you up in a nice hotel and you can educate us in all our wrong testing. Just contact us through our website.

 

[JimWelsh]

Have you ever cracked open a chemical oceanography textbook? While you are correct that I can't tell you what you are doing wrong, you are clearly doing something wrong, as evidenced by your own numbers, which violate the "Law of Constant Proportions". We have invited you, several times, to explain the discrepancy between your numbers and well known oceanography. You have chosen repeatedly to dodge the question, and hurl insults back instead. I'm done here.

 

[DSC reef]

It seems when other members here that actually know what they are talking about when it comes to actual chemistry cigar shark just hurls insults when asked legitimate questions. Interesting. So now that we know you don't do any of your own testing @cigarshark why were you questioning ATI on who has the PhD? You failed to answer any real question posted and others were not rude to you.

 

[Randy Holmes-Farley Verified Community Expert]

Have you tested the water yourself and looked at the intensities of each element at the various wavelengths?
.

I have, yes. I have a good understanding of ICP.

That said, an understanding of how the method works or even what method was used is not needed to see that the values you give for natural seawater samples do not match the understanding that chemical oceanographers have of the major ions in seawater.

As I said above, I do not know why:

"The natural seawater samples do not follow the expected ratios of the major ions in normal seawater. That is probably due to testing errors on them, but might also be due to electing locations for testing that are unusual (that is, near surface run off)."

Which is why I asked you to shed some light on the possible explanations.

Let's look at two ratios as an example: bromide to chloride and sulfate to chloride.

The bromide/chlorinity and sulphate/chlorinity ratio in sea water
http://www.sciencedirect.com/science/article/pii/0011747166906012

"Water samples collected from the world's oceans for the National Institute of Oceanography for the study of the inter-relationships between chlorinity, electrical conductivity and density have been analysed for bromide and sulphate. Bromide determinations carried out on 219 samples showed that the bromide/chlorinity ratio was 0·003473 ± 0·000012. Sulphate determinations were performed on 345 samples and gave a sulphate/chlorinity ratio of 0·14000 ± 0·00023. No significant deviations from these ratios were found for any locations with the exception of the Baltic; figures for the latter have been omitted when calculating the above ratios."

Let's look at bromide to chloride first:

"the bromide/chlorinity ratio was 0·003473 ± 0·000012. "
that corresponds to a range from 0.003461 to 0.003485 (note: this is a weight ratio, not a mole ratio)
the range around the average corresponds to 0.35% of the average

In this thread

https://www.reef2reef.com/threads/did-i-pick-the-wrong-icp-testing-company.339369/

The OP posted on Nov 23, 2017 that you reported these results:

Fiji water: 81.72 bromide and 19,415.27 chloride, which gives a ratio of 0.00421
Saint Thomas Water: 40.31 bromide and 19554 for chloride, which gives a ratio of 0.00206

So the scientific paper shows a very tight range in different ocean samples for the bromide to chloride ratio, and it is about 0.00347 with a range of about 0.35% on either side of this value.

Your natural seawater data gives two samples, one with a Br/Cl ratio of 0.00421 (21% above the average ocean value) and one with a Br/Cl ratio of 0.00206 (40.7% below the ocean average value).

How do you reconcile your data with the scientific literature?

Do you think that is the correct value for those locations?

 

[Randy Holmes-Farley Verified Community Expert]

For the sulfate to chloride ratio:

"Sulphate determinations were performed on 345 samples and gave a sulphate/chlorinity ratio of 0·14000 ± 0·00023. "
Range = 0.1398 to 0.14023
Range = average +/- 0.16% (very, very tight)

You present your data as sulfur and not sulfate, so we need to multiply your sulfur values by 3.00 to get sulfate weight in the water.

You report:

Fiji 19,415 for Cl and 951.56 for S (= 2854.6 for sulfate) for a ratio of 2854.6/19415 = 0.1470 (5% over the ocean average)
Florida 19,283 for Cl and 1155.25 for S (=3465.8 for sulfate) for a ratio of 3465.8/19283 = 0.1797 (28.4% over the ocean average)
Hawaii 20454 for Cl and 1163.54 for S (=3490.6 for sulfate) for a ratio of 3490.6/20454 = 0.1707 (21.9% over the ocean average)
St Thomas 19554.8 for Cl and 975.75 for S (=2927.3 for sulfate) for a ratio of 2927.3/19554.8 = 0.1497 (6.9% over the ocean average)

So like the bromide to chloride ratio, the range of sulfate to chloride you show is very much larger than in the literature.

Why do you think that is?

 

[Ranjib]

You are right I know nothing about your company. BUT, I am an expert chemist with a PhD from Harvard and I know a lot about ICP and have run them on many sorts of materials, including seawater for many articles I have written.

You may do things perfectly well, but your poor description does not lead to confidence and I'd suggest you change it before coming on and blasting my comments as being equivalent to the National Enquirer.

Now I stop being nice.

Your sentence about alkalinity is total nonsensical crap. It is not simplified. It is just wrong, so very wrong.

There is no reason anyone should have confidence in your data with such an utterly incorrect definition of a term at the very heart of chemical reef keeping:


" 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."

That is not true. One can lay some confidence on his effort/shop, because the test and equipment are from agilent, its not that he is running a snake oil titration method. Albeit, the wording on website may not be the best. But hey, communication has always been a hard problem., and you as an expert looking at it with a very high/accurate expectation. The fact that he is trying to explain his stance shows some level of integrity. We are human first, having some empathy will go a long way. If his stuff does not give confidence to you, say so, but calling crap and other derogatory word are not useful, it has never been useful... it just reflects our inner frustration.

Pointing finger is very easy, let me give you a taste, 80% of scientific article are not reproducible, even if they are worded correctly https://www.nature.com/news/1-500-scientists-lift-the-lid-on-reproducibility-1.19970 . Does that make 80% of PhD holder bad .. never.. their hardwork on a domain will yield some level of expertise,

Coming back to the subject. I am thankful that there is USA based company thats doing ICP analysis. This means things will be faster and cheaper for us. More options for us. Whether the vendor is good or bad, will be determined in due time anyway. reefing scene in CO & CA is thriving. This is a very good news for us.