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    Thread: PP question

    1. #21
      Koi Story's Avatar
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      Fish cannot live in a pond with a noticeable hydrogen sulfide odor; the pH would have to be too low (~5) and / or the H2S concentration too high.

      ks
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      For that which longer nurseth the disease,
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    2. #22
      Bill OTMS's Avatar
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      Quote Originally Posted by Roddy Conrad
      Like others say, if there is pink or purple color, the PP is still active, and if there is no trace of pink of a sample taken in a white 5 gallon bucket, you know it is gone.
      Also, in general, an ORP reading above 400 indicates residual active PP.
      As a sideline to this discussion, a test for chlorine after a PP dose shows active chlorine when there is none, since the chlorine test simply indicates whether an active oxidizer is present or not. Also, for about 12 hours after the PP is spent or reversed, the chlorine test will give a positive reading even though the PP is completely spent or reversed. The point is a chlorine test is meaningless for at least 12 hours and perhaps 24 hours after a pond has been dosed with PP.
      Now, that's good to know. Thanks, R.

      Oh, yea. Just coming into the thread.
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    3. #23
      schildkoi is offline Inactivated
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      You taught me something Roddy

      I didn't know that a gas such as Hydrogen Sulfide could be oxidized. So i did a little reading up and found out that you were absolutely correct! But, I am sure glad you are a chemist because the literature I read says that it can be unpredictable and dangerous!

      Potassium Permanganate

      Potassium permanganate is a strong oxidizing agent that can react with hydrogen sulfide in a variety of ways, depending on whether the stream is acidic or alkaline. In acidic conditions, the following reaction takes place:

      Pic 1 below









      Under alkaline conditions the following takes place:

      Pic 2 below





      Under conditions that are in between acidic and alkaline pHs, a variety of reactions occur, yielding elemental sulfur, sulfate, thionates, dithionates and manganese sulfide end products. Potassium permanganate has been fairly effective when added to the sludge dewatering operation, where it is added to the suction side of the sludge pumps feeding the dewatering unit.



      Disadvantages: Dosages are difficult to predict and control in most liquid applications. The high cost and high dose, 6 or 7 parts of potassium permanganate are needed for each part of hydrogen sulfide, are discouraging. Safety precautions are required for handling and storage.
      Based on this, it wouldn't seem that 2 ppm of PP would be effective in this process. Perhaps the Hydrogen sulfide was off gassed due to the airation you set up instead?

      Steve
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    4. #24
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      What did he say
      The will of God will not take you where the grace of God cannot keep you. .....
      "I contend that for a nation to try to tax itself into prosperity is like a man standing in a bucket and trying to lift himself up by the handle." -Winston Churchill Zone 7a
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    5. #25
      Roddy Conrad's Avatar
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      Steve said that the oxidation of hydrogen sulfide requires a ratio of potassium permanganate 6 to 7 times the hydrogen sulfide to be effective at the oxidation. Since the odor of hydrogen sulfide is detectable at values as low as 0.01 ppm, adding 2 ppm PP gives a ratio of 200, which is many times the minimum level to oxidize it.

      So Steve verified by checking up on me that this old chemist was taking care of his fish by making sure any hydrogen sulfide in the muck was oxidized to safe sulfate ions before I cleaned out my water gardens in the Spring.

      Like I said before, I only did this once, when it was obvious I had a serious water quality problem from a faint odor of hydrogen sulfide when I started to clean it up. I stopped in my tracks, set up the PP, and oxidized it quickly with those twenty sequential 2 ppm PP treatments before continuing to clean up the pond to get it ready for the summer ponding season.

      Glad to see Steve is trained in looking up chemical reactions!
      Your koiphen chemist and environmental scientist.

    6. #26
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      okay am i right the 2ppm is the dosage for cleaning not bug zapping
      The will of God will not take you where the grace of God cannot keep you. .....
      "I contend that for a nation to try to tax itself into prosperity is like a man standing in a bucket and trying to lift himself up by the handle." -Winston Churchill Zone 7a
      I believe it can happen... Koi World Peace
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    7. #27
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      No Roddy, that is NOT what I said

      You said:

      Steve said that the oxidation of hydrogen sulfide requires a ratio of potassium permanganate 6 to 7 times the hydrogen sulfide to be effective at the oxidation. Since the odor of hydrogen sulfide is detectable at values as low as 0.01 ppm, adding 2 ppm PP gives a ratio of 200, which is many times the minimum level to oxidize it.
      That is NOT what I said. You infer that you only had .01 ppm Hydrogen sulfide. How did you know? I said that you were more likely degassing through the airation. In addition, you were most probably stirring up all of that muck with the airation.

      Noahsnana, In a clean pond, 1.5 ppm PP does the trick. Dose every other day for 2 doses. Gets Costia and Trich, Deep rooted Costia may require additional and varying treatments but this is the abnorm (1 in 100 cases). Some people use higher concentrations...usually due tro not having a clean system to start with.

      Steve

    8. #28
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      Quote Originally Posted by schildkoi

      Noahsnana, In a clean pond, 1.5 ppm PP does the trick. Dose every other day for 2 doses. Gets Costia and Trich, Deep rooted Costia may require additional and varying treatments but this is the abnorm (1 in 100 cases). Some people use higher concentrations...usually due tro not having a clean system to start with.

      Steve
      I understand :thumbsup:
      The will of God will not take you where the grace of God cannot keep you. .....
      "I contend that for a nation to try to tax itself into prosperity is like a man standing in a bucket and trying to lift himself up by the handle." -Winston Churchill Zone 7a
      I believe it can happen... Koi World Peace
      "The problem with socialism is that eventually you run out of other people's money." - Margaret Thatcher
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    9. #29
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      Steve;

      The formula's you posted are just two of them. I can name three more routes to end products using KMnO4 and H2S as the inputs. And it needs to be realized that all of the formulas you posted are EMPIRICAL and GENERAL in nature and reflect neither equilibrium effects, or time, redox levels, trace metals nor the catalytic effects of the manganate byproducts being produced. Essentially there aren't any hard and fast answers so the blanket statement that it takes 6 to 7 times the amount of H2S isn't accurate. You can actually get places rather quickly with anywhere from 2 to 25x the amount of H2S.

      No flame... just correcting a few assumptions.

      Roark
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    10. #30
      Roddy Conrad's Avatar
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      Any time the water develops a bad odor on any of my ponds and aquariums, out comes the PP and very soon my nose is very pleased at the absence of odor.

      Now when Lizzie puts on her favorite perfume, Sung by Alfred Sung, I leave the purple cloud "in the can", and enjoy the smell!

      We can write lots of pretty chemical equations, but my nose leads the way on this issue.
      Your koiphen chemist and environmental scientist.

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    11. #31
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      But Roddy

      My point is that the Hydrongen sulfide is trapped in the muck and very little releases when undisturbed. When disturbed I am betting is far above that .01 ppm youo quoted and thus the previous post of mine is even more applicable.

      Steve

    12. #32
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      Any time the water develops a bad odor on any of my ponds and aquariums, out comes the PP and very soon my nose is very pleased at the absence of odor.
      Roddy...please...... if your ponds are getting to the point that you can smell them then please give up this hobby and go back to stamp collecting....you should never be able to smell your pond or an aquarium. You're falling down on the job!!!

      Can you imagine when I had 80+ aquariums in my parents basement...probably 1800+ gallons of water if they could smell H2S or methane or dead algae or that general bad aquarium smell that comes with bad husbandry...I would have been living on the street............Please learn some husbandry for ornamental fish

      Alfred Sung, a Canadian btw...wouldn't cover that smell

      G

    13. #33
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      Talking

      Steve, your numbers are a bit skewed. This stuff makes for good reading, so I'll post it as a general addition to your reading list:

      - The lower odor detection limit (human, 50%, B=1.3) for H2S is 0.01 ppm to 0.047 ppm, (depending on the reference, with 0.01 ppm being OHSA's number and the higher number being from the Bureau of Mines, each of which tends to have some rather well-documented differences in opinion due to their obvious polarizations).

      - Goldfish (Carassius auratus) showed "observed stress" after a 96 hour exposure to 10,000 ug/L [Bull.Bur.Fish.No.22, U.S.Dep.Commerce]

      - Bluegill (Lepomis macrochirus) showed only a perceptible reduction in growth after a 200 day exposure to 1.5 ug/L [Chronic Effects of Low Levels of Hydrogen Sulfide on Freshwater Fish, Smith, L.L.J., and D.M. Oseid, 1975, Prog.Water Technol. 7(3/4):at 599-605]

      - Even Rainbow Trout fry (Oncorhynchus mykiss) which are routinely used as a rather fragile "benchmark" species in chemical testing managed to survive 24 ug/L for 72 hours [Effects of Hydrogen Sulfide on Fish Eggs and Fry, Smith, L.L., and D.M. Oseid, 1972, Water Res. 6(6):at 711-720]

      So while its clear that H2S is not a good thing, the truth is you can often detect it before it kills fish. Lord knows I've been to plenty of ponds where the water stank to high heaven and the fish, while not particularly happy, were still swimming. And eating. And would have throttled the pond owner if they had fingers and AK-47's with a banana clip.

      Put another way: If H2S was indeed toxic at the lower limits of human detection, AquaScapes would be bankrupt. hehehehe.

      Again... no flames... just data.

      Roark
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    14. #34
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      [QUOTE=Roddy Conrad] Since the odor of hydrogen sulfide is detectable at values as low as 0.01 ppm,
      Like I said before, I only did this once, when it was obvious I had a serious water quality problem from a faint odor of hydrogen sulfide when I started to clean it up. QUOTE]

      Quote Originally Posted by Roark
      - The lower odor detection limit (human, 50%, B=1.3) for H2S is 0.01 ppm to 0.047 ppm, (depending on the reference, with 0.01 ppm being OHSA's number and the higher number being from the Bureau of Mines, each of which tends to have some rather well-documented differences in opinion due to their obvious polarizations).

      Roark

      Does this mean that 0.01 ppm of H2S dissolved in water can be detected by smell?
      At what pH?

      ks
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      For that which longer nurseth the disease,
      Shakespeare, Sonnet CXLVII

    15. #35
      Roddy Conrad's Avatar
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      Roark's references and mine on the odor threshold of hydrogen sulfide are different. The hydrogen sulfide odor threshold varies from person to person from 0.001 ppm to 0.13 ppm in the references I found on the subject.

      I have had hydrogen sulfide detectable odors in my ponds and aquariums without any obvious adverse health symptoms of the fish. Since the values measured for fish health from hydrogen sulfide is very low as given below, I assume my personal odor threshold is fairly low, since it varies from person to person over such a huge range.

      TLM = Threshold Limit Value for death for the type of fish in water with this much hydrogen sulfide:
      TLm (Lepomis macrochirus, bluegill sunfish) 96 hours = 0.0448 mg/L
      at 21-22 deg C
      TLm (Pimephlaes promelas, fathead minnow) 96 hours = 0.0071-0.55
      mg/L
      TLm (Salvenilis foninalis, brook trout) 96 hours = 0.0216-0.038 mg/L at
      8-12.5 deg C
      Your koiphen chemist and environmental scientist.

    16. #36
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      I guess its just me

      From Roddy's and Roarks post, it would seem that Hydrogen sulfide is a non issue in a pond since you can "smell" it before it gets to a lethal level and that these low levels are such that 20, 2 ppm PP in 4 hours is more than enough to handle what hydrogen sulfide there may be.

      But now for the confusing part. How do Koi ever die from these levels (and they do die from Hydrogen sulfide poisoning)? Could it actually be that these levels can actually be much higher? Could it actually be that this gas is trapped in the muck at the bottom of the pond? Could it go undected until such time and this muck is disturbed? Could it be that TWA (time waited average) levels have little to do with it and that lethal levels can be triggered in a very short period of time? Could it also be that hydrogen sulfide could be in the total gas saturation measurement of the pond as well (at non lethal levels until muck is disturbed)?

      Final point:
      I think using PP as a pond cleaner is a very dangerous practice....short term or long term, take your pick and for a vast variety of reasons. 20, 2 ppm PP doses in 4 hours is, for lack of a better term, a very dumb practice, especially for typical hobbyists. Even at those rates the ability to use PP to clean the pond thoroughly (including all the muck in a "very dirty pond") is doubtful at best and the remaining "left overs" would still require removal (as well as the Koi during the cleaning).
      Steve

    17. #37
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      "Roark's references and mine on the odor threshold of hydrogen sulfide are different. The hydrogen sulfide odor threshold varies from person to person from 0.001 ppm to 0.13 ppm in the references I found on the subject". Roddy Conrad

      If this is about H2S dissolved in water a pH and a temperature have to be specified, because H2S ionizes in water. At a pH of 8 and at 77° F, 100% of the H2S is ionized (1)--not in gas form--and it cannot be smelled (neither degassed). Could you please post the reference?
      (1) The Nalco Water Handbook. Nalco Chemical Co., Frank N. Kemmer editor. Page 14.5, fig. 14.6.

      The following is from: http://aquanic.org/publicat/state/il-in/as-503.htm#Water's%20Chemical%20Factors (a link posted by HanoverKoiFarms)

      Appendix 1
      TABLE 3 Suggested water-quality criteria for aquaculture hatcheries or production facilities. Salmonid quality standards with modification for warm water situations. Concentrations are in ppm (mg/L). (Source: Modification from Wedemeyer, 1977; Piper, etc al. (Larsen), 1982)
      Chemical Upper Limits for Continuous Exposure and/or Tolerance Ranges
      Hydrogen sulfide 0.002 ppm (Larsen - 0.0 ppm)

      ks
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      For that which longer nurseth the disease,
      Shakespeare, Sonnet CXLVII

    18. #38
      Roddy Conrad's Avatar
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      Hey, you can post as much stuff as you want about this subject, it does not change the essentials.

      Those are:

      1. If you have potted plants in your pond, or rocks at the bottom of your pond, or gravel at the bottom of an aquarium, or you don't clean the pond bottom often enough, you will develop some hydrogen sulfide in these described situations. Disturb the hydrogen sulfide, and I guarantee you it will be detected by your nose! And it is not a good thing, we all agree about that!

      2. If you have some hydrogen sulfide, there is no doubt it is easily oxidized by potassium permanganate, in theory or practice. I described doing it in practice, Childers didn't like it much, okay, I agreed it is better to maintain your pond in a way that the hydrogen sulfide does not become detectable, and you don't need to react it away with PP. But there are still some readers of this board with Aquascapes ponds with rock bottoms, or a bunch of potted plants, so I thought maybe some of them might want a clue how to deal with emergency situations involving hydrogen sulfide in their ponds and pond water.

      2. Since we have folks "demanding sources", here is a direct quote from that set of books with the name "Encyclopedia of Chemical Technology" which sit handy on my shelves both at work and at home and get used regularly: "Hydrogen sulfide is readily oxidized by many oxidizing agents. The oxidation products depend on the oxidizing agent, its concentration, its molal ratio to the hydrogen sulfide, and the conditions of the reaction." A table is presented which shows, for example, hydrogen peroxide oxidizes hydrogen sulfide to sulfur at a neutral pH, and to sulfate at an alkaline pH.

      3. Hydrogen sulfide CAN exist in pond water for sure! There is no doubt about that! Aqueous solutions of hydrogen sulfide are weakly acidic. Hydrogen sulfide will react with sodium carbonate at a pH of 10 to 11 to make NaHCO3 (baking soda) and NaHS, but it won't react with NaHCO3 (sodium bicarbonate or baking soda) at normal pond pH ranges.

      4. My main source for the odor threshold and fish toxicity values come from primary MSDS (material safety datasheet) information for hydrogen sulfide. I could trace that information back to original source if I wanted, but I don't wantta, it is a pleasant hobby after all for me, not an obsession.

      5. You are better off managing your ponds and aquariums so they don't develop a detectable (by your nose) hydrogen sulfide odor. We run 9 ponds and 9 aquariums as a hobby, sometimes I don't do the maintenance of every pond and every aquarium on my preferred schedule, since at age 64 I still work a 50 to 60 hour work week at a demanding technical job, and plan to continue doing so for many years more. When I smell the stuff, I take care of it with PP quickly. You do it any way you want. But if you start stirring up the hydrogen sulfide pockets with fish present, without oxidizing it first with PP, you are very likely to have a pond or aquarium full of dead fish in a hurry.

      And, hey, flame away, I am used to it.
      Your koiphen chemist and environmental scientist.

    19. #39
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      Roddy I could pic away at the above post but but I won't....I think that what we are all kind of saying here is lets teach ponders the right way, the correct way........that's not to let things in your pond, be it a Koi pond or an AS pond, or an aquarium, get to the point where toxic gases are being produced...That is just poor husbandry.


      Yes they show up in plant pots and under some coping rock but they are not supposed to show up from crap build up. Especially at a point where a ponder ia afraid to touch the silt or has to use oxidizing chemicals to neutralize them.

      If a person can't maintain the system so that doesn't happen then they need to change things.......I'd love to have 80 tanks again and be breeding Discus, Angels, Oscars, Jacks and little SA's again but I know that I could never maintain them now so I don't have them. Maybe you should look at selling off some of those tanks

      G

    20. #40
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      Quote Originally Posted by Roddy Conrad

      4. (...) I could trace that information back to original source if I wanted, but I don't wantta, (...)

      And, hey, flame away, I am used to it.
      The above statement should have sufficed.

      “[the post was intended], not to contradict and confute, nor to believe and take for granted, nor to find talk and discourse, but to weight and consider.” Lord Bacon

      Thanks anyway,

      ks
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