Quickly(?), here's a few reasons why the patent doesn't persuade me that ClorAm-X etc would protect from ammonia in a hobby saltwater setting. (It may, but what's presented isn't convincing at all.)
Looking at the example experiments in the patent:
Example 1 is a freshwater test using 10 Normal NaOH to push the pH of the ammonia chloride solution so high (not measured) that presumably ~100% of the ammonia is NH3, so it can all be measured with the ion selective electrode. (The electrode doesn’t measure total ammonia, NH3+NH4, it measures NH3 only).
The amount of NH3 is 0.5 to 5ppm free ammonia and the pH is who-knows-how high. Reef hobbyists want to handle stuff more in the ballpark of ~0.1ppm NH3 at pH 8.
But even at very high NH3 and very high pH, the product only reduced 0.5ppm NH3 by 10%. The % reductions got better at very high NH3, and worse at the "low" concentrations, suggesting that in our ballpark of ~0.1ppm NH3 and below, the removal might be unobservable in a real saltwater system.
Examples 2, 3, and 4 are test tube reactions directly between high concentrations of ammonium hydroxide and the product. Would the same reactions occur at single digit ppm concentrations in saltwater?
Example 5 is about the dechlorinating property, which it verifiably does.
Example 6 is observation that it doesn't make any weird reactions by adding the product to fresh or saltwater.
No Example 7
Example 8 is that the product itself is not toxic to freshwater fish in high doses.
Example 9 shows that it protects freshwater fish from chlorinated tap water.
Example 10 shows that overdoses of the product don't hurt condy anemones in saltwater.
Example 11 was a freshwater test involving a large number of fish. It seems that the only toxic condition that the fish were subjected to was water changes with tap water, and if I read it right, a normal dechlorinator and ClorAm-x both kept the fish alive (with statistically insignificant exceptions).
Example 12 is saltwater data at some aquarium-relevant ammonia and pH levels that looks like it shows reduction of ammonia. So let’s take a minute and unpack, since it's the most relevant.
First, in one part the experimenter is trying to measure tiny amounts of free ammonia (total ammonia = 1.0, pH 6.0, so
free ammonia is 0.00032 ppm NH3 ). Ion-Selective Electrodes like
this from Hach (or
orion) don’t go near that low - only to 0.01mg/L NH3. To get around the fact that the starting concentration is 1/20th of the normal lower range of these meter and what’s wanted is to measure reduction below that…. here’s what was done: mix the concentration to 1.00ppm TOTAL ammonia, recalibrate the Ion Selective Electrode to tell the meter that it is actually 1.00ppm FREE ammonia (NH3) and then track the reduction with the meter from that point on. This is reported as relative decrease in ammonia. So table 5 is saying that the electrode measured a 32% decrease in free ammonia NH3 from 0.00032 mg/L to 0.00022mg/L. Seems that detection of a decrease of 1 tenth of a part per billion NH3 would be really hard to replicate.
I don’t trust that just calibrating the meter at way below its lower detection limit gets around the lower limits of such devices, but that’s what was done.
Let's just assume for now that the calibration method worked and the meter gave real values, maybe it did. The more fundamental issue is that no mention is made of how pH of saltwater was set to 6.0, 7.0, 8.0, and 9.0 for the various tests, and no mention is made of any attempt to control or measure pH during the application of the product.
This is fundamental because when I measure pH of adding ClorAm-X to saltwater, it drops the pH by a tenth at low doses and several tenths at high doses (with or without ammonia present).
@Dan_P also measured a similar pH drop. So did
this paper, that needed to buffer the constant low pH while using ClorAm-X in intensive culture.
“ClorAm-X is an alkali metal formaldehydebisulfite that binds to unionized ammonia creating an aminomethanesulfonate salt and thereby reducing TAN. This molecule is nontoxic and does not interfere with the nitrogen cycle (Kuhns 1987). The neutralizing of free ammonia releases a hydrogen ion, lowering pH.
To buffer the system, 5 g of sodium bicarbonate/d was added to the ClorAm-X solution”
To see why the pH is a thing to be nitpicky about, take the data from the most applicable situation for the reef hobbyist - Table 11 (Ion Selective Electrode is well within its range here).
Saltwater at 1.020 s.g. was set to total ammonia of 5.0ppm and pH of 8.0.
The reduction in measured free ammonia (NH3) that was achieved after 2 hrs was 40%. It had basically leveled off by 30 minutes, with almost no change from 30 min to 2 hours.
I took my tank water, diluted to 1.020s.g. and added 5ppm total ammonia, and measured the pH with ClorAm-X addition. It was initially stable at 7.89 pH, and when adding ClorAm-X, it dropped to 7.74 pH by 2 hours with most of the initial drop recorded in the first ~10 minutes.
Running these pH values into the calculator, predicts a reduced NH3 from 0.1272 to 0.0907 or ~30% just from pH. Comparing to table 11’s measured 40% reduction, it’s hard to see what it is that ClorAm-X is supposed to have done to the ammonia. It looks like the “reaction” documented in the most relevant data may have just been a pH drop from ClorAm-X and maybe little else.
But even if it were a completely real NH3-binding reaction and pH were controlled, the data says that reduction of NH3 in a saltwater tank is limited and never actually goes low enough to be acceptable (5ppm to 3ppm total ammonia).
Example 13 shows that they took marine livestock, shipped them in bags from the Virgin Islands to Kansas City over 48hrs. The product was added to every bag and the animals survived. No attempt was made to ship some without the product to show a difference and no measurements of any kind (pH, NH3) were done.
Example 14 is the same exercise as example 12, but in hard freshwater instead of saltwater.
Example 15 is much the same as example 12, but used solid product instead of dissolved. Again, 1ppm total ammonia at pH 6.8 is a very tiny free ammonia amount (0.002 mg/L NH3) and is below detection limit for the NH3 Ion Selective Electrodes that I can find from Hach and Orion.
And that’s all the example data in the patent. And I see nothing that persuades me that it reacts to neutralize ammonia in saltwater in any significant degree, nor was any attempt made to demonstrate that saltwater livestock fared better with the product than without.
So big picture - why bother with something that may do nothing but lower pH a tenth or two? especially when you consider that you can dump in a bottle of Fritz Turbo Start and go from 8ppm to zero in under a day, and Biospira in high doses can be nearly as fast - there’s really no reason I can see to rely on hydroxymethanesulfonate to address elevated ammonia.
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