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BIOCHEMICAL OXYGEN DEMAND. BIOCHEMICAL OXYGEN DEMAND (BOD). BOD the amount of oxygen required by bacteria while stabilizing decomposable organic matter under aerobic condition. Organic matter serve as food for bacteria. Organic matter. Energy +. oxygen.
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BIOCHEMICAL OXYGEN DEMAND D.Akgul
BIOCHEMICAL OXYGEN DEMAND (BOD) • BOD the amount of oxygen required by bacteria while stabilizing decomposable organic matter under aerobic condition. Organic matter serve as food for bacteria Organicmatter Energy + oxygen D.Akgul
BOD testusedtodeterminepollutionalstrenght of domesticandindustrialwastes in terms of oxygenthattheywillrequireifdischargedintonaturalwatercources wastewater DO O2 Org. matter D.Akgul
BOD test • Bioassayprocedure. • Measuresoxygenconsumedbylivingorganismswhileutilizingorganicmatterpresent in waste. • Conditions as similar as possibletothosethatoccur in nature • To be quantitative protectfromtheairtopreventreaeration. • Env. conditionsshould be suitableform.o. • No toxicsubstance. D.Akgul
D.O should be presentthroughoutthe test. O2solubility~9 mg/L DO used ~ amount of organic in sample Strongwastesmust be diluted D.Akgul
Allnecessarynutrientsneededforbacterialgrowth. (N,P, traceelements) • Diversegroup of m.org. (seed) carrytheoxidationto CO2 • BOD test a wetoxidationprocess • Livingorganismsserve as themediumforoxidation of org. mattertowaterandCO2 D.Akgul
Oxygenrequirementtoconvert org. compoundto CO2 , water , ammonia. CnHaObNc + ( n + a/4 - b/2 – 3c/4 ) O2 nCO2+ (a/2 – 3c/2)H2O+ cNH3 • Temperatureeffectsareheldconstantbyperformingthe test at 20C D.Akgul
İnfinite time is requiredforcompletebiologicaloxidation of organicmatter • Practicallythereactionconsideredcomplete in 20 days =>BOD ultimate • Largepercentage of the total BOD is exerted in 5days • The test has beendeveloped on thebasis of a 5-dayincubationperiod.=> 5 day BOD • 5 day test wasselectedalsoto minimize interferencefromoxidation of ammonia. D.Akgul
BOD ReactionKinetics • Firstorderrxnkinetics Rxn rate proportionaltotheamount of oxidizableorganicmatterremaining at any time. (Ifmopopulation is nearlyconstant) • -dc /dt ˜ C • -dc/dt = k’C C: Conc. of oxidizable org matter K: rate constant • Rate decreases as C decreases D.Akgul
In BOD considerations; • C L (ultimatedemand) • -dL/ dt=k’L • Lt/L = e-k’t • Lt=L* e-k’t • e-k’t= 10–kt • k=k’/ 2.303 D.Akgul
k’ : BOD rxnconstant (d-1). Typically k’ ˜0.1 to 1 d-1 fordegradable org. matter in naturalwater at ambienttemp 10 < T < 30 °C BOD t = L (1-10–kt ) BOD t : BOD at any time t, L: BOD ultimate D.Akgul
Theoxygenconsumed in the time intervalfromzeroto t is called BOD t • BOD t : BOD consumedwithin time t • Lt : Potential BOD remaining at time t • BODt = L –Lt = L – L. e-k’t = L (1- e-k’t) D.Akgul
Example 1: Determine 1 day BOD andultimate BOD for a wastewaterwhose 5 day , 20 °C BOD is 200 mg/ L. • Thereactionconstant k ( base e) = 0.23 d-1 D.Akgul
Itspossibletodeterminereactionconstant k at a temp. otherthan 20 °C. • VantHoff – Arrheniusrelationship : • Kt = k20 Ɵ ( t-20) • Ɵ = 1,056 (20<T<30 °C) • Ɵ = 1,135 ( 4<T<20 °C) D.Akgul
Example 2: Calculate rate constantfor T=24C k=0.23 d-1 (@ 20C) Ɵ=1.047 D.Akgul
Oxygenused Organicmatteroxidized ( DirectRatio) ~ Oxygenused D.Akgul
Influence of Nitrification on BOD • BOD oroxygen-usedcurve is similartoorganicmatteroxidationcurveduringthefirst 8-10 days. • Forpropermeasurement of BOD, culturesused in BOD test shouldcontainheterotrophicbacteriaandotherorganismsthatutilizethecarbonaceousmatter. D.Akgul
Additionallytheycontaincertainautotrophicbacteria, particularlynitrifyingbacteria. • nitrifyingbacteriaoxidizesnoncarbonaceousmatterforenergy • Nitrifyingbacteriapresentsmallamounts in untreateddomesticww. • @20 °C theirpopulations do not becomesufficientlylargetoexertoxygendemanduntil 8-10 days. • Interference of nitrificationeliminatedbytaking test period 5 days BOD 5 D.Akgul
Untreateddomesticwwcontainslittleamount of nitrifyingbacteria, but effluentfrombiological treatment unitssuch as ActivatedsludgeandTricklingfilter do containnitrifyingbacteriathat can alsoconsume D.O. in 5 days. • Inhibittheaction of nitrifyingbacteriabyspecificinhibitingagents 2-Chloro-6 ( trichloromethyl) pyridine (TCMP) orAllylthiourea (ATU). D.Akgul
BOD Test • Method is based on determination of D.O. DirectmethodDilutionmethod D.Akgul
DirectMethod : IfBOD 5 < 7 mg/L no dilutionrequired. Ex: Riverwaters Adjustthesampleto20 °C , aeratewithdiffusedairtoincreaseordecreasedissolvedgascontenttonearsaturation. Fill BOD bottles. Measure D.O. İmmediately in firstbottle. Incubate 5 day Measure D.O. BOD =DO1-DO2 D.Akgul
DilutionMethod Rate at whichoxygen is used in dilution of wastes is in directratiotopercent of waste in dilution. 10% dilutionusesoxygen at 1/10 the rate of a 100% sample. D.Akgul
Controlallenvironmentconditions in thebioassay test. • Free of toxicmaterials • FavourablepHandosmoticcond. • Presence of availablenutrients • Standard Temp. • Presence of mixedorganisms of soilorigin D.Akgul
Industrialwastesmay be free of m.org. Andnutrients • Domesticww Contain org. Nutrients N, P, • Dilutionwaterused in BOD mustcompensatethesedeficiences. Dilutionwater Naturalsurfacewater Tap water=>possibility of toxicityfromchlorineresiduals. Syntheticdilutionwaterpreparedfromdistilled, demineralised w.***thebest Dilutionwatermust be free of toxicsubs. Chlorine, Chloroamines, copper. D.Akgul
Seeding: (maintainnecessarymicroorganism) • Domesticwastewaters Blank (dilutionwater) Dilutedsample Seed Nutrient pH buffer Nitrificationinhibitor Dilutionwater D.Akgul
Dilutions of wastes Set threedilutions Ifstrenght is known twodilutions Somecasesupto 4dilutions • Samplesshoulddeplete at least 2 mg/L D.O. • At least 0.5 mg/L of D.O. remaining at theend of incubation. DO1-DO2=2-7 mg/L D.Akgul
Example 3:Calculatethepercentage of wasteshould be addedto a BOD bottleifthe BOD range is; 200/2=100 100/100=1 % 40/2=20 100/20=5 % 20,000/2=10,000 100/10000=0.01% D.Akgul
Incubationbottles: • Glassstoppers • Preventairtrappingduringincubation • Waterseal. • Bottlesshould be free of organicmatter. • Cleanwithchromicacidordetergent. • Rinsecarefully • Allcleaningagentsremovedfrombottle • 4 rinsewith tap water, • final rinsewithDistilledor deionized water D.Akgul
Calculation of BOD BOD(mg/L)= DOb=DO found in blank at theend of incubation DOi=DO found in dilutedsample at theend of incubation DOs= DO thatoriginallypresent in undilutedsample D.Akgul
Respirometricmeasurement OXYTOP Respirometricmethod:Respirometric methods provide direct measurement of the oxygen consumed by microorganisms from an air or oxygen-enriched environment in a closed vessel under conditions of constant temperature and agitation. D.Akgul
Rate of BiochemicalOxidations Differs in diff. Wastes D.Akgul
Effluentfrombioligicalwwtpdifferentfromrawwastes • Nature of the org. Matter • Theability of theorganismspresenttoutilizethe org. Matter • Rate of hydrolysisanddiffusion • Ex: Glucose high k • Lignin, Syntheticdetergents slowlyattackedbybacteria D.Akgul
BODLandTheoreticalOxygenDemand • Total BOD or L = ThODconsideredto be equal • Oxidation of glucose C6H12O6 + 6O2 6CO2+ 6H2O 180 192 D.Akgul
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 theoreticalamount Not alltheglucoseconvertedto CO2andwater 300*192/180=320 mg/L D.Akgul
Org. Matter Foodmaterial • Energy • Growth • Reproduction Part of org. Matter Convertedtocelltissue Celltissuewillremainunoxidizedtillendogeneousrespiration • Whenbacteriadietheybecomefoodmaterialforothers. • FurthertransformationtoCO2 , H2O andcelltissue • Livingbacteria + Deadones Foodforhigherorganisms Protozoans D.Akgul
A certainamount of organicmatterremains in thesetransformations. • Resistanttofurtherbiologicalattack. • Humus amount of org. mattercorrespondingtodiscrepancybetween total BOD andThOD. D.Akgul
Analysis of BOD Data Calculation of k value is neededtoobtain L using BOD5. k and L aredeterminedfrom a series of BOD measurements. Methods: • Leastsquares • Thomas Method • Methods of moments • Daily-differencemethod • Rapidratiomethod • FujimotoMethod D.Akgul
Leastsquaresmethod: Fitting a curvethroug a set of data points. Sum of thesquares of theresidualmust be minimum. (Differencebetweenobservedandthefittedvalue) D.Akgul
dy/dt (t=n) = k (L-yn) • Forthe time series of BOD measurements on thesamesampleEqn. May be writtenforeach of thevarious n data points. • k and L unknown D.Akgul
If it is assumeddy/dtrepresenttheslope of thecurveto be fittedthroughall data pointsfor a given k and L value, twosideswill not be equalbecause of experimentalerror. Difference R R=k(L-y)-dy/dt R=kL-ky-y’ a=kL -b=k R=a+by-y’ D.Akgul