Chapter 4

TABLE OF CONTENTS Dissolved Oxygen Measure ent

!age

Section 1: Dissolved Oxygen (DO) Introduction.................................................................................. Section 2: Glossary.............................................................................................................................. Section 3: Approved et!ods..............................................................................................................

2 2 3 3%" "%& & & ( (%1 1

Section ": Sa#ety and $ygiene............................................................................................................. Section &: Sa'pling............................................................................................................................. Section (: )##ects o# *e'perature on DO............................................................................................ Section +: Interpretations..................................................................................................................... ,ui- ".1................................................................................................................................................ Section .: odi#ied /in0ler et!od....................................................................................................

,ui- ".2................................................................................................................................................ Section 1: *!e )lectro'etric eter

et!od........................................................................................ 1%11 12 12

,ui- ".3................................................................................................................................................ Section 12: ,A3,4..............................................................................................................................

Ans5ers to ,ui--es.............................................................................................................................. 13%1" Appendix A: 6e#erences Appendix 7: Dissolved Oxygen 6eagents Appendix 4: Sa'ple 7enc! S!eets

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Chapter 4
D"SSOL#ED O$%&EN MEAS'(EMENT
Se)tion * + D"SSOL#ED O$%&EN ,DO- "NT(OD'CT"ON *!e DO deter'ination 'easures t!e a'ount o# dissolved (or #ree) oxygen present in 5ater or 5aste5ater. Aero8ic 8acteria and a9uatic li#e suc! as #is! 'ust !ave DO to survive. Aero8ic 5aste5ater treat'ent processes use aero8ic and #acultative 8acteria to 8rea0 do5n t!e organic co'pounds #ound in 5aste5ater into 'ore sta8le products t!at 5ill not !ar' t!e receiving 5aters. /aste5ater treat'ent #acilities suc! as lagoons or ponds: tric0ling #ilters and activated sludge plants depend on t!ese aero8ic 8acteria to treat se5age. *!e sa'e type o# aero8ic 5aste5ater treat'ent process occurs naturally in strea's and ponds i# organic 'atter is present: turning t!ese 8odies o# 5ater into ;aero8ic 5aste5ater treat'ent plants.< I# su##icient oxygen is not naturally supplied t!roug! 5ind and tur8ulence to replace t!e depleted oxygen: t!e 8ody o# 5ater 5ill develop a lo5 DO and 8eco'e anaero8ic (or septic). *!e results o# septic 5ater 8odies include #is! 0ills and anaero8ic odors. I# t!e a'ount o# #ree or DO present in t!e 5aste5ater process 8eco'es too lo5: t!e aero8ic 8acteria t!at nor'ally treat t!e se5age 5ill die. *!e process 5ill not operate e##iciently and septic conditions 5ill occur. *!e DO test is used to 'onitor t!e process to ensure t!at t!ere is enoug! dissolved oxygen present to 0eep t!e process #ro' 8eco'ing septic.

Se)tion .+ &LOSSA(% Aero/i)+ A condition in 5!ic! ;#ree< or DO is present in an a9uatic environ'ent. Anaero/i)+ A condition in 5!ic! ;#ree< or DO is not present in an a9uatic environ'ent. "ndi)ator solution+ A solution used to deter'ine t!e endpoint (usually a color c!ange) 5!en titrating. Titrate+ *o titrate a sa'ple: a c!e'ical solution o# 0no5n strengt! is added on a drop 8y drop 8asis until a color c!ange: precipitate or p$ c!ange in t!e sa'ple is o8served.

4!apter " % 2

Se)tion 0+ A!!(O#ED MET1ODS 6e'e'8er: al5ays re#er to your =>D)S >er'it and "2 4?6 >art 13( #or approved 'et!ods. *!e 1.t! )dition o# ;Standard et!ods #or t!e )xa'ination o# /ater and /aste5ater< includes t5o 'et!ods #or t!e deter'ination o# DO in 5aste5ater: including t!e /in0ler 'et!od (a-ide 'odi#ication) and t!e electro'etric 'et!od using 'e'8rane electrodes and a DO 'eter. *!e /in0ler 'et!od is 8ased on t!e a8ility o# t!e DO in a sa'ple to oxidi-e c!e'icals added to t!e sa'ple. *!e a-ide 'odi#ication o# t!e /in0ler 'et!od 5as developed to correct #or t!e presence o# nitrites in a sa'ple. *!ese co'pounds: #ound in al'ost all 5aste5ater sa'ples: inter#ere 5it! t!e ot!er 'odi#ications o# t!e /in0ler procedure. *!e 'e'8rane electrode procedure utili-es a 'eter and electrode: and is 8ased on t!e rate at 5!ic! oxygen 'olecules di##use (or pass t!roug!) a 'e'8rane covering a set o# electrodes. *!e oxygen 'olecules react 5it! an internal #illing solution to develop a s'all electrical c!arge 8et5een t!e electrodes 5!ic! can 8e read on a 'eter. *!e readings on t!e 'eter correspond directly to t!e a'ount o# DO present in t!e sa'ple.

Se)tion 4+ SAFET% AND 1%&"ENE /!en testing #or dissolved oxygen: t!e concerns #or sa#ety involve 5aste5ater !a-ards and exposure to c!e'icals. >recautions to #ollo5 include: 1. 2. 3. ". &. (. 4over all a8rasions and 5ear good 9uality latex gloves 5!en in direct contact 5it! ra5 5aste5ater. /as! !ands #re9uently: and al5ays 5as! !ands prior to eating or s'o0ing. 4lean up all spills o# 5aste5ater or 8u##ers i''ediately. /ear a protective s'oc0: apron or la8 coat: and surgical or ru88er gloves 5!en 5or0ing in t!e la8oratory to protect clot!es and s0in. 6ead all la8els care#ully and 0no5 5!at to do in case o# a spill. Al5ays use a pipette 8ul8. =)@)6 pipette anyt!ing 8y 'out!.

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+.

Al5ays pour acids or 8ases into 5ater: never add 5ater to t!e acid or 8ase. acids or 8ases 5it! 5ater can create a signi#icant a'ount o# !eat.

ixing concentrated

Se)tion 2+ SAM!L"N& /!en using t!e electro'etric 'et!od: analy-e i''ediately. *!e pre#erred 'et!od is in%strea' analysis in t!e #ield. >roper sa'pling is necessary i# la8oratory testing is to 8e accurate. *!e sa'ple 'ust 8e representative and !andled care#ully. =o 'atter !o5 accurate t!e actual testing is: i# t!e sa'ple is not representative: t!e results o# t!e test 5ill not re#lect actual conditions and can lead to poor plant per#or'ance. *!e dissolved oxygen deter'ination re9uires a gra8 sa'ple. *!e sa'ple 'ust 8e analy-ed as 9uic0ly as possi8le. Select a sa'pling location 5!ere 'ixing is t!oroug! and t!e 5aste5ater 9uality is uni#or'. *!e !ig!er t!e a'ount o# solids in t!e sa'ple: t!e 'ore i'portant a 5ell%'ixed sa'ple 8eco'es. I# testing is not done on an !ourly 8asis: c!oose ti'es 5!en t!e sa'ple 8est represents t!e 5aste c!aracteristics so t!at c!anges can 8e spotted 9uic0ly. Since variations 5ill occur #ro' plant to plant and 5it! t!e ti'e o# day: it is necessary to develop a testing progra' 5!ic! gives t!e 'ost accurate representation o# t!e c!aracteristics o# t!e #lo5. SAM!LE !(ESE(#AT"ON /!en using t!e electro'etric 'et!od: analy-e i''ediately. *!e pre#erred 'et!od is in%strea' analysis in t!e #ield. Alt!oug! DO tests s!ould 8e per#or'ed as 9uic0ly as possi8le: sa'ples 5!ic! are to 8e tested using t!e 'odi#ied /in0ler procedure 'ay 8e preserved 8y eit!er o# t!e #ollo5ing 'et!ods: 1. I# t!e sa'ples 'ust 5ait #or a ti'e period o# up to t5o !ours 8e#ore testing and !ave no iodine de'and: t!ey 'ay 8e stored 8y adding 'anganous sul#ate solution: al0aline%iodide%a-ide solution: sul#uric acid solution and s!a0ing 5ell ('a0ing sure t!at no air 8u88les are trapped or #or'ed). (>rotect t!e sa'ples stored at t!is point #ro' strong sunlig!t and titrate as soon as possi8le.) 2. *!ose sa'ples 5!ic! !ave an iodine de'and 'ay 8e preserved #or " to . !ours 8y adding 2.+ 'A concentrated sul#uric acid ($2SO") and 1.2 'A sodiu' a-ide solution (2.2 g =a=33122 'A distilled 5ater) to t!e DO 8ottle. *!is 5ill stop t!e 8iological activity and 'aintain t!e dissolved oxygen levels i# stored at t!e sa'e te'perature as t!e sa'ple or i# 5ater%sealed and 0ept at a te'perature o# 12 to 22B4. As soon as possi8le: co'plete t!e procedure using 2.2 'A 'anganese sul#ate solution: 3.2 'A Al0aline%iodide%a-ide solution and 2.2 'A concentrated sul#uric acid.

4!apter " % "

SAM!LE CONTA"NE(S ?or t!e /in0ler analysis: sa'ples s!ould 8e collected in narro5%'out! glass%stoppered 7OD 8ottles 5it! 322 'A capacity 5it! tapered: ground%glass: pointed stoppers and #lared 'out!s. Sa'ples 'ust 8e ta0en so t!at t!e 8ottle 5ill 8e co'pletely #illed 5it! li9uid t!at !as not 8een in contact 5it! air and no air is trapped under t!e stopper. An A>$A type sa'pler: or e9uivalent s!ould 8e used to collect sa'ples #or dissolved oxygen deter'ination. ?or dept!s greater t!an 2 'eters use a Ce''erer%type sa'pler: or e9uivalent. SAM!LE CONTA"NE( !(E!A(AT"ON Sa'ple containers 'ust 8e clean: dry and #ree o# conta'inants. *!e 8est 'et!od to prepare sa'ple containers is 8y acid cleaning 5it! dic!ro'ate cleaning acid: 5!ic! can eit!er 8e 8oug!t already prepared: or 'ixed at t!e plant. CA'T"ON+ D"C1(OMATE "S E$T(EMEL% 1A3A(DO'S AND CAN CA'SE SE#E(E B'(NS4 "N CASE OF CONTACT O( S!"LL5 ("NSE T1O(O'&1L% 6"T1 LA(&E 7'ANT"T"ES OF TA! 6ATE(4 /ear ru88er gloves and sa#ety glasses 5!enever using cleaning acid. A#ter cleaning 5it! acid: rinse 5it! tap 5ater: #ollo5ed 8y distilled 5ater. I# possi8le: allo5 t!e containers to dry upside%do5n on a rac0. I# cleaning acid is not availa8le: use a la8oratory grade detergent t!at is lo5 in p!osp!orus and nitrates. /as! 5it! a good cleaning 8rus!: and rinse t!oroug!ly 5it! tap 5ater: #ollo5ed 8y distilled 5ater. Allo5 t!e 8ottles to dry in an upside%do5n position. All sa'ple containers s!ould 8e cleaned i''ediately a#ter t!e test !as 8een co'pleted to prevent accu'ulation o# residues in t!e containers 5!ic! can a##ect t!e test. Se)tion 8+ EFFECTS OF TEM!E(AT'(E ON DO *!e solu8ility o# oxygen in 5ater is greater at cooler te'peratures. /!en using t!e 'e'8rane electrode 'et!od to 'easure DO: t!e 'eter 'ust 8e te'perature cali8rated to produce accurate results. Se)tion 9+ "NTE(!(ETAT"ONS So'e co''on ranges #or DO are listed 8elo5: Sa'ple In#luent >ri'ary )##luent Secondary )##luent &2G to 1&G saturationE ( to . is excellent Oxidation >onds Activated SludgeE Aeration tan0 outlet 1 to 2& 1 to 3 4o''on 6ange ('g3A) Dsually 2E F1 is very good Dsually 2E F1 is good F& is good

4!apter " % &

7ui: 44* 1. /!at is dissolved oxygen (DO)H 2. /!at are t!e sa'pling re9uire'ents #or a DO sa'ple t!at is to 8e tested in t!e la8oratoryH 3. /!at are t!e approved 'et!ods #or deter'ination o# DOH ". 4an a DO sa'ple 8e preservedH I# so: !o5H

Se)tion ;+ MOD"F"ED 6"N<LE( MET1OD DETE(M"NAT"ON OF D"SSOL#ED O$%&EN DESC("!T"ON OF TEST *!e sa'ple is treated 5it! 'anganous sul#ate: al0aline%iodide%a-ide reagent and #inally sul#uric acid. *!e #irst t5o c!e'icals co'8ine 5it! dissolved oxygen to #or' a co'pound 5!ic!: 5!en acid is added: releases #ree iodine (#ro' t!e potassiu' iodide). 7ecause t!e a'ount o# iodine released is e9ual to t!e a'ount o# oxygen present: t!e sa'ple can 8e titrated 5it! eit!er sodiu' t!iosul#ate or p!enylarsine oxide (>AO) to deter'ine t!e a'ount o# dissolved oxygen present. Dnder speci#ic conditions: t!e a'ount o# sodiu' t!iosul#ate or >AO used is e9uivalent to t!e a'ount o# dissolved oxygen present in t!e sa'ple. E7'"!MENT AND (EA&ENTS FO( MOD"F"ED 6"N<LE( MET1OD (EA&ENTS See Appendix 7 #or t!e procedures #or preparation o# t!e reagents used in t!is 'et!od. 1. 2. 3. ". &. (. anganous sul#ate solution I Al0aline potassiu' iodide%sodiu' a-ide solution I3J Sul#uric acid ($2SO"): concentrated J Starc! indicator solution Sodiu' t!iosul#ate (=a2S2O3 &$2O): 2.22& = I >!enylarsine oxide (>AO): 2.22& = I

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+. ..

>otassiu' 8i%iodate (C$(IO3)2): 2.22& = Distilled or deioni-ed 5ater I J *!ese reagents are poisonous and s!ould 8e !andled 5it! extre'e caution. *!ese reagents are corrosive and s!ould 8e !andled 5it! extre'e caution.

E7'"!MENT 1. 2. 3. ". &. (. +. .. 7urette: graduated to 2.1 'A 7urette stand 322 'A glass stoppered 7OD 8ottles &22 'A 5ide%'out!ed )rlen'eyer #las0s >ipettes 5it! elongated tips and 'ini'u' volu'e o# 1.2 'A (J3% 2.1 'A) >ipette 8ul8 2&2 'A graduated cylinders Distilled 5ater rinse 8ottle LABO(ATO(% !(OCED'(E FO( MOD"F"ED 6"N<LE( MET1OD 1. 2. 3. ". &. (. +. 4ollect t!e sa'ple to 8e tested in a 322 'A 7OD 8ottle ta0ing special care to avoid adding air to t!e li9uid 8eing collected. ?ill 8ottle co'pletely and add stopper. 6e'ove 8ottle stopper and add 1 'A o# t!e 'anganous sul#ate solution at t!e sur#ace o# t!e li9uid. Add 1 'A o# t!e al0aline%potassiu' iodide%sodiu' a-ide solution at t!e sur#ace o# t!e li9uid. 6eplace t!e stopper: avoid trapping air 8u88les and s!a0e 5ell 8y inverting t!e 8ottle several ti'es. 6epeat s!a0ing a#ter #loc !as settled !al#5ay. Allo5 #loc to settle a second ti'e. Add 1 'A o# concentrated sul#uric acid 8y allo5ing t!e acid to run do5n t!e nec0 o# t!e 8ottle a8ove t!e sur#ace o# t!e li9uid. 6estopper: rinse t!e top o# t!e 8ottle to re'ove any acid and s!a0e 5ell until t!e precipitate !as dissolved. *itrate a volu'e o# treated sa'ple 5!ic! corresponds to 222 'A o# t!e original sa'ple. *!is corrects #or t!e loss o# so'e sa'ple during t!e addition o# reagents. *!is volu'e calculated using t!e #or'ula: 'A o# sa'ple to titrate K 222 x L3223(322%2)M K 221 'A .. >our 221 'A o# sa'ple #ro' t!e 7OD 8ottle into an )rlen'eyer #las0.

NOTE+ Since variations occur in t!e actual volu'e o# eac! 7OD 8ottle: do not pour 11 'A o# sa'ple out o# t!e 7OD 8ottle and assu'e t!at 221 'A 5ill 8e le#t.

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1.

I# t!e solution is reddis!%8ro5n in color: titrate 5it! 2.22&2 = sodiu' t!iosul#ate or 2.22&2 = >AO until t!e solution is a pale yello5 (stra5) color. 6ecord t!e a'ount o# titrant used. Add a s'all 9uantity o# starc! indicator and proceed to step 11.

12. I# t!e solution !as no reddis!%8ro5n color: or is only slig!tly colored: add a s'all 9uantity (approxi'ately 1 'A) o# starc! indicator. I# no 8lue color develops: t!ere is -ero dissolved oxygen. I# a 8lue color develops: proceed to step 11. 11. *itrate 5it! 2.22&2 = sodiu' t!iosul#ate or 2.22&2 = >AO to t!e #irst disappearance o# t!e 8lue color. 6ecord t!e total nu'8er o# 'A o# sodiu' t!iosul#ate or >AO used. CALC'LAT"ONS FO( MOD"F"ED 6"N<LE( MET1OD 4alculate t!e concentration o# DO in t!e sa'ple using t!e #ollo5ing #or'ula: 'g3A DO K ('A titrant x nor'ality o# titrant x .222)3e9uivalent volu'e o# sa'ple titrated )xa'ple: I# 12.2 'A o# titrant are used: t!en: 'g3A DO K (12.2 x .22& x .222)3222 K 12.2 I# t!e nor'ality o# t!e titrant is exactly 2.22& = and an e9uivalent volu'e o# 222 'A o# sa'ple is titrated: t!e a'ount o# oxygen dissolved in t!e original sa'ple (in 'g3l) 5ill 8e e9ual to t!e nu'8er o# 'A o# sodiu' t!iosul#ate or >AO used in t!e titration. "NTE(FE(ENCES 6"T1 MOD"F"ED 6"N<LE( MET1OD In t!e deter'ination o# DO 8y t!e /in0ler 'et!od: t!ere are various 'aterials 5!ic! cause inter#erences: including iron salts: organic 'atter: excessive suspended 'atter: sul#ide: sul#ur dioxide: residual c!lorine: c!ro'iu': cyanide: and certain oxidi-ing and reducing agents. I# t!e sa'ple contains & 'g3A or 'ore o# #erric iron salt: add potassiu' #luoride as t!e #irst reagent in t!e a-ide 'odi#ication. Alternately: eli'inate #erric iron (?e III) inter#erence 8y using 12G p!osp!oric acid ($3>O") instead o# sul#uric acid #or acidi#ication. (*!is procedure !as not 8een tested #or ?e III concentrations a8ove 22 'g3A). !(EC"S"ON AND ACC'(AC% 6"T1 MOD"F"ED 6"N<LE( MET1OD DO in a 5ater sa'ple can 8e deter'ined 5it! a standard deviation o# J3% 2.222 'g3A in distilled 5ater and a8out J3% 2.2(2 'g3A in 5aste5ater and secondary e##luents. In t!e presence o# an inter#erence: even 5it! t!e proper 'odi#ications: t!e standard deviation 'ay 8e as !ig! as J3% 2.12 'g3A. Still greater errors 'ay occur in 5aters !aving !ig! organic suspended solids or !eavy pollution. Avoid errors due to carelessness in collecting sa'ples: 5aiting too long to co'plete testing: or i'proper testing tec!ni9ues.

4!apter " % .

7ui: 44. 1. /!at reagents are re9uired #or DO deter'inations using t!e 'odi#ied /in0ley titration 'et!odH 2. /!at e9uip'ent: apparatus or instru'entation is re9uired #or DO deter'inations using t!e 'odi#ied /in0ler titration 'et!odH 3. /!at inter#erences a##ect DO deter'inations 8y t!e 'odi#ied /in0ler titration procedureH ". I# 222 'A o# a prepared DO sa'ple re9uires ..( 'A o# 2.22+& = sodiu' t!iosul#ate titrant: 5!at is t!e DO in 'g3AH

Se)tion =+ T1E ELECT(OMET("C METE( MET1OD FO( DETE(M"NAT"ON OF D"SSOL#ED O$%&EN DESC("!T"ON OF TEST *!ere are t5o types o# DO pro8es availa8le: including a la8oratory pro8e and a #ield pro8e. 7ot! types operate on t!e sa'e principle. *!e la8oratory pro8e is designed to 8e used in t!e la8oratory only: 5!ile t!e #ield pro8e 'ay 8e used in t!e #ield or t!e la8oratory. I# t!e #ield pro8e is used in t!e la8oratory: a 'agnetic stirrer is re9uired. An advantage o# t!e #ield pro8e is t!at it eli'inates t!e need to collect: transport and t!en per#or' analysis on a sa'ple. *!e #ield pro8e allo5s t!e dissolved oxygen to 8e deter'ined on%site: 5it!out special sa'pling e9uip'ent. Oxygen%sensitive 'e'8rane pro8es contain t5o solid 'etal electrodes i''ersed in an electrolyte solution 5!ic! allo5s t!e passage o# an electrical current. *!e electrode pair is covered 5it! a se'i% per'ea8le 'e'8rane 5!ic! allo5s t!e passage o# DO 'olecules. /!en t!e oxygen 'olecules pass t!roug! t!e 'e'8rane: t!ey cause t!e electrical current already present to c!ange. *!is c!ange is re#lected 8y t!e 'ove'ent o# t!e needle on t!e 'eter. *!e 'ore DO t!at is present in t!e sa'ple: t!e 'ore t!e current 5ill c!ange and t!e !ig!er t!e reading on t!e 'eter 5ill 8e. *!e 'eter is designed so t!at t!e a'ount o# DO can 8e read directly. E7'"!MENT AND (EA&ENTS FO( ELECT(OMET("C METE( MET1OD (EA&ENTS 6eagent c!e'icals are only re9uired #or t!e 'e'8rane procedure i# t!e 'odi#ied /in0ler 'et!od is used to cali8rate t!e DO 'eter. E7'"!MENT 1. 2. 3. DO 'eter DO pro8e: la8oratory or #ield >ro8e 'e'8rane 0it

4!apter " % 1

".

)9uip'ent needed #or /in0ler 'et!od to cali8rate DO 'eter Special care is re9uired in !andling la8 e9uip'ent. DO pro8es and 'eters cannot ta0e roug! !andling. Do not drop or !it pro8es or 'eters against !ard o8Nects as t!is can 8rea0 pro8es and 0noc0 'eters out o# align'ent. Avoid !itting 'e'8ranes against 8ottle lips: as t!ey puncture and tear easily and 5ill !ave to 8e replaced #re9uently. LABO(ATO(% !(OCED'(E

FO( ELECT(OMET("C METE( MET1OD Since t!ere are 'any 'odels and 'anu#acturers o# DO 'eters and pro8es: t!is 'anual 5ill not descri8e t!e operating procedures #or all 'eters. ?or 8est results: #ollo5 t!e 'anu#acturerOs instruction #or operation o# 'eters and pro8es. 4ondensation 'ay collect on t!e 'e'8rane. *!is 5ill inter#ere 5it! t!e readings. S!a0e o## excess 5ater and gently 8lot dry 5it! a la8oratory tissue. *!e 'e'8rane 'ust 8e stretc!ed tig!tly across t!e pro8e and 5ill not 5or0 correctly i# air 8u88les are present in t!e pro8e underneat! t!e 'e'8rane. 7e sure t!at t!e O%ring !olding t!e 'e'8rane to t!e pro8e #its securely. Allo5 t!e instru'ent to 5ar' up #or at least 1& 'inutes 8e#ore ta0ing t!e #irst reading o# t!e day. Aeave t!e instru'ent on 8et5een 'easure'ents. *!is 5ill eli'inate t!e need #or 5ar'%up periods 8et5een tests. 4ali8rate at least once per day. Distilled or deioni-ed 5ater: and not e##luent: s!ould 8e used #or t!e pro8e cali8ration. Al5ays stir t!e sa'ple 5!ile ta0ing a reading. METE( CAL"B(AT"ON FO( ELECT(OMET("C METE( MET1OD *o 8e certain t!at t!e DO 'eter reading provides t!e correct DO content o# t!e sa'ple: t!e pro8e 'ust 8e cali8rated. *!ere are t!ree accepta8le 'et!ods #or t!e cali8ration o# t!e 'eter: 'odi#ied /in0ler: saturated air: and saturated 5ater. It is reco''ended t!at t!e /in0ler 'et!od 8e used periodically i# one o# t!e ot!er 'et!ods is used on a regular 8asis. A. 4ali8ration /it! 1. 2. 3. ". &. (. odi#ied /in0ler et!od

*a0e a sa'ple (distilled: deioni-ed or tap 5ater) t!at does not contain su8stances 5!ic! inter#ere 5it! eit!er t!e pro8e reading or t!e 'odi#ied /in0ler procedure. 4are#ully divide t!is re#erence sa'ple into " clean 7OD 8ottles. >repare 3 o# t!e 8ottles #or t!e /in0ler titration procedure. *itrate all o# t!e prepared portions and average t!e results. >lace t!e pro8e in t!e #ourt! 7OD 8ottle o# t!e sa'ple #or 3 to & 'inutes 5!ile agitating or stirring. 4ali8rate t!e pro8e reading to agree 5it! t!e averaged results o# t!e 'odi#ied /in0ler 'et!od.

NOTE+ Any error in t!e 'odi#ied /in0ler 'et!od 5ill a##ect t!e cali8ration o# t!e pro8e. 7. 4ali8ration /it! Saturated /ater

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1. 2. 3.

Aerate sa'ple #or 12%1& 'inutes. easure te'perature: t!en loo0 up t!e cali8ration value on t!e DO concentration vs te'perature c!art. 4orrect as necessary #or altitude or salinity o# sa'ples. >ut pro8e in sa'ple: 5ait 3 to & 'inutes: and cali8rate.

NOTE+ *!is 'et!od depends on 122G saturation o# DO in t!e sa'ple. Since 122G saturation is di##icult to ac!ieve: an error 'ay 8e introduced. 4. 4ali8ration /it! Saturated Air 1. 2. 3. >lace pro8e in 'oist air cali8ration c!a'8er (suc! as a 7OD 8ottle #illed !al#5ay 5it! distilled 5ater). Do not turn on pro8e stirrer. /ait & 'inutes. easure t!e air te'perature: loo0 up t!e cali8ration value: correct as necessary #or altitude or salinity o# sa'ples and cali8rate. CALC'LAT"ONS FO( ELECT(OMET("C METE( MET1OD *!ere are no calculations #or t!is 'et!od. *!e DO concentration is read directly #ro' t!e 'eter. "NTE(FE(ENCES OF ELECT(OMET("C METE( MET1OD *!ere are very #e5 su8stances 5!ic! 5ill inter#ere 5it! t!e DO 'et!od 5!en utili-ing t!e electro'etric 'eter. Salinity caused 8y dissolved inorganic salts (suc! as sea 5ater: estuaries: and industrial or 'anu#acturing processes) can in#luence t!e pro8eOs readings. 6eactive co'pounds and gases (li0e !ydrogen sul#ide and ot!er sul#ur co'pounds) can inter#ere 5it! t!e reading 8y reducing pro8e sensitivity. 4!lorine residual can create a positive inter#erence. 6ead t!e 'anu#acturerOs instructions #or t!e care and !andling o# t!e DO electrode and 'eter #or speci#ic re'edies: i# any: #or t!ese inter#erences. !(EC"S"ON AND ACC'(AC% 6"T1 T1E ELECT(OMET("C METE( MET1OD Dsing 'ost co''ercially availa8le 'e'8rane electrode syste's: an operator can o8tain an accuracy o# J3% 2.1 'g3A DO and a precision o# J3% 2.2& 'g3A DO.

7ui: 440

4!apter " % 11

1. /!at e9uip'ent: apparatus or instru'entation is re9uired #or t!e DO deter'inations 8y t!e 'e'8rane electrode 'et!odH 2. /!at are t!e accepted 'et!ods o# cali8ration o# t!e DO 'eter and electrodeH 3. /!at inter#erences can a##ect DO deter'inations 8y t!e 'e'8rane electrode procedureH

Se)tion *>+ 7A?7C A ,uality Assurance3,uality 4ontrol progra' is re9uired 8y t!e =>D)S per'it. ,uality Assurance (,A) is a set o# operating principles t!at 'ust 8e #ollo5ed during sa'ple collection and analysis. Aa8 8enc! s!eets 'ust 8e 'aintained t!at docu'ent 5!en t!e sa'ple 5as collected: !o5 it 5as preserved: and 5!at results 5ere o8tained. ,uality 4ontrol (,4) includes any testing 5!ic! is done to prove t!at t!e results are relia8le. One o# every ten sa'ples analy-ed s!ould 8e a ,uality 4ontrol c!ec0. *!is 'ay include duplicate sa'ples: spi0e sa'ples: reagent 8lan0 analyses and 0no5n ,4 sa'ples o8tained #ro' outside sources. Duplicate sa'ple analysis involves analy-ing t!e sa'e sa'ple t5ice and co'paring t!e results. *!e closer t!e results: t!e 'ore accurate t!e analysis. 6esults s!ould not di##er 8y 'ore t!an 12G. Spi0e sa'ple analysis involves adding 0no5n a'ounts o# analyte to a sa'ple and calculating t!e percent recovery. *!ese are discussed #urt!er in 4!apter 12. In DO testing: a ,4 progra' includes c!ec0ing DO results #ro' di##erent locations in tan0s and strea's to deter'ine t!e 'ost representative location #or testing. Duplicate sa'ples s!ould 8e analy-ed 5!en utili-ing t!e /in0ler et!od to test #or varia8ility. Dse t!e /in0ler et!od to c!ec0 t!e cali8ration o# t!e DO 'eter 5!en using t!e 'e'8rane electrode 'et!od. Sa'ple 8enc! s!eets are included in Appendix 4.

Ans@ers to 7ui::es 7ui: 44* 1. /!at is dissolved oxygen (DO)H The a ount oA dissolved or Aree oxygen present in @ater .

4!apter " % 12

2.

/!at are t!e sa'pling re9uire'ents #or a DO sa'ple t!at is to 8e tested in t!e la8oratoryH Sa ples Aor DO easure ent in the la/oratory ust /e )olle)t in a .2> B 0>> L BOD /ottle4

3.

/!at are t!e approved 'et!ods #or deter'ination o# DOH 6inCler ,a:ide odiAi)ation- and e /rane ele)trode ethods4

".

4an a DO sa'ple 8e preservedH I# so: !o5H %es5 iA the 6inCler ethod is to /e used Aor the DO deter ination4 Add the reagents oA the 6inCler pro)edure and store Aor up to t@o hours5 prote)ted Aro strong sunlight5 or add sulAuri) a)id and store at *> to .>DC Aor up to ; hours4

7ui: 44. 1. /!at reagents are re9uired #or D.O. deter'inations using t!e 'odi#ied /in0ler titration 'et!odH Manganous sulAate solution5 alCalineBpotassiu iodideBsodiu a:ide solution5 )on)entrated sulAuri) a)id5 phenylarsine oxide or sodiu thiosulAate and star)h indi)ator4 2. /!at e9uip'ent: apparatus or instru'entation is re9uired #or DO deter'inations using t!e 'odi#ied /in0ler titration 'et!odH 0>> L BOD /ottle5 2>> L Erlen eyer AlasC5 .2> L graduated )ylinder5 .2 or 2> /urette and stand5 * to *> L easuring pipettes5 and pipette /ul/4 3. /!at inter#erences a##ect DO deter'inations 8y t!e 'odi#ied /in0ler titration procedureH "ron salts5 organi) atter5 ex)ess suspended solids5 sulAide or sulAur dioxide5 residual )hlorine5 )hro iu or )yanide5 and )ertain oxidi:ing and redu)ing )o pounds4 7ui: 440 1. /!at e9uip'ent: apparatus or instru'entation is re9uired #or t!e DO deter'inations 8y t!e 'e'8rane electrode 'et!odH Dissolved oxygen eter and ele)trode ,la/oratory or Aield 6inCler pro)edure reagents and eEuip ent4 2. odels-5 BOD /ottle5 ModiAied L

/!at are t!e accepted 'et!ods o# cali8ration o# t!e DO 'eter and electrodeH ModiAied 6inCler )o parison5 saturated air5 and saturated @ater4

3.

/!at inter#erences can a##ect DO deter'inations 8y t!e 'e'8rane electrode procedureH Chlorine residual and salinity.

4!apter " % 13

A!!END"$ A (eAeren)es Standard et!ods #or t!e )xa'ination o# /ater and /aste5ater: A>$A%A//A%/)?: 1.t! )dition: 1112: et!od "&22%O. et!ods #or 4!e'ical Analysis o# /ater and /astes: D.S. )>A (223"%+1%222: "2&.1. NOTES+ arc! 11+1: et!od

4!apter " 3 Appendix A 3 >age 1

A!!END"$ B Dissolved Oxygen (eagents FO( MOD"F"ED 6"N<LE( MET1OD *4 Manganous sulAate solution a. Dissolve ".2g nSO " "$2O: or "22g nSO" 2$2O: or 3("g nSO" $2O in distilled 5ater: #ilter and dilute to 1 liter. *!is solution s!ould not produce a 8lue color 5it! starc! indicator 5!en added to an acidi#ied potassiu' iodide (CI) solution. a:ide solution

.4

AlCalineBiodideBsodiu a.

Dissolve &22g =aO$ (or +22g CO$) and 13&g =aI (or 1&2g CI) in (22 to +22 'A o# distilled 5ater.

CA'T"ON+ *!is 'ixture produces a great deal o# !eat and caustic #u'es. *a0e extre'e care in 'ixing and !andling. Dse a 8orosilicate glass (>yrex: Ci'ax: etc.) 8ea0er and avoid 8reat!ing #u'es or 8odily contact 5it! t!e solution. 8. c. A#ter t!e solution !as cooled: dilute to 1 liter 5!ile slo5ly and care#ully stirring. (I# possi8le: t!e use o# a 'agnetic stirrer is !ig!ly reco''ended.) Dissolve 12 g sodiu' a-ide (=a=3) in "2 'A distilled 5ater.

CA'T"ON+ This solution is poisonous4 d. Add t!e =a=3 solution: 5it! constant stirring: to t!e cooled al0aline iodide solution. Allo5 #inal 'ixture to cool to roo' te'perature 8e#ore using.

NOTE+ Sodiu a:ide @ill de)o pose over ti e and is no good aAter 0 onths4 =ote t!at sodiu' and potassiu' salts can 8e used interc!angea8ly. *!is reagent s!ould not produce a 8lue color 5it! starc! indicator 5!en diluted and acidi#ied. 04 SulAuri) a)id ,1.SO4-5 )on)entrated Dse concentrated reagent%grade acid ($2SO"). $andle 4are#ully: *!is c!e'ical 5ill 8urn !ands and clot!ing. 6inse a##ected parts 5it! large 9uantities o# tap 5ater to prevent inNury and re'ove conta'inated clot!ing: as residual 'ay still da'age s0in. CA'T"ON+ /!en 5or0ing 5it! al0aline a-ide and sul#uric acid: 0eep a near8y #aucet running #or #re9uent !and rinsing. 44 Star)h indi)ator solution Dse eit!er an a9ueous solution or solu8le starc! po5der 'ixture. >repare an a9ueous solution 8y dissolving 2 g o# la8oratory grade solu8le starc! po5der and 2.2 g o# salicylic acid (as a preservative) in 122 'A o# !ot distilled 5ater.

4!apter " 3 Appendix 7 3 >age 1

24

Sodiu a. 8. c.

thiosulAate standard solution5 >4>.2> N

Dissolve (.22& g =a2S2O3 &$2O in distilled 5ater. Add 1.& 'A ( = =aO$ or 2." g solid =aO$ and dilute to 1 liter. Standardi-e 5it! 8i%iodate solution. thiosulAate

Standardi:ation oA sodiu a. 8. c.

Dissolve approxi'ately 2 g CI: #ree #ro' iodate: in an )rlen'eyer #las0 5it! 122 to 1&2 'A distilled 5ater. Add 1 'A o# (= $2SO" or a #e5 drops o# concentrated $2SO": t!en 22.2 'A standard 8i%iodate solution. Dilute to 222 'A and titrate 5it! t!e sodiu' t!iosul#ate titrant solution. Add starc! 5!en a pale stra5 color is reac!ed and co'plete t!e titration until t!e 8lue color #irst disappears. I# t!e sodiu' t!iosul#ate is t!e proper strengt!: 22.2 'A 5ill 8e used in t!e titration. I# not: adNust t!e solution to t!e proper nor'ality. /iBiodate solution5 >4>.2> N

84

Standard potassiu

Dissolve .12." 'g o# potassiu' 8i%iodate (C$(IO 3)2) in distilled 5ater and dilute to 1 liter. 94 Standard phenylarsine oxide5 >4>.2> N 4o''ercially prepared 2.22&2 = >AO is availa8le #ro' several scienti#ic supply co'panies. As an alternative 2.22&2 = >AO 'ay 8e prepared 8y diluting a !ig!er nor'ality solution. CA'T"ON+ !AO is very poisonous4 Care reagent4 ;4 Copper sulAateBSulAa i) a)id solution a. Dissolve 32 g tec!nical grade sul#a'ic acid (=$2SO2O$): 5it!out !eat: in "+& 'A distilled 5ater. Dissolve &2 g tec!nical grade copper sul#ate (4uSO " &$2O) in &22 'A distiller 5ater. ix t!e copper sul#ate and sul#a'ic acid solutions toget!er and add 2& 'A glacial acetic acid (4$34OO$). ust /e taCen in preparation and handling oA this

8. c.

4!apter " 3 Appendix 7 3 >age 2

A!!END"$ C Sa ple Ben)h Sheets ?acility =a'e: DO analysis date:PPPPPP ti'e:PPPPPP 8y:PPPPPP Sa'ple 4ollected Date:PPPPP ti'e:PPPP 8y :PPPPPP DO >lant )##luent >lant In#luent Aeration *an0 Q1 Aeration *an0 Q2 Aeration *an0 Q3 Aeration *an0 Q" Digester Q1 Digester Q2 4o''ents: Te p4

4!apter " 3 Appendix 4 3 >age 1

?acility =a'e: DO eter 4ali8ration R aintenance Aog

(note 8eside date 5!en 'e'8rane is replaced) ont!: eter odel Q: eter Serial Q: Date 1. 2. 3. ". &. (. +. .. 1. 12. 11. 12. 13. 1". 1&. 1(. 1+. 1.. 11. 22. 21. 22. 23. 2". 2&. 2(. 2+. 2.. 21. 32. 31. 4o''ents: Ti e Sear:

Te p

Cal4 Set

Te)h4

4!apter " 3 Appendix 4 3 >age 2

DO METE( CAL"B(AT"ON LO& ont!: Sear: eter Serial Q: eter odel: 6ead Tero 5it! Sodiu' *!iosul#ate Solution: Date 1. 2. 3. ". &. (. +. .. 1. 12. 11. 12. 13. 1". 1&. 1(. 1+. 1.. 11. 22. 21. 22. 23. 2". 2&. 2(. 2+. 2.. 21. 32. 31. Cal4 Std4 44>> Cal4 Std4 *>4>> Che)C 94>> (eading Slope Sa ple Te p4 "nitials Ti e

4!apter " 3 Appendix 4 3 >age 3