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May 18th, 2013, 10:58am
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Chlorine residual and BOD (Read 873 times)
paula
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Chlorine residual and BOD
Apr 24th, 2012, 12:37pm
 
I work at an activated sludge treatment plant with a design capacity of 14.2 MGD (stormwater, household and industry). Our final sampling point is after our secondary clarifiers (before chlorination). We use automatic samplers to collect 24 hour composite samples for BOD analysis.  I run a total residual chlorine check monthly on the composite just to document that the value is at or below the required 0.05 mg/L Cl2. I did the monthly check today and the result was 0.09 mg/L, and therefore needed dechlorination before BOD analysis. I have been checking this for a year and a half and haven't had a value greater than 0.03 mg/L. Any thoughts?

One thing that might make this day different than the others I have tested is that we had very heavy flows (>30mgd) yesterday due to rain. This caused us to have a high TSS value in the composite. Can solids affect the TRC test? Also, due to filamentous bulking we were chlorinating the RAS lines for 9 days. The chlorine was shut off this past Sunday though. Is it possible to have a residual from that even though it's been off for 3 days? Is it possible the solids are "holding" chlorine?

Any advice is appreciated.
Thanks!
Paula
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David S.
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Re: Chlorine residual and BOD
Reply #1 - Apr 25th, 2012, 9:07am
 
I guess the first question is how are you testing for residual chlorine?  There could be inherent, slight positive interferences that have emerged in the light of your recent heavy stormwater.  One obvious one is mentioned in your post, suspended solids.  That is mostly going to be a factor when doing a colorimetric determination.

Another thing to consider is that fact that most chlorine tests aren't actually testing specifically for chlorine.  Rather, they test for compounds that behave like chlorine does, specifically its oxidizing properties.  Witness the fact that potassium permanganate can be used as a standard for your residual chlorine test.  This is not because it is naturally the pink color of the DPD result, but because it reacts like chlorine does with the DPD reagents.

Is there any particular reason you have a limit of 0.05 mg/L chlorine as your limit?  Standard Methods does not specify a lower limit of chlorine.  The only guidance it gives is in how to neutralize the chlorine detected.  Since you neutralize to the removal of color from the starch-iodine reaction, that has always been the detection method I utilized for the presence of absence of chlorine when doing BOD.
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paula
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Re: Chlorine residual and BOD
Reply #2 - Apr 25th, 2012, 10:28am
 
David,

I use the DPD colorimetric method to test for TRC. I agree that it was most likely the solids or other oxidizing compounds in the water.

Our "limit", which is more of a guidance, comes from our Department of Environmental Protection. We are permitted through the state, and not a NPDES permit. The instructions are that if the value is less than or equal to 0.05 mg/L, no dechlorination is necessary. Between 0.05-0.09 mg/L, the sample could be kept by the window for an hour to allow the chlorine to dissipate. Above 0.1 and dechlorination with sodium sulfite must be done.

During chlorination season, our effluent limit is 0.24mg/L TRC

What level of chlorine do you think is considered enough to warrant dechlorination for the BOD procedure?

Thank you for your response.
Paula
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Re: Chlorine residual and BOD
Reply #3 - Apr 25th, 2012, 11:01am
 
I don't have a hard and fast number for what qualifies as needing treatment.  We always would check for oxidizers in our BOD samples by slightly acidifying the sample, adding the potassium iodide solution, and then adding a few drops of starch indicator.  If there was any blue color we would titrate with sodium sulfite to remove the blue and add that proportionately to the sample to be incubated.
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Re: Chlorine residual and BOD
Reply #4 - Apr 26th, 2012, 1:16pm
 
Like others, I can't think of a range of values like you describe for dealing with "chlorine" in samples for BOD analysis.  Most commonly I see analysts do a visual check with DPD...any visible pink and they run a titration and adjust samples accordingly.

Typically, solids/particles in the sample will be "zeroed" out with a sample blank and the resulting value after addition of the DPD.  I'd suspect your samples have low TSS, but perhaps the higher flows bumped this up?  Make sure you are running a sample zero.

Drinking water plants in some areas run a chlorine-destruct sample prep to determine how mucn non-chlorine interference is present (typically from manganese).  Perhaps overkill for your situation, but it is an option to see if its non-chlorine components reacting with the DPD.

Might want to run a few more TRC's to get a feel for trend vs flow for your own knowledge.
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Re: Chlorine residual and BOD
Reply #5 - May 24th, 2012, 7:54am
 
If we have any chlorine present we must dechlor.  We check by the method stipulated in SM 5210 B.  Any color presents and we remove it with the sulphite solution and then proportionate to remainder of sample volume.

Chlorine will reduce the number of bugs in your samples and give you a lower result which is a false value.  

~Eric
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Re: Chlorine residual and BOD
Reply #6 - May 30th, 2012, 7:47am
 
I would expect a higher residual at higher flows, if the dosage is the same, as the retention time is less and the contaminates that contribute chlorine demand has less time for reaction.
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