BOD and COD Measurement

What is the correlation?

November 15, 2011 Derek Walker, Applications Development Manager Mick Dollenmayer, Regional Sales Manager
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Agenda

1. 1 2. 3. 3 4. 5.

Applications f BOD and COD measurement A li ti for d t COD and BOD: What are we really measuring? Methods used for compliance monitoring Understanding plant baselines and trends Correlation between COD and BOD measurement

6. Question and Answer Session

Why measure BOD and COD?

Why measure BOD and COD?

Evaluate the efficiency of treatment process and removal of organic compounds Effluent impact to receiving waters low oxygen demand For process control:
Activated sludge process: do we have enough O2? Food / Biomass ratios Ad anced treatment processes Advanced

Because we have to! (NPDES Permits and Reporting) Any other reasons?
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What are we measuring with BOD and COD?

BOD (biochemical oxygen demand): a measure of oxygen demand occurring when bacteria oxidize organic matter
Oxygen depleted by microorganisms (bugs) found in a water sample Strength of the waste stream

COD (chemical oxygen demand): a measure of the oxygen demand of a sample that is susceptible to oxidation by a strong chemical oxidant
O Oxygen depleted b chemical oxidation d l t d by h i l id ti Organics: carbohydrates (sugars/cellulose), proteins, hydrocarbons from waste streams

How do we Measure Organics?

SAC (UV254)
Mineral Oils

BOD
COD TOC
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Are All Methods Equal?

Type yp BOD CBOD Definition Bio-available organics and other compounds that can be oxidized through consumption of dissolved oxygen Bio available Bio-available organics with an inhibiting agent added to prevent nitrogen oxidation through consumption of dissolved oxygen Chemical oxygen demand, measuring the reduction of yg g chromium: Cr2O72- (orange-colored) Cr3+ (greencolored) Chemical oxygen demand, measuring the reduction of manganese: Manganese Mn(III) purple-colored Mn(II) Total organic carbon, measuring the amount of CO2 generated after oxidation of carbon Spectral absorbance coefficient, measuring the absorbance of 254nm by certain organic molecules with double & triple bonds * As determined by recovery of a known standard Accuracy* y 15% 15%

COD (Cr) COD (Mn) TOC SAC

<3% <3% <3% Trending Tool

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Biggest Issues with Organic Measuring

BOD: Is there anything that is good about it? Comparing BOD, TOC, UV, COD: can this be done? Can it be used to tune the food to microorganism ratio (F/M)? Waiting 2 hours or 5 days doesnt allow me to see what is coming i t my plant right now, h i into l t i ht how d I k do know if I h have a large organic slug?
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Key BOD & COD Methods

BOD & cBOD

Average number of hours/week a typical WW facility spends on BOD? Average number of bottles set per week for BOD? Average number of times per week BOD is run? 15 hours 21 bottles 2 sets

Percent of BOD tests that FAIL to meet Standard Methods Guidelines? Industrial waste streams or slugs can also be problematic for the BOD test!

5-10%

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Issues and Root Causes

Failure
Blank depletion Effluent fails to achieve 2 ppm depletion Fail G/GA reference

Key Root Cause(s)

Organic contamination in dilution water or bottles Drift in DO sensor Insufficient nutrient or seed Toxicity Inaccurate G/GA Toxicity Insufficient seed

www.boddoctor.com
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Timethe Achilles Heel of Organics Measurements

BOD5 = 5 Day Procedure COD = 2-3 Hour Procedure COD not affected by industrial/toxic samples l

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Chemical Oxygen Demand COD is a measure of the oxygen demand of a sample th t i susceptible t oxidation b a strong l that is tibl to id ti by t chemical oxidant Digestion required: 2 hours @ 150 C

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Common Uses of COD How do you use COD?? y Food estimate? Tracking industrial dischargers? y g g Anyone charging industrial discharges based on COD instead of BOD?

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COD Methods
Dichromate micro digestion (0.7 15,000 mg/L COD)
Dichromate = strong oxidizer; good digestion Interference from chlorides occurs > 2,000 mg/L Mercury waste must be disposed of properly and recycled

Manganese III micro digestion (25 1,000 mg/L COD)

M Mercury f reagent easier to dispose of free t i t di f Mn III is not as strong of an organic oxidizer Chlorides can be removed via precipitation with silver salts, filtered, or centrifuged
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Plant Baselines, Trends, and Correlations

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Organics Trend = Load Equalization

Inlet of plant Equalisation to aeration

400

BOD (UV) [mg/l] D

300 200 100 0 0 24 48 72 96 120 144 168

time [h]

Target: Steady loading to the aeration basin

->optimal denitrification and biological phosphorus removal

Solution: - Bypass the primary clarifier during low loading

- supplement external carbon sources
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Can we make correlations?

True or False? There is NO general correlation between BOD and COD COD

However: Correlations can be made on samples with consistent composition

COD can be used to estimate BOD le els sed levels Useful relationships can be made for some samples

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email Perry Brake: pudljumper1@ comcast.net

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What correlations are useful?

Standards Effluent Some influent streams, if consistent! Is your influent consistent? y COD: Use to estimate BOD to calculate required dilutions Use ratios as a quality check for procedures procedures, results, and proficiencies
Recommended by Standard Methods!
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BOD:COD Example
New Belgium Brewery BOD removal before discharging to municipality U Uses COD f d il process for daily control No longer running BOD daily COD:BOD ratio usually 100:1 for influent, 10:1 effluent COD #1 parameter used to give operators the big picture
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COD for Rapid Organic Estimates

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Take Home Messages

BOD and COD evaluate the efficiency of treatment processes and removal of organic compounds COD can be a time saver and is not affected by toxicity Correlations can be made on samples with consistent composition for process control BOD COD ratios can b a great way t assess results of BOD:COD ti be t to lt f BOD test and proficiency samples!
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Any questions?

Thank you for your time!

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Additional Slides

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Products for BOD

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LDO for BOD

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LDO Method Approval

Green: Approved - No data needed Blue: Approved with Performance Data* - Est. total time 2-8 Lab hrs/ 30-90 days Orange: Tier 1 Submission
http://www.hach.com/hqdguide-do
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The COD ProblemWaste EZ COD recycling

Fill bucket with used COD Vials Heritage Environmental will pick up and recycle

Mercury Free COD

TNTplus packaging Not EPA approved Only for low-chloride waters

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Products for COD

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Comparison between SAC/TOC and SAC/COD

G a n g lin ie n v e r g le ic h d e r G e r te T O C T A X u n d U V A S p lu s a m A b la u f e in e r V o r k l r u n g
m g /l T O C (T O C T A X ) m g /l D O C u v (U V A S p lu s )

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Konzentration [mg/l TOC bzw. mg/l DOCu uv]

140 120 100 80 60 40 20 0 28. S ep 29. S ep 30. S ep 1. O kt 2. O kt 3. O kt 4. O kt

SAC / TOC Primary Effluent

600 CSB [mg/l] 500 400 300 200 100

Differences because of particulate COD

60 SAK [1/m] 50 40 30 20 10 t [h] 0 120

SAC / COD Raw Influent

0 0 24 48 72 96

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