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Assoc. Prof. Kozet YAPSAKLI

Assoc. Prof. Kozet YAPSAKLI - Marmara Üniversitesimimoza.marmara.edu.tr/~kyapsakli/enve202/Lecture3_Biochemical... · Nitrification inhibitor Blank (dilution water) Diluted sample

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Assoc. Prof. Kozet YAPSAKLI

What is BOD?

Biochemical Oxygen Demand

It is just what it sounds like, it is the oxygen required by biochemical processes.

What is BOD? In the presence of free oxygen, aerobic bacteria use the

organic matter in wastewater as “food”.

The BOD test is an estimate of the “food” available in the sample.

The more “food” present in the waste, the more Dissolved Oxygen (DO) will be required.

The BOD test measures the strength of the wastewater by measuring the amount of oxygen used by the bacteria as they stabilize the organic matter under controlled conditions of time and temperature.

BOD testused to determine pollutional strength of domestic and industrial wastes in terms of oxygen that they will require if discharged into natural watercources

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wastewater

Org. matter

O2

DO

How is BOD different than dissolved oxygen?

BOD isn’t really there.

BOD is the amount of oxygen that would be consumed given sufficient time, bacteria and oxygen to completely decompose the organic matter.

How is BOD different than dissolved oxygen?

“Dissolved oxygen” is there. It is a measure of how much oxygen is dissolved in a water sample. It is a measure of oxygen content.

BOD is the amount of oxygen that would be consumed to completely decompose the organic matter in a water sample. It is not an indication of oxygen content. It is an indication of the amount of organic material present.

The Reaction Complete oxidation (combustion) of organic materials

yield identical products no matter what the organic starting material.

CnHaObNc + O2 → CO2 + H2O + NH3

(unbalanced)

The Balanced Equation

CnHaObNc + (n+a/4 - b/2 -3c/4) O2 →

n CO2 + (a/2 – 3c/2)H2O + c NH3

Note: Don’t get too hung up on the numbers, we don’t use the stoichiometry very often.

How would you determine BOD? Add bacteria.

Add oxygen quantitatively.

Wait until all of the organic material is gone.

Report on the amount of oxygen used.

What is the problem with that little scheme?

What bacteria? There are millions of different kinds.

How long? What if it takes 10 years for all the organic material to disappear? What if some of it NEVER decomposes?

Other factors: Temperature? Amount of light present? Concentration of oxygen?

Source: www.dnr.wi.gov

BOD - loss of biodegradable

organic matter (oxygen demand) Lo

Lt

L o

r B

OD

rem

ain

ing

Time

Lo-Lt = BODt

BOD Bottle

BOD Bottle

BOD Bottle

BOD Bottle

BOD Bottle

Ex: Nitrogenous Oxygen Demand

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Direct Method

Adjust the sample to 20 °C , aerate with diffused air to increase or decrease dissolved gas content to near saturation.

Fill BOD bottles. Measure D.O. immediately in the first bottle.

Incubate 5 day Measure D.O. BOD =DO1-DO2

Dilution Method

Control all environmental conditions in the bioassay test.

Free of toxic materials

Favourable pH and osmotic cond.

Presence of available nutrients

Standard Temp.

Presence of mixed organisms of soil origin

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Industrial wastes may be free of m.o. and nutrients

Domestic ww Contain org. Nutrients N, P,

Dilution water used in BOD must compensate these deficiences.

Dilution water

Natural surface water

Tap water=>possibility of toxicity from chlorine residuals.

Synthetic dilution water prepared from distilled, demineralised water

Dilution water must be free of toxic subs. Chlorine, Chloroamines, copper.

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Seeding: (maintain necessary microorganism)

Domestic wastewaters

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Dilution water

Seed Nutrient pH buffer Nitrification inhibitor

Blank (dilution water)

Diluted sample

Allyl-thiourea (ATU)

Dilutions of wastes

Set three dilutions

If strength is known two dilutions

Some casesup to 4 dilutions

Samples should deplete at least 2 mg/L D.O.

At least 0.5 mg/L of D.O. should remain at the end of incubation.

DO1-DO2=2-7 mg/L

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Sample calculation

Determine the 5-day BOD for a 15 ml sample that is diluted with dilution water to a total volume of 300 ml when the initial DO concentration is 8 mg/l and after 5 days, has been reduced to 2 mg/l.

D0 = 8 D5 = 2 P = 15 ml/300ml = 0.05 BOD (mg/l) = _______ = 120

0.05

8 - 2

If all the DO is used up the test is invalid, as in B above

Need for a blank The dilution water containing the seeding material

will contain organic materialaddition of the diluting water to the sample will increase the amount of oxidizable organic matter.

A correction must be applied BOD analysis of the seeded dilution water

Calculation of BOD

f: fraction of the seed in the incubated sample

Calculation of BOD

Reaction rates-BOD Kinetics

It’s all about the kinetic model BOD reactions have “1st order kinetics”

“1st order kinetics” refers to the dependence on concentration

Rate = - Δ[react] = ∆ [prod] = k [react]1

∆time ∆time

The Rate Law Rate = - Δ[react] = ∆ [prod] = k [react]1

∆time ∆time

What’s that “k”?

k is called the “rate constant”, it’s the only thing that is constant in this kinetic scheme.

A word about k The “rate constant”, k :

Depends on the reaction

Depends on the type of bacteria (in the case of BOD)

Depends on the temperature

Rate of reaction is proportional to the concentration of food:

It is customary to describe biodegradable organic matter in terms of its equivalent oxygen consumption potential:

In many cases, the interest is in how much oxygen has been consumed, rather than how much BOD remains:

In the BOD test, it is y which is measured rather than Lt

Ultimate BOD If you determine the BOD after 5 days, this is called

“the 5 day BOD” (BOD5). If you determine the BOD after 20 days, this is called “the 20 day BOD” (BOD20). These are really BOD exerted values.

The “ultimate BOD” is the amount of oxygen

required to decompose all of the organic material after “infinite time”. This is usually simply calculated from the 5 day data. (Who can wait for infinity?)

k´ of raw domestic ww 0,40 per day

Why do such differences in reaction rates occur?

The nature of the organic matter

The ability of organisms present to utilize the organic matter.

Glucose high k Lignin, Synthetic detergents slowly attacked by bacteria

Rate of hydrolysis and diffusion

Some industrial wastes particularly containing synthetic chemicals with structure not found in natural compıundslag period

How to overcome: • Seed from the river where the ww is

discharged • Use adapted seed developed in the lab

BODL and Theoretical Oxygen Demand

Ultimate BOD or L0 = ThOD considered to be equal for a biodegradable substance

Oxidation of glucose

C6H12O6 + 6O2 6CO2+ 6H2O

180 192

192 g O2 /mole of glucose

OR

1.065 mg O2 /mg glucose

300 mg/L of glucose ThOD=

Experimentally;

BOD measurements (20 day)

BOD(L)= 250-285 mg/L

85% of theoretical amount

Not all the glucose converted to CO2 and water

300*192/180=320 mg/L

Org. Matter Food source

Energy Growth

Part of org. matter Converted to cell tissue Cell tissue will remain unoxidizedtill endogeneous

respiration

When bacteria die they become food material for others.

Further transformation to CO2 , H2O and cell tissue

Living bacteria + Dead ones Food for higher organisms

Protozoans

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A certain amount of organic matter remains in these transformations.

Resistant to further biological attack.

Humus amount of org. matter corresponding to discrepancy between total BOD and ThOD.

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Analysis of BOD Data

Calculation of k value is needed to obtain L0 using BOD5.

k and L0 are determined from a series of BOD measurements.

Methods:

Least squares

Thomas Method

Methods of moments

Daily-difference method

Rapid ratio method

Fujimoto Method

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Least Squares Method

y6=

22=

Thomas Method

Thomas Method

Thomas Method

Thomas Method-Example

From a BOD test we have the following data:

Time, Days BOD, mg/L

2 10

4 16

6 20

Slope = 0.545

Intercept = 0.021

k1 = 6(0.021/0.545) = 0.64 day-1

L = 1/[6(0.021)(0.545)2] = 26.7 mg/L

k’

L0