A Deep Dive on Ammonia Neutralizer Chemistry - Prime, ClorAm-X, Rongalite and friends.

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taricha

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Here is my sniff report.

For both products, the aroma did seem that intense, snorting the head space was needed rather then wafting it towards my nose to get a good whiff.

Aqueon - dead snail aroma

Prime - rubber tire aroma with overtone of dead snail
Always jealous of the trained chemistry nose.
Such a useful analytical tool.
 
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taricha

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So if im understanding things, it seems like these products do little to nothing in reality when used in a saltwater tank as far as neutralizing ammonia.
Do they work properly in freshwater where there isn’t all the extra stuff (salts) in there?
Good Qs.

I obviously didn't look at the freshwater side much at all compared to the salt, but I did do a few runs with highest recommended dose of ClorAm-X. Here's what I wrote in notes.
"I tried lake water, buffered and unbuffered distilled water, Tankwater diluted to 10%. pHs of 6 to 8. ammonia from 1 to 10 ppm total. Nothing has shown more significant binding than maybe 30% on the seachem NH3 disks."
(+-30% on those disks is about how much you need to know there's anything, so maybe just barely detectable effect. Wasn't the clear result I was looking for.)
This might feel wrong - you'd guess that reaction would work way better without a bunch of seawater ions in the way, but...
Even in the Kuhns patent for HMS measuring with ion-selective electrodes, the data on NH3 removal from freshwater and saltwater tanks was not much different (and all pretty much explainable as the pH drop from HMS dissociation.)

so, the ammonia removal part may be similarly difficult to do in freshwater with these reactions.

Additionally I know this was about ammonia but do they do what they say and actually neutralize chlorine? (Like when doing a freshwater tank water change)
yes, to varying degrees, they all dechlorinate Chlorine / Chloramine. Rongalite is an instant dechlorinator with a reaction that goes to completion, HMS is slower and does not go to completion unless you raise the pH.
regarding HMS...
Note that at pH 9, the dechlorination is very rapid at around the expected 1:1 molar ratio - that is about 0.002mM of HMS dechlorinates 0.002 mM of bleach almost instantly. Also note that the amount of treated tankwater (plotted on x-axis as mmoles of HMS) needed for rapid dechlorination increases with each 0.5 pH unit decrease. At lower pH, a smaller and smaller portion of the HMS rapidly dissociates into available sulfite and formaldehyde, and the dechlorination depends on this release of sulfite. At lower pH, most of the HMS remains as the compound and does not react with chlorine, requiring much larger than the theoretical 1:1 molar ratio to dechlorinate rapidly.

and rongalite
One of the relevant differences for aquarium applications is that rongalite is a more effective dechlorinator than HMS. A mole of rongalite can dechlorinate two moles of chlorine/chloramine, while HMS only dechlorinates in a 1:1 ratio. This is because of the different adducts with formaldehyde in each. HMS has sulfite attached to formaldehyde, and the sulfite, SO32- can only be oxidized once before going to sulfate SO42- and becoming essentially non-reactive. Rongalite has a sulfoxylate, SO22- attached to formaldehyde, and it can be oxidized twice before becoming sulfate.
The other way in which Rongalite is a superior dechlorinator is that it reacts with chlorine rapidly regardless of pH, whereas HMS only reacts with chlorine to the extent that it dissociates and releases a sulfite, which is a pH-dependent process as illustrated in fig 6. This means that in an aquarium context, Rongalite will complete the dechlorination reaction in seconds, and HMS will take minutes, perhaps hours if the pH drops to near 7 or below.

This fact that HMS is slower to dechlorinate is probably why few common hobby products are HMS alone.
Fritz ACCR measures like HMS + thiosulfate, and Prime is HMS + rongalite.
 
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I checked 3 Prime bottles of different ages for the question of smell and stability. I measured dissolved O2 and pH in the bottles as well.

BottleOdordissolved O2pH
never openedbarely detectable0%9.37
opened 4 monthsstrong0%9.33
over a year (frequent use in past)made me recoil20%7.69

On the question of expiration they say "No, as long as Prime® has been stored properly, it will last indefinitely." (my emphasis)

But, overall it's clearly reactive with Oxygen, so repeated usage of say, the drop-dispenser bottles (like the oldest one) where new air comes in with each use and the product is inverted each time is going to keep mixing O2 into the solution.
The Rongalite and the HMS (dissociating to sulfite) are oxygen scavengers so they'll continue to react - slowly - with new O2 getting into the bottles. The oldest bottle seems to have actually depleted its O2 scavenging ability enough that it wasn't zero O2 in the bottle even though it hadn't been touched in some months.
Additionally, this reaction with O2 is also obviously degradation of the product, leading to increased dissociation and thus pH drop, and this seems to correlate to the strength of smell.

As a practical matter, the bottle opened 4 months probably wasn't much chemically different from the unopened. And in my testing for the report, I found similar - that a months-old bottle of Prime was within 20-30% of the ingredient amounts of a new bottle.

So the opposite of "store properly" - open a bottle, get new air in, cap and shake every day. I bet you'd be able to degrade it pretty quickly.

This discussion applies to all the other products as well, of course - HMS alone seemingly degrades faster than rongalite or rongalite+HMS mix, just from personal observation.
 

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I checked 3 Prime bottles of different ages for the question of smell and stability. I measured dissolved O2 and pH in the bottles as well.

BottleOdordissolved O2pH
never openedbarely detectable0%9.37
opened 4 monthsstrong0%9.33
over a year (frequent use in past)made me recoil20%7.69

On the question of expiration they say "No, as long as Prime® has been stored properly, it will last indefinitely." (my emphasis)

But, overall it's clearly reactive with Oxygen, so repeated usage of say, the drop-dispenser bottles (like the oldest one) where new air comes in with each use and the product is inverted each time is going to keep mixing O2 into the solution.
The Rongalite and the HMS (dissociating to sulfite) are oxygen scavengers so they'll continue to react - slowly - with new O2 getting into the bottles. The oldest bottle seems to have actually depleted its O2 scavenging ability enough that it wasn't zero O2 in the bottle even though it hadn't been touched in some months.
Additionally, this reaction with O2 is also obviously degradation of the product, leading to increased dissociation and thus pH drop, and this seems to correlate to the strength of smell.

As a practical matter, the bottle opened 4 months probably wasn't much chemically different from the unopened. And in my testing for the report, I found similar - that a months-old bottle of Prime was within 20-30% of the ingredient amounts of a new bottle.

So the opposite of "store properly" - open a bottle, get new air in, cap and shake every day. I bet you'd be able to degrade it pretty quickly.

This discussion applies to all the other products as well, of course - HMS alone seemingly degrades faster than rongalite or rongalite+HMS mix, just from personal observation.

this set of observations may be especially important for people using these products to dechlorinate tap water, which is likely the main time some would use it frequently for an extended period.
 
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this set of observations may be especially important for people using these products to dechlorinate tap water, which is likely the main time some would use it frequently for an extended period.
Yep, that was exactly how I was using the oldest bottle (before I switched to thiosulfate based product).
Dechlorination of a gallon or two here and there repeatedly.
 

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Very interesting paper and discussion. Do you know how Brightwell Erase CL stacks up as far as its ingredients? I had been way overdosing a boxfish in QT with that (3.5x the dose that allowed, daily for 3 weeks). He is exhibiting twitching behavior (skin scrape ruled out parasites, hyposalinity 1.009 for 45 days). Vet seemed it ammonia burn but also told us to stop using the binders stating it could irritate his skin. Having read your paper I am anxious now about toxicity. Vet said the binders can stay in systems for 2 months. You might know more. We've done massive water changes since.

Also, could you confirm, ammonia salicylate tests are not accurate when you dose binders? Thanks.
 
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Very interesting paper and discussion. Do you know how Brightwell Erase CL stacks up as far as its ingredients?
Thanks. Not sure how I missed Brightwell's product, probably because the product name just suggests chlorine.

It claims ammonia removal and includes this language "Testing for Ammonia: When using this product, be sure to measure ammonia with a test kit featuring ammonia salicylate reagent rather than Nessler’s reagent; Nessler’s reagent will give an incorrect positive reading of ammonia due to the manner in which the reagent interacts with the active components of Erāse-Cl."

this language is common with the products containing HMS (hydroxymethanesulfonate). So yes, I expect that's true here.
I think it's unlikely the dose is high enough for the product itself to cause toxicity, but the fact that it is not actually removing ammonia may be a concern.

Yes, and these products certainly interfere with salicylate total ammonia test.
 
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(Finally....)

Part 6: Extras - Overdose toxicity concerns, nitrification effects. Test method interference.
In part 5 we see that the amount of HMS / rongalite provided is far too small to achieve a significant ammonia removal effect (Fig 11), but if it were overdosed well beyond the recommended dosage (Fig 12) then it would remove measurable ammonia. So why not simply add more, and far exceed the allowed label maximum dosages - for instance using 30x ClorAm-X instead of the maximum recommended of 10x? This 30x dose would be 7.4mM of HMS and according to the trend in fig. 11, might allow 48hr lowering of ammonia to ~60% of original. There are a number of potential chemical concerns with such a high amount.
To get an estimate of how much dissociation would occur immediately when this amount of ammonia remover is added, pH and the acidification - in meq/L is shown below.


AD_4nXebpXspwWn-3yQr-8Cj5gv8Jig70Dga87io-vUfQuPlSPaTvfzcZ76cv08J6mecCzwX9K2s8xYyh37cyplNrEDmNZi0qdBiNEnx27SOi86eZXIQP0jhUOBUl7FaYvHQZB-xRYcL8t8rKDQRjou8Y5Y9qlOP


Figure 13. The molar equivalent of a 30x dose of ClorAm-X (7.1mM of HMS, rongalite or mix) was added to aquarium water while stirring. The initial pH drop over 3 minutes is shown, and the equivalent acidification in meq/L is annotated. The dissociation of HMS is 0.180 mM out of 7.1mM or ~2.5% at this high dose.

Using the above estimate of 2.5% initial dissociation for HMS, we can think about some of the chemical concerns with such a high hypothetical dose. The table below lists some of these.
overdose_table.png

Table 4. Some amount comparisons for adding a high dose of HMS that would be significantly effective at ammonia removal in under 48hrs. The amounts in the middle column are what would be released if the compound fully dissociated. This would happen over a number of days to weeks. The right column gives estimates of the released amounts by initial dissociation.

Adding this amount of HMS makes it a major constituent of saltwater, out-massing Ca, K, and everything else except Na, Cl, Mg, and SO4. The separate parts of sulfite and formaldehyde would certainly be concerning if released at once, but that does not occur. Instead some small percentage is released initially, and more dissociates over subsequent days. Encountering chlorine, or buffering that kept pH elevated, more mechanically or biologically active water would all speed the dissociation, making this an uncertain estimate.
Additionally, as the compound dissociates, base is removed and pH measurements show a drop below 7 for saltwater, see below.


AD_4nXf60pYCpvW2YG1QLPIBaqHPVy6klaRjyZLQY_B7oPfPrj3O4i37-q5Xgg9sJxH27V8lEn2hvwspoD49DcSsE_boPrtyxnOES9XmdAjwl2JSIHBOwM1ByiCad4YDfruWDPGuF1c4BcvcrURZoOgOUMch7ow

Figure 14. The ClorAm-X doses up to 30x (7.1mM of HMS) were added to aquarium water of initial pH 8.2, the highest dose pushed pH below 7.0 - and below pH measurement indicator range, while lower doses had modest and temporary pH drops.

The sulfite (or sulfoxylate) contained is also capable of scavenging many times the amount of O2 that the water can hold but this would happen quite slowly. The formaldehyde bound in the compound is much higher than a typical recommended fish-theraputic dose of ~9ppm HCHO (1mL / 10 gallons of 37% HCHO). Again, only a small percentage of this is ever released at once.

Apparently, toxicity concerns of such a high ammonia remover dose are not simply theoretical. A study that tested Prime in shipping bags [11] found that fish treated with approximately this level of Prime (0.5% by volume = 6.5 mM of combined HMS+rongalite) suffered toxicity “Although no ammonia accumulation was detected in the bag amended with the chemical ammonia remover, one fish was deceased, and another fish would have perished without intervention.” The fish - banggai cardinals - both suffered toxicity/mortality within 24 hours, even though O2 was kept over 70%, and pH stayed in the 7’s - while all fish in other treatments including untreated ammonia appeared normal for 3 days. Also, from personal observation on two occasions, cultured tigriopus copepods suffered significant (>50%) mortality in < 6 hours when exposed to 7.4mM and 9.8mM HMS in pH 8.4 saltwater with or without ammonia present - compared to little observed mortality in the copepods exposed to 30ppm ammonia with no HMS. Under this level of HMS or rongalite, nitrification activity is also measurably interfered with as detailed below.
Identifying which of the water-stressing properties of HMS & rongalite is responsible for these observed toxicity effects is difficult, and the purpose of this discussion is not to determine some safe dose. The intent is simply to point out that the maximum label-allowable dose recommendations from these products have some basis in water quality, and exceeding these doses in hopes of greater ammonia removal seems to create poorer water quality than just the ammonia toxicity alone that the compounds are meant to remove.

Effect on cycling bacteria
The hobbyist might wonder if the small effect of ammonia removal available by these chemicals could be stacked with the activity of nitrifying bacteria to help remove ammonia faster. On the other hand, nitrifying bacteria sellers have suggested that ammonia removers prevent the bacteria from working effectively.
In this experiment, aquarium water was spiked to 10ppm total ammonia, and bottled bacteria (Fritz + Tetra) were added. Ammonia removal chemicals in the form of HMS or rongalite were added once nitrite production was observed the next day. The amounts added ranged from molar equivalents of 1x to 30x doses of ClorAm-X (0.24 to 7.1mM of HMS or rongalite). The samples were in sealed beakers with 50% water volume and headspace and placed on orbital shaker. Each beaker also had an 0.15mL Red Sea scoop of dry aragonite sand to buffer against the extreme pH lowering seen in Fig 14. Twice a day the beakers were opened and air in headspace changed, re-sealed and shaken for 3-5 times to allow O2 and other gas exchange. Ammonia (total ammonia, and NH3 films), nitrite, and pH were monitored.
Below is the ammonia clearance and nitrite production of the first week.
AD_4nXdA9thWkPbU3eYuQYAmVcTM_T0afUZAsXMkBthKT3eRnAuy-qVV86zg19uJgXxQ8_QjYU4UdthbK1pJxDnonyFhA48QaJXuQC6ojVlPyw42t-RrdAoVC6zlUY6BSQ3covz9btUdQMTSoblLZqvfc2cPNZI

Figure 15a. Total Ammonia (more interference) and nitrite (less interference) tests show that the zero and lowest chemical treatment levels 0.24mM, 0.71mM, and 2.4mM brought ammonia to zero and nitrite near max by days 5-6. The highest chemical treatment level is harder to evaluate but nitrite is being produced, though slower.
AD_4nXedMEAHP8a0wFfn7299XRTjPvEBCWroXfbIhXoGaUsrcN-hXYdCVIe5HwifdQUJN-BeYdJS_cgT57ccptvqgyiQOrixJ8b4I-Mz2kEhFCy4yIy0JVZ2gzlYXi9XM9xlOAt_gSukwWhzfXinDauc36BMJso

AD_4nXe3nEK5BUPsx93HDcuDy16_GcVx9kf-PAqy3sH5bmgt5XhPrpbvbBq82VWz4BErN1UlkKNR7KnfxxBpUoGQYuDZPIy15e_Z29MaKfiUzZ2lCh8Fym5Jx1QWEJvBymomZ87CoFLhcw77Av2skX6heYSblDhZ


Figure 15b (top). Free Ammonia, NH3 on day 4 - showing that the highest concentrations of HMS (bottom beakers) and rongalite (top) were a little slower on removing ammonia - slightly more green. Blue disk is the control that got no bacteria.
Figure 15c (bottom). Free Ammonia, NH3 on day 6 (beakers in same orientation) the higher concentrations (beakers on the right) retained none or only slightest flush of green, which was cleared by day 8.

The NH3-sensing films avoid the interference and corroborate that ammonia is being removed by the bacterial products, though it took slightly longer to do so in the samples with high enough ammonia-removal chemicals to be semi-effective.

Later, however, the effects on cycling were more pronounced, as seen below.

AD_4nXd3l2nkXJuduq-g3yMeom1jp5dhXE3kXqfmKk0vwwzbQRKkT-NN-e3WK8z4Q8l42U8tYHdkBzD2FQ0XIPKarh8VZTNtmn98yntfLV8jzC03Ulfibs3RGkPvIWcFEcvjJ_3LPR2KMEiUVentqeJy3JS1Rirg


Figure 16a. Total Ammonia and nitrite tests show that in the highest HMS and rongalite samples, ammonia reappeared around days 23 (HMS) and 29 (rongalite). The ammonia was no longer being cleared by the bacteria as it was in the first week, and nitrite similarly was not being cleared either.

AD_4nXe4DaqojkA2UYrQt1Qd2IEFj5iNAuatKD5Kig0y7ZjzEu_mccLoUizTf99UP18VFU6kI6tfkMBjtljerShHXXwTGL9YfciY96cc1R3hKWMxJNls4B24WXAFXq0df-R2f6jfT0fHE1_Im5VqJeeD05mx06aC

Figure 16b. The NH3-sensitive disks agree with the total ammonia tests that ammonia was increasing starting around days 23 (HMS - left beakers) and days 29 (rongalite - right beakers).

A straightforward explanation (but not the only possible one) is that the ammonia removing chemicals at the highest concentration had bound some fraction of ammonia consistent with testing demonstrated earlier, and once that bound ammonia product - aminomethylsulfonate - eventually broke down, the ammonia was detected again weeks later. In the meantime, it’s clear that the conditions in these beakers had become unsupportive of nitrification, both ammonia oxidation and also clearly nitrite oxidation. It also suggests that under these conditions, the bound ammonia product is not available to nitrifying bacteria. The pH data also below suggests a timeline for the breakdown of the HMS and rongalite products and byproducts similar to the ammonia data.
AD_4nXe2BYEsGUE4VMxtpiqhVbErd5Y7ISNWzKBMmADaZtb5e9fqOKxgQerd1zqVujGr1iEXa58b7zS5z8hrRtsrD49P4fDQ-lgR35MszIhCTPDRmbVGdKsB0WsFT_rGYWM7_qQmKsXBLvRaHx_C8OjLeMm3tVjo


Figure 17a (left). The pH data indicates that most breakdown activity had finished in the lower concentration samples weeks earlier than in the highest concentration set.
Figure 17b (right). Nitrate increase as measured by change in Hanna NO3 was seemingly textbook across all samples that cleared nitrite, NO2. The highest HMS and rongalite samples couldn’t be measured because ammonia, nitrite or both were still not cleared by day 42.

The pH data above suggest that at the high HMS and rongalite concentrations, there is breakdown of these chemicals and byproducts that is ongoing for longer the higher the concentration - at the overdose level explored here, the process takes weeks even though the samples had constant gas exchange.
The nitrate data suggests that no detectable fraction of ammonia or nitrite was chemically removed in a way that bypassed the nitrification process. Some products claim nitrite removal, likely on the basis of the known reaction between sulfoxylate and nitrite that converts nitrite to nitric and nitrous oxides [8]. Since those would be lost from the sample via gas exchange, we can say no such reaction occurred here to any detectable degree.


Test method interferences

In Part 1 it was discussed briefly that HMS and rongalite create significant difficulty in correctly measuring ammonia due to interference with various chemical tests. There are a large number of sources of all kinds - from patents [6] to hobby product descriptions [12][13][14][15], aquaculture publications[16][17], and academic publications [18],[19],[20],[21],[11],[22] etc… that either explicitly or implicitly suggest that a salicylate total ammonia test is appropriate for measuring ammonia when treating with HMS or rongalite. Despite these sources, there is in fact significant interference with the salicylate total ammonia method that makes such measurements unreliable.

Hach describes that the salicylate total ammonia test uses hypochlorite to react with ammonia in the sample to form monochloramine as an intermediate, which then reacts with salicylate. Then that aminosalicylate is oxidized (nitroprusside used as a catalyst) to form a blue product, which in the yellow test solution appears green [23]. The entire reaction takes place at elevated pH >9.
Under these conditions, based on the chemistry of HMS and rongalite explored in parts 3, 4, and 5, we can clearly say how HMS and rongalite would affect the test - by reacting with the hypochlorite almost instantly. If the amount of dechlorination from HMS or rongalite is too great, then the hypochlorite remaining would be too small to fully complete the reaction. If the HMS or rongalite concentration is small compared to the hypochlorite in the test reagent, then the dechlorinating sulfite/sulfoxylate portion of HMS/rongalite is rapidly converted to sulfate and all the containing formaldehyde is released.
The formaldehyde itself interferes with the functioning of the salicylate ammonia test kit and shows erroneously low values for ammonia - small amounts can have considerable interference as shown below.
AD_4nXcggV4BlL79SwSj0Khaetxih5mKBrPP_QonJwe-_-1H9gRK_eVQVtL0EYrvsQMAcvm3AxbUXHCP2cMULIuGdcnsQzi0YGMqqhAWJjZEWJxpmio8F0BgsQjFXm-J36dT3PXwKuCDqM7tlq97BLustQXujzM

Figure 18. Total ammonia salicylate method is significantly interfered with by formaldehyde at even a few ppm. A standard 1x dose of ClorAm-X contains ~7.4ppm formaldehyde, when liberated.
The lowering of the measured value of ammonia is significant, but formaldehyde does not actually remove ammonia or bind it in a meaningful way. This was previously demonstrated in fig. 8 where formaldehyde alone did not actually cause any lowering in the true ammonia level - unless it was accompanied by sulfite to complete the reaction scheme involving HMS from the thesis by Brown[4].
While almost no sources addressed the idea of test kit interference, one source [24] explicitly considered the question of whether formaldehyde actually lowered ammonia in aquaculture settings or simply interfered with the test methods. They concluded “The Nessler method was found to give an intense yellow color and erroneously high ammonia values in the presence of formaldehyde…The salicylate method failed to detect TAN in the presence of formaldehyde, giving readings of 0.0 and 1.0 mg/L TAN for paired samples with and without addition of 100 ppm formalin, respectively. However, ammonia probe measurements were not affected by 100 ppm formalin, indicating that ammonia and formaldehyde did not react under the conditions in the system." Thus if ammonia measurements are needed in the presence of HMS, rongalite, or formaldehyde then both Nessler and salicylate kits are ineffective and measurements of NH3 by gas-permeable membranes such as in ion selective electrodes (“ammonia probe” in the above paper) or color-changing films as done in this report are necessary - and the pH changes that affect the NH3/NH4+ ratio must be tracked.
In fact, the patent [6] claiming removal of ammonia and chloramine by rongalite (unintentionally) demonstrates that the apparent ammonia decrease from rongalite in a total ammonia chemical test is the same as for formaldehyde, and thus the rongalite effect presented is simply the interference from the formaldehyde contained in the rongalite as shown below.
AD_4nXdqQsgHatixnPS7jEAstR9XHls-ngQQhFfaM1MS0D12ZDzDSym0MuTZt7B0k-W5geALfjuUrEQQr8V10ZyAOUzuRsZdUpaHnFXjQmq9xQuui8sZhUguMJSdbu6nIv1IgdiJBwq_mY7u3liBzK_IMhR-7I0U


Figure 19. Data from Tetra rongalite patent demonstrates that the measurement of total ammonia by (salicylate) chemical test with rongalite is almost exactly the same as with formaldehyde alone. Ratios of 1:1 to 1:3 between ammonia and rongalite/HCHO and reactions in de-ionized, tap, and sea water all show equal results between rongalite and equimolar amount of formaldehyde.
In short, although there have been considerable numbers of published papers, articles, patents etc that discuss the reactions of ammonia with HMS and rongalite in an aquaculture context, very few have explicitly considered whether the measurement methods themselves are interfered with by the substances examined. And since HMS and rongalite each dissociate into two parts that both have the potential to interfere with chemical tests - these considerations are required to properly interpret what reactions may or may not be happening.


References
1. EPA. (2000). Wastewater technology fact sheet dechlorination. Environmental Protection Agency.
https://www3.epa.gov/npdes/pubs/dechlorination.pdf

2. Song, S., Ma, T., Zhang, Y., Shen, L., Liu, P., Li, K., ... & McElroy, M. B. (2021). Global modeling of heterogeneous hydroxymethanesulfonate chemistry. Atmospheric Chemistry and Physics, 21(1), 457-481.

3. Kuhns, J. F. (1987). Method and product for removal of chloramines, chlorine and ammonia from aquaculture water. U.S. Patent No. 4,666,610. Washington, DC: U.S. Patent and Trademark Office.

4. Brown, K. H. (1999). Kinetic studies on the reaction of formaldehyde with amines in the presence of sulfite (Doctoral dissertation, Durham University).

5. Danehy, J. P., & Zubritsky, C. W. (1974). Iodometric method for the determination of dithionite, bisulfite, and thiosulfate in the presence of each other and its use in following the decomposition of aqueous solutions of sodium dithionite. Analytical chemistry, 46(3), 391-395.

6. Gunter, R. (1988). Agent for the elimination of active chlorine compounds from water. U.S. Patent No. 4,786,434. Washington, DC: U.S. Patent and Trademark Office.

7. Makarov, S. V., Horváth, A. K., Silaghi-Dumitrescu, R., & Gao, Q. (2016). Sodium dithionite, rongalite and thiourea oxides: chemistry and application.

8. Wikipedia contributors. (2024, May 14). Sulfoxylic acid. In Wikipedia, The Free Encyclopedia. Retrieved June 2024, from https://en.wikipedia.org/w/index.php?title=Sulfoxylic_acid&oldid=1223734514

9. Garrick, A. (2009) Formaldehyde Determination by Sodium Sulfite Method. Oregon Department of Environmental Quality

10. Wikipedia contributors. (2024, May 26). Sodium thiosulfate. In Wikipedia, The Free Encyclopedia. Retrieved June 2024, from https://en.wikipedia.org/w/index.php?title=Sodium_thiosulfate&oldid=1225820101

11. Urakawa, H., & Sipos, A. J. (2020). Application of the consortia of nitrifying archaea and bacteria for fish transportation may be beneficial for fish trading and aquaculture. Aquaculture research, 51(8), 3429-3442.

12. AquaScience Research Group, Inc. (2001). ClorAm-X® Ammonia, Chlorine & Chloramine Remover. In Thepondoutlet.com. Retrieved June 2024, from
https://www.thepondoutlet.com/shop/images/ClorAm-XDataSheet.pdf

13. Kordon LLC. (2024). AmQuel®The Original AmQuel Product For Chlorine, Chloramine, And Ammonia Detoxifier. In kordon.com. Retrieved June 2024, from
https://www.kordon.com/kordon/products/water-conditioner/amquel#contraindications-toxicity!

14. Seachem Laboratories, Inc. (2024). Seachem Prime FAQ. In seachem.com. Retrieved June 2024, from https://www.seachem.com/prime.php

15. Fritz Aquatics. (2024). Fritz A.C.C.R. Liquid | Directions and Dosage. Fritz A.C.C.R. Liquid. Retrieved June 2024, from https://fritzaquatics.com/products/fritz-accr-liquid

16. Francis-Floyd, R., Watson, C., Petty, D., & Pouder, D. B. (2009). Ammonia in aquatic systems. UF/IFAS University of Florida (UF)/Institute of Food and Agricultural Sciences (IFAS), FA, 16, 1-4.

17. Strange, R. (2004) Recirculation Aquaculture: Water Quality: 5. Ammonia. University of Tennessee Knoxville Retrieved June 2024, from https://web.utk.edu/~rstrange/wfs556/html-content/05-ammonia.html

18. Riche, M., Pfeiffer, T. J., & Garcia, J. (2006). Evaluation of a sodium hydroxymethanesulfonate product for reducing total ammonia nitrogen in a small-scale rotifer batch culture system. North American Journal of Aquaculture, 68(3), 199-205.

19. Sharma, A., & Semmens, K. EFFECT OF SODIUM HYDROXYMETHANESULFONATE ON AMMONIA AND RELATED WATER QUALITY PARAMETERS.

20. Abdel Rahman, S., Attallah, M., Abu Zeid, M., Hellal, A., & Abdel Razek, F. (2016). Evaluation of an intensive culture system for the culture of the rotifer, Brachionus plicatilis using ammonia removers. Egyptian Journal of Aquatic Biology and Fisheries, 20(1), 15-21.

21. Bentley, C. D., Carroll, P. M., Watanabe, W. O., & Riedel, A. M. (2008). Intensive rotifer production in a pilot‐scale continuous culture recirculating system using nonviable microalgae and an ammonia neutralizer. Journal of the World Aquaculture society, 39(5), 625-635.

22. Cebreros, A. H. R., Castro, L. I., Carlock, E. G., Sánchez, J. L., & Lajonchère, L. A. (2017). Pilot-scale production of the rotifer Brachionus sp. under different culture systems. Revista de biología marina y oceanografía, 52(3), 539-549.

23. Hach. (2024). Ammonia and Ammonium. Hach.com. Retrieved June, 2024, from
https://www.hach.com/parameters/ammonia?

24. Heinen, J. M., Weber, A. L., Noble, A. C., & Morton, J. D. (1995). Tolerance to formalin by a fluidized‐bed biofilter and rainbow trout Oncorhynchus mykiss in a recirculating culture system. Journal of the World Aquaculture Society, 26(1), 65-71.
 

Dan_P

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@taricha, loved Part 6 extras.

Just a question about growing nitrifying bacteria in glass beakers. I typically see a bit of dust or fuzz develop on the container bottom when I grow denitrifying bacteria in an acrylic or polyethylene container. Did you observe anything like this?
 
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taricha

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@taricha, loved Part 6 extras.

Just a question about growing nitrifying bacteria in glass beakers. I typically see a bit of dust or fuzz develop on the container bottom when I grow denitrifying bacteria in an acrylic or polyethylene container. Did you observe anything like this?
I do see particulates in these containers, but it's never been obvious to me if the particulates are greater than what was added when I inoculated the container. Sometimes the inside of the container feels slimy (biofilm) after culturing.
 

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My take after reading 100 plus posts that mostly flew over my head and gave me flashbacks of high school where sitting next to a pretty girl only reason I stayed awake being if I need to solve for spikes in ammonia or new setups best have a bottle of Fritz Turbo 900 in the fridge and go old school nature at it's best vs relying on these marketing hyped solutions that at best might be a placebo and fact they work only because fish might be more tolerant of ammonia based on another thread by Randy. Yeah, that works for me :thinking-face:
 
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@GARRIGA I don't think you missed the point at all :)
That's, in part, a takeaway for me as well.
 

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I do see particulates in these containers, but it's never been obvious to me if the particulates are greater than what was added when I inoculated the container. Sometimes the inside of the container feels slimy (biofilm) after culturing.
OK thanks. Something to sort out on a rainy day.
 

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A question. I have a seneye Reef v6. I find it puzzling that for 6 months, NH3 has sat at 1.001-1.005, despite the Hanna TAN tester showing anywhere from 0.06-0.50. Maybe that proves your point as I am dosing Erase CL. Basically calculating NH3 from Hanna TAN using Hamza, I obviously get to much higher numbers than 0.005, so I basically just started ignoring the thing. Should I ignore the Hanna TAN and solely rely on the seneye reading? It also has an NH4 reading which I don't get at all, it shows around 20ppb usually. Since you mentioned seneye in this research I thought you might have some knowledge on this.
 

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A question. I have a seneye Reef v6. I find it puzzling that for 6 months, NH3 has sat at 1.001-1.005, despite the Hanna TAN tester showing anywhere from 0.06-0.50. Maybe that proves your point as I am dosing Erase CL. Basically calculating NH3 from Hanna TAN using Hamza, I obviously get to much higher numbers than 0.005, so I basically just started ignoring the thing. Should I ignore the Hanna TAN and solely rely on the seneye reading? It also has an NH4 reading which I don't get at all, it shows around 20ppb usually. Since you mentioned seneye in this research I thought you might have some knowledge on this.
Just to clarify, your Seneye device is reading 1 ppm free ammonia and the Hanna ammonia Checker indicates a total ammonia of 0.06 ppm?
 

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Just to clarify, your Seneye device is reading 1 ppm free ammonia and the Hanna ammonia Checker indicates a total ammonia of 0.06 ppm?
Apologies, I was unclear. The Seneye Reef v6 reads 0.001 to 0.005 ppm NH3 and around 15-20 ppb NH4 (attaching sample screenshot from yesterday). Hanna was reading around 0.30 ppm TAN yesterday with dosing Erase CL (5ml 2x day). I'm not sure what to believe now that I've read your paper. Seneye was not calibrated, not sure how since it has no adjustment setting it seems pointless.

Detail is Seneye NH3 lowers from 0.005 to 0.002 when I dose Erase CL. I suspect it's because of the pH decrease it causes. Thanks Dan.

Screenshot_20240729-125715.png
 
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Dan_P

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Apologies, I was unclear. The Seneye Reef v6 reads 0.001 to 0.005 ppm NH3 and around 15-20 ppb NH4 (attaching sample screenshot from yesterday). Hanna was reading around 0.30 ppm yesterday with dosing Erase CL (5ml 2x day). I'm not sure what to believe now that I've read your paper. Seneye was not calibrated, not sure how since it has no adjustment setting it seems pointless.

Detail is Seneye NH3 lowers from 0.005 to 0.002 when I dose Erase CL. I suspect it's because of the pH decrease it causes. Thanks Dan.

Screenshot_20240729-125715.png
The Seneye unit calculates the total ammonia to be 20 ppb which is 0.02 ppm. If the Seneye temperature and pH are not accurate, or the free ammonia reading is off, this calculation will be off as well.

If Erase CL is a dechlorinator, this could cause the Hanna Checker to read low. I would trust the Checker for measuring total ammonia if a declorinator is not used.

And yes, if Erase CL lowers the pH, free ammonia will decline.
 
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