New Salt Mix Data?

[WaterKeeper]

Welcome back Randy.

You alluded in another thread that there was a presentation on trace metals in salt mixes reported at MACNA. I was wondering if these data will be published and where?

I've always been somewhat skeptical of earlier salt studies and would welcome new information on background metals in ASW mixes.

[Randy Holmes-Farley]

Yes, Tim Hovanec from Aquarium Systems/Marineland presented data that he will publish in Advanced Aquarist for the next 3 months. ICP-MS analysis of a bunch of salt mixes, along with sea urchin survival tests. He ripped Ron's experiments, and shows his own with different techniques.

The short story is that all of the salt mixes had very low copper levels in his analysis (all below 3 ppb), and that urchin survival was not correlated with metals, nor was it worse in IO than in NSW.

[WaterKeeper]

Thanks Randy. That has conclusion has been in the back of my mind for some time now.

[Boomer]

He ripped Ron's experiments

I can hardly wait

[jfinch]

Tim made a stop at our local reef club last June and presented that same data. It's amazing how different his analysis was compared to Bingman's. And he really did rip Dr. Ron's study... from his technique to interpretation of results.

[WaterKeeper]

I'm not out to rip anyone but I've done analysis myself on salt mix, IO mainly, and it never had levels like those presented in Craig's study. I also wondered why all the mixes had almost the same concentration of trace metals. I would expect more variation between batches from a single manufacturer much less those made my multiple sources.

Ron's data were more in line with my own measurements but for some reason he chose to ignore his own values and use Craig's. I sure wish I had retained my analysis, there were several, but most were done in the early to mid 80's and I didn't think anyone would be interested.

I'll be awaiting these new results as they may change some of the current attitude about DSB and OTS.

[Randy Holmes-Farley]

FWIW, in the audience of Tim's talk were, among others, Habib, myself, Craig Bingman, and Tom Frakes. While there was substantial discussion of the results and comments on whether some of Tim's criticisms were valid, many of his criticisms of Ron's work were not particularly challenged, including the fact that Craig's data was rather different than his and others. My limited testing looks more like those that are different than Craig's as well.

The point that Tom and Tim both made, and that I agree with, is that a NSW control is by far the best way to ensure that some result in not coming from artifacts.

[tonylamas]

Originally posted by WaterKeeper

I'll be awaiting these new results as they may change some of the current attitude about DSB and OTS.

Forgive my ignorance on this, but could you elaborate on this a little bit? I was not there, and am not familiar with the other studies...(though I have some time for reading should you be able to point me in the right direction).

[Randy Holmes-Farley]

FWIW, Tim's first of 3 articles should come out on about the 15th at www.advancedaquarist.com

[WaterKeeper]

Hi Tony,

Your gonna need to spend a lot more time reading to get on top of this hot topic.

I'll give you the overview first. Doc Ron, Ron Shimek, did a series of articles on data he collected from various volunteer's aquariums. With these data he produced a series of articles for Reefkeeping Magazine. The "It's in the Water..." series discussed this data and in the final couple of installments proposed that heavy metals contained in salt mixes accumulated in the sand bed overtime. At some point these metals were released from the bed at toxic levels and poisoned the tank, what is known as Old Tank Syndrome, OTS. He later did a bioassay in which IO was shown to have a toxic effect on sea urchin larvae.

Needless to say this created quite a stir in the entire aquarium community. Ron was accused, wrongly in my opinion, of doing all this to promote a low metal salt mix. It became very ugly and Ron just dropped out of the debate.

Anyway, much hinged on data that was contained in this study, "Atkinson, M. and C. Bingman. 1999. The Composition of Several Synthetic Seawater Mixes. March 1999 Aquarium Frontiers On-line.". The salts analyzed in this study indicated elevated levels of trace metals in all mixes and, amazingly, all had a very similar composition in regard to these metals.

Ron also had a single sample of IO analyzed when he did the tank analysis. The results for this sample were significantly lower than those reported in the Atkinson-Bingman study. When Ron did a statistical analysis for his series he ignored his own findings for IO and used the Atkinson-Bingman data instead. Using their data it painted a pretty poor picture of the quality of most commercial salt mixes.

Anyway here are some of the articles by Ron-

It's Still in the Water

What We Put in the Water

Our Coral Reef Aquaria...Effects of Trace Element Toxicity

The Toxicity of Some Freshly Made Salt Mixes...

That should give you a bit of reading around bedtime.

Thank for the heads-up Randy. This should become a hot topic Again

[Boomer]

When Ron did a statistical analysis for his series he ignored his own findings for IO and used the Atkinson-Bingman data instead. Using their data it painted a pretty poor picture of the quality of most commercial salt mixes.

He did more than that wrongly, he split the data. Some from the AB report and some from the S-15 report.

[LiquidShaneo]

Just so you know, Tim's article is now online: http://www.advancedaquarist.com/issu...04/feature.htm

Also, there is a typo in Figure 1 (dashed vs. dotted lines) that we're working to get resolved.

Shane

[simonh]

Originally posted by WaterKeeper
Ron's data were more in line with my own measurements but for some reason he chose to ignore his own values and use Craig's.

So, Ron's original article (1 and 2) with the data on metal levels in aquariums may not have been too far off the mark. It's just when he switched to using Bingman's analyses near the end of article 2 and the following studies of urchins that things went off track.

[Randy Holmes-Farley]

There was a lot of discussion at the meeting of whether folks were testing everything in the salt (as Craig did with acidification), or were testing the settled liquid.

[WaterKeeper]

I did total metals with an HNO3 digestion. Used furnace AA with matrix matching and my levels were way below the Atkinson-Bingman results and somewhat lower than Ron's. Using AA I was more limited in the number of metals analyzed, I think it was 12, than those using ICP. Many of Ron's conclusions would have been more convincing if he had used his own results for IO but, of course, that would have made far less of a splash, so to speak.

Off to the link--Thanks Shane.

[tonylamas]

Hmmm. I just finished reading the links Tom provided. I will read the new article later. But is seems like my train of thought has not been too far off of what Ron is/was thinking. Every several years, it will be necessary to restart the system. A. Calfo suggests replacing pieces of LR every year or so...perhaps this is just a delay tactic as the rock attracts the metals. Even without considering the salt mix, several thing accumulate in large amounts.

Kinda depressing, really. Makes me want to do 75% water changes every few months.

[tonylamas]

Ok, now that I've digested some of the info, I have a couple of question regarding Tom's statement on reassessing DSB and OTS.

I'll be awaiting these new results as they may change some of the current attitude about DSB and OTS.

1) One of Ron's conclusions was that regardless of salt mix, many of the toxic metals accumulate...to surprising levels in around 4 years...even with water changes. As I understand it, this is due to input from feeding more than anything else. His idea was that this is a major reason for OTS.

How does a new analysis of elements in salt mixes address this? Metals will still accumulate (since we will still feed) and partition themselves between the water column and substrate (DSB and/or LR).

2) In the new article, there is discussion about variability of NSW depending upon, for instance, depth of collection. At upper levels (where light is sufficient for photosynthesis), many of the toxic metals are taken up by bacteria and algae, so their concentration in the water column is much lower than in deeper levels.

Sounds like a really good argument for refugiums/algae turf scrubbers. Also sounds like one could examine the skimate from those dosing vodka/sugar to see if this method exports significant amounts of accumulated metals. While I'm not endorsing the idea, vodka may be a solution to impending OTS.

I'm interested to hear about how many people with an efficient refugium experience OTS.


I'm just thinking out load, and hoping for your thoughts as well.

[MiddletonMark]

But could you not just have the rock somewhere else, with cleaner water and drive it either algae-wise or bacteria wise and somewhat clean out the rock every few years?

Or so the response to your question, though I'm no expert at all.

Very interesting to hear thoughts of others who saw him - he gave much the same presentation at IMAC, less refined I'd guess.

[WaterKeeper]

I think what Ron was saying that the main accumulation is in the DSB. If I read him right he postulates that the anaerobic conditions in the bed produce hydrogen sulfide which reacts with the metals to form insoluble sulfides. The next part of the hypothesis is that at some point in time a condition develops that causes extremely acidic conditions in the bed that releases these same metals back into solution and then you have die-off form OTS. The exact mechanism that causes this release was never fully explained in the articles or the follow-up posts..

Much of Ron's argument to this conclusion was based on the fact that the tanks in the study had lower trace metals than the salt mixes themselves; at least if you use the metal levels from the Craig's paper. Now if we find that is not the case, that the salt mixes have metal levels lower than the tanks in the study, then some gapping holes appear in the entire theory. On top of that, it would then appear water changes would help offset the accumulation of metals from feeding.

I really haven't had time to read the paper in depth, much less do the math. Maybe my more learned brethren have and will comment shortly.

And I'll certainly leave the Vodka to them.

[Habib]

Those who have seen the results Tim presented ad MACNA , and perhaps also IMAC (don't know if it was the same presentation) might want to (re)read parts of:

http://archive.reefcentral.com/forum...68#post1118168

[tonylamas]

Originally posted by WaterKeeper
I think what Ron was saying that the main accumulation is in the DSB.

Hmm. The article to which I was referring did mention that LR and DSB could accumulate metals, but I do not remember a control for just DSB. I'll go back and look.

There are some problems in the study, mostly the fact that the analysis was not done in duplicate or triplicate, but for an analytical lab not associated with the LAPD or the FBI, it would be surprising to me that the values were erring that consistently high. Sample handling is also an issue that was not controlled.

Also, the water columns were tested and nearly all of them had very high concentrations of Sn, Ni, and Zn....even with water changes. Again, I don't remember numbers saying that these elements were correlated with DSB.

It would be nice if there were more controls and larger sample sizes with multiples of each analysis performed, but the data presented is disturbing.

What has kept him on the DSB band-wagon if his own work is this disturbing?

[WaterKeeper]

I tell you I must be the Evil Emperor of RC. I posted a link to the new article on the TRC forum and Scott is already asking where I'm going to start a thread on the salt mix debate.

Well, it appears that has already started here and since I'm tired of all the MACNA banter, I'll just continue in this thread until Randy shuts me down. By the way, the only real thing to do in Boston is to take a date down to the banks of The Charles to watch the "submarine races" at night. , Ahh, for my younger years..

In his articles Ron really never comes out and say that using commercial salt mixes will cause metal build-up in the DSB, he just alludes to it.

From Our Coral Reef Aquaria-Our Own Personal Experiments In the Effects of Trace Element Toxicity
Even with the best of care and intentions, however, there are a lot of “inexplicable events� or “strange deaths� in coral reef aquaria. These odd events include such occurrences as animals that have thrived for many years suddenly, and without apparent cause, starting a downward spiral in their health leading, eventually, to their death. Other similar events include the wholesale decline of older tanks, much to the frustration and sorrow of the aquarist who often strives mightily to keep those systems healthy.

My hypothesis is that a primary cause of many, if not all, of these unexplained mortalities is heavy metal poisoning. I believe this metal poisoning is specifically due to the excessively high concentrations of some of the trace elements that are present in tank water.

As toxic trace elements will likely accumulate in live rock and sediments, there is likely a finite life span for a reef tank. As a guess, I would suspect that for hobbyists that have to rely on artificial sea water, it will be prudent to breakdown and re-establish a tank every four or five years, perhaps more frequently.

Now that was well and good but we then had the usual debate over the whole series of articles in these threads-

Starting with Why do Water Changes? thenThe EVIL Waterkeeper Strikes Back followed by What salt do YOU use to poison your Tank?, a retort Ron Strikes Back and, finally, DBS RIP. This does not include, thankfully, some others like the one Habib posted earlier in this thread.

Anyway, that brings us back to the current study by Dr. Hovanec. As I said earlier, much of this hinges on the Atkinson-Bingman study of trace metals in salt mixes. Doc Shimek used their data in statistical analysis that indicated a major decline in tank water compared to metals in the various salt mixes. If we look at the new data things change. Sorry the attachment didn't attach here. See the post below for the spreadsheet (you need to be able to view Excel .xls files to open it.)

As you can see with all but Chromium and Lead, the tank values were equal to or below the average salt mixes tested and the lead level in the salts was below the detection limit in the tank study so it may have been present.

This is a very preliminary look. I only read the article late last night and have not really had time to digest it. I did the comparison spreadsheet on the fly and it is not intended to provide statistical inference of any kind.

What I did want to make clear is that this new study indicates that metals do not appear to be depositing in the substrate or rock. Tank values are not exceedingly lower than the salt mix values. This was not the case in the earlier comparisons.

This is a really strange debate overall as both Ron and I still push for DSB and, as Ron states in his article, for water changes. I'm sure these data from the new study will bring much comment. I hope it is constructive.

OK Scott, you can start selling the popcorn and soft drinks to the TRC members. The game is afoot.

[WaterKeeper]

Sorry it didn't appear above-

[traveller7]

Originally posted by WaterKeeper
I tell you I must be the Evil Emperor of RC. I posted a link to the new article on the TRC forum and Scott is already asking where I'm going to start a thread on the salt mix debate.

As we get older, even Evil Emperors need a little push ;>)

Originally posted by WaterKeeper
OK Scott, you can start selling the popcorn and soft drinks to the TRC members. The game is afoot.

Concession stand is open to all. Looking into an automatic paypal deduction to be sure we can keep up with demand

fwiw: The report numbers are interesting, but I would still like to see multiple batch testing by at least 2 labs if we are going to use the values to craft actions.

I'll leave the real discussion to those actions much smarter then I

[Randy Holmes-Farley]

As toxic trace elements will likely accumulate in live rock and sediments, there is likely a finite life span for a reef tank. As a guess, I would suspect that for hobbyists that have to rely on artificial sea water, it will be prudent to breakdown and re-establish a tank every four or five years, perhaps more frequently.

The metals accumulation somewhere in the system is a reasonable, but unproven hypothesis. The part about salt mixes being different in this regard than NSW is, IMO, incorrect.