Chapter 10

TABLE OF CONTENTS Quality Control

Page

Section 1: Introduction to Quality Control........................................................................................... Section 2: Glossary............................................................................................................................. Section 3: Quality Assurance.............................................................................................................. Section 4: Quality Control................................................................................................................... Section 5: Duplicate Samples............................................................................................................. Section : Spi!e Samples................................................................................................................... Section ": #ea$ent %lan!s.................................................................................................................. Section &: '(ternal Standards............................................................................................................ Section ): Data Quality....................................................................................................................... Section 1*: Si$ni+icant ,i$ures........................................................................................................... Section 11: #oundin$ -++.................................................................................................................... Section 12: .a/oratory 0or! S1eets.................................................................................................. Qui2 1*.1.............................................................................................................................................. Section 13: Quality Control................................................................................................................. Ans3ers to Qui2 1*.1........................................................................................................................... Appendi( A: #e+erences Appendi( %: Sample %enc1 S1eets Appendi( C: 4et1od C1ec!list Appendi( D: .a/ C1ec!list

2 2 3 3 3-4 4 4 5 5 5 5 5-

"

C1apter 1* - 1

Chapter 10
QUALITY CONT OL
Se!tion 1" INT O#UCTION TO QUALITY CONT OL 5o o/tain meanin$+ul data on 3ater 6uality7 t1e la/oratory must +irst collect a representati8e sample and deli8er it unc1an$ed +or analysis. 51e analyst must t1en per+orm t1e analysis correctly usin$ t1e proper met1od. ,inally7 t1e results o+ t1e analyses must /e recorded accurately and permanently +or +uture use. 51e entire process must /e carried out in a consistent7 deli/erate manner accordin$ to an o8erall plan esta/lis1ed /y la/oratory personnel. In t1is c1apter7 3e 3ill discuss 1o3 6uality assurance and 6uality control are de8eloped and maintained. Se!tion $" %LOSSA Y A!!ura!y" 51e com/ination o+ /ias and precision o+ an analytical procedure 31ic1 re+lects 1o3 close t1e measured 8alue is to t1e true 8alue. Bia&" Consistent de8iation o+ measured 8alues +rom true 8alues caused /y systematic errors in a procedure. Cali'ration !he!( &tan)ar)" 51e standard used to determine 31et1er or not an instrument is properly cali/rated. Chain o* !u&to)y" 9rocedures and associated documents desi$ned to trace t1e custody o+ a sample +rom t1e point o+ ori$in to +inal analysis 3it1 t1e intent o+ le$ally demonstratin$ t1at custody remained intact and t1at no tamperin$ occurred. #upli!ate" 9er+ormin$ t1e analysis o+ a sample t3ice to determine reproduci/ility. Also7 t3o samples ta!en at t1e same time +rom one location. La'oratory !ontrol &tan)ar)" A standard7 usually certi+ied /y an outside a$ency7 used to measure t1e /ias in a procedure. Pre!i&ion" A measure o+ t1e a/ility to reproduce analytical results. It is $enerally determined t1rou$1 t1e analysis o+ duplicate samples. Quality a&&e&&+ent" 51e procedure +or determinin$ t1e 6uality o+ la/oratory measurements usin$ data +rom internal and e(ternal 6uality control measures. Quality a&&uran!e" A de+initi8e plan +or la/oratory operation t1at speci+ies t1e measures used to produce data o+ !no3n precision and /ias. Quality a&&uran!e progra+" 0ritten policies and procedures t1at outline 1o3 t1e la/oratory intends to produce data o+ !no3n and accepted 6uality. Quality !ontrol" A set o+ measures 3it1in a sample analysis met1od to assure t1at t1e process is in control. Se!tion ," QUALITY ASSU ANCE Quality assurance :QA; is a set o+ operatin$ principles t1at7 i+ strictly +ollo3ed durin$ sample collection and analysis7 3ill produce data o+ !no3n and de+ensi/le 6uality. A 6uality assurance pro$ram must /e de8eloped 31ic1 includes $uidelines +or la/ personnel to +ollo3 31en collectin$ and preser8in$ samples7

C1apter 1* - 2

selectin$ 31ic1 met1ods to use +or t1e analyses7 and detailed procedures +or t1e actual testin$. 51e QA pro$ram s1ould include trainin$ re6uirements +or employees7 e6uipment pre8entati8e maintenance procedures7 cali/ration procedures and 6uality control testin$. Guidelines +or data assessment and reportin$ are also included and may in8ol8e t1e use o+ c1arts or ta/les 31ic1 document trends and QC sample results. .a/ /enc1 s1eets must /e maintained t1at document 31en t1e sample 3as collected7 1o3 it 3as preser8ed7 and 31at results 3ere o/tained. Se!tion -" QUALITY CONT OL Quality Control :QC; includes any testin$ 31ic1 is done to pro8e t1at t1e results are relia/le. -ne o+ e8ery ten samples analy2ed s1ould /e a QC c1ec!. 51is may include duplicate samples7 spi!e samples7 rea$ent /lan! analyses and !no3n QC samples o/tained +rom outside sources. ,or <9D'S .a/ 3or!7 you must :as re6uired /y <9D'S permit; de8elop a =Quality Assurance>Quality Control? plan +or all parameters on your permit. 51is re6uirement includes any contract la/s as 3ell as your in 1ouse la/. In any e8ent7 it is t1e <9D'S permit 1olders responsi/ility. Se!tion ." #UPLICATE SA/PLES Duplicate sample analysis is used to determine reproduci/ility or consistency in t1e met1od. Duplicates :or split samples; are t3o samples ta!en +rom t1e same source7 di$ested7 distilled or ot1er3ise processed7 and t1en analy2ed identically. 51e accepta/le le8el or 8ariation /et3een duplicates 8aries /y test and /y concentration o+ analyte. 5a/le 1*-1 s1o3 acceptance le8els +or duplicate samples in 3ater and 3aste3ater. 51e percent di++erence is calculated /y di8idin$ t1e di++erence /et3een t1e t3o results /y t1eir a8era$e as +ollo3s: @ di++erence A :( - y; > ::( B y;>2; ( 1**@ 31ere ( A result o+ +irst analysis y A result o+ second analysis ,or e(ample7 an e++luent sample is tested t3ice +or p1osp1orous and t1e results o/tained are *.1*) and *.115 m$>.. @ di++erence A :*.115 - *.1*); > A :*.** > *.112; ( A 5@ ::*.115 B *.1*);>2; ( 1**@ 1**@

%y c1ec!in$ 5a/le 1*-1 3e see t1at a 5@ di++erence +or a lo3 le8el nutrient analysis is accepta/le.

C1apter 1* - 3

Ta'le 1001 Acceptance .imits +or Duplicate Samples and Cno3n Additions to 0ater and 0aste3ater e!o1ery o* 2no3n A))ition& 5 <utrients 4etals Inor$anics &* - 12* &* - 12* &* - 12* Pre!i&ion o* Lo3 Le1el #upli!ate& 5 25 25 25 Pre!i&ion o* 4igh Le1el #upli!ate& 5 1* 1* 1*

Analy&i&

Se!tion 6" SPI2E SA/PLES Spi!e sample analysis :or !no3n addition; is used to test t1e met1od at 8aryin$ concentrations o+ analyte. Cno3n amounts o+ analyte are added to a sample and t1e percent reco8ery is calculated. I+ inter+erences are present in t1e sample7 results may /e o/tained 31ic1 are si$ni+icantly 1i$1er or lo3er t1an t1e actual concentration. 51e accepta/le percent reco8ery o+ !no3n additions 8aries /y test and is s1o3n in 5a/le 1*-1. 51e percent reco8ery is calculated /y di8idin$ t1e sample result /y t1e e(pected result as +ollo3s: '(pected spi!e result A sample result B standard conc. 9ercent reco8ery A spi!e result di8ided /y e(pected result ( spi!e 8olume o8er ori$inal 8olume ( 1**@ ,or e(ample7 a 1** m. '++luent sample is spi!ed 3it1 1 m. o+ 1** m$>. Ammonia nitro$en standard yieldin$ t1e +ollo3in$ results: '++luent sample result: *.1"4 m$>. Spi!ed '++luent sample result: 1.21 m$>. Conc. o+ 1 m. o+ 1** m$>. standard in 1** m.: 1.** m$>. '(pected spi!e result A sample result B standard conc. A *.1"4 B 1.** A 1.1"4 9ercent reco8ery A spi!e result di8ided /y e(pected result ( spi!e 8olume o8er ori$inal 8olume ( 1**@ A 1.21 di8ided /y 1.1"4 ( 1*1>1** ( 1**@ A 1*4@ Se!tion 7" EA%ENT BLAN2S

Analy2e rea$ent /lan!s anytime ne3 rea$ents are used and as o+ten as re6uired /y speci+ic met1ods. %lan!s monitor t1e purity o+ rea$ents7 la/ distilled 3ater7 and t1e cleanliness o+ $lass3are and e6uipment. Also7 analy2e a rea$ent /lan! a+ter any sample o+ 1i$1 concentration t1at may cause carryo8er to t1e +ollo3in$ sample.

C1apter 1* - 4

Se!tion 8" E9TE NAL STAN#A #S QC samples 3it1 !no3n concentrations o+ analytes can /e purc1ased +rom a 8ariety o+ c1emical manu+acturers. 51ese s1ould /e used to demonstrate t1at cali/ration cur8es are accurate7 t1at t1e analysis is /ein$ properly run7 t1at cali/ration standards are accurate7 and to 8eri+y t1e results o+ analyses on plant samples. #esults o+ all QC testin$ must /e recorded. Sample /enc1 s1eets are included in Appendi( %. Se!tion :" #ATA QUALITY 51e most important indicators o+ data 6uality are its /ias and precision 31ic17 31en com/ined7 e(press its accuracy. -nly results 31ic1 1a8e $ood precision and lo3 /ias are accurate. %ias is a measure o+ systematic or in1erent error. It may /e a result o+ t1e met1od7 itsel+7 or t1e la/Ds use or interpretation o+ t1e met1od. #esults t1at are consistently lo3er or 1i$1er t1an t1e true 8alue re+lect 1i$1 /ias. 9recision is a measure o+ t1e closeness o+ replicate sample results. Ei$1 8aria/ility amon$ duplicates re+lects lo3 precision. Consistently close results re+lect 1i$1 precision. 9recision can /e determined /y calculatin$ t1e standard de8iation o+ t1e results. Accuracy re+ers to t1e de$ree o+ di++erence /et3een t1e measured 8alue and t1e true 8alue. ,actors a++ectin$ accuracy include contaminated $lass3are7 improperly maintained e6uipment7 carelessness in measurin$ samples or rea$ents7 and +ailin$ to +ollo3 t1e met1od consistently. Due to increased le$islation re$ulatin$ plant per+ormance and e++luent 6uality7 reported 8alues may /e used or c1allen$ed in court. Analysts must ma!e e8ery attempt to produce accurate results 3it1 lo3 /ias and 1i$1 precision. Se!tion 10" SI%NIFICANT FI%U ES 5o a8oid reportin$ results t1at are inaccurate or decei8in$7 =si$ni+icant +i$ures? are used. Si$ni+icant +i$ures $i8e an indication o+ t1e relia/ility o+ t1e analytical met1od used. #eported 8alues s1ould contain only si$ni+icant +i$ures. A 8alue is made up o+ si$ni+icant +i$ures 31en it contains all di$its !no3n to /e true and one last di$it in dou/t. ,or e(ample7 i+ a 8alue is reported as 1&. m$>.7 t1e =1&? must /e a +irm 8alue 31ile t1e =*. ? is some31at uncertain and may /e ="? or =5?. 51e num/er o+ si$ni+icant +i$ures +or a met1od is esta/lis1ed /y testin$ replicate samples and determinin$ 8aria/ility. ,or e(ample7 i+ an e++luent sample is tested 4 times +or ammonia and t1e results are: *.2*)7 *.2*"7 *.2117 and *.2* 7 t1e a8era$e s1ould /e reported as *.21 and not *.2*& since t1ere is 8aria/ility in t1e 1undredt1Ds di$it. Se!tion 11" OUN#IN% OFF

51e roundin$ o++ o+ num/ers is a necessary part o+ analytical reportin$. All instruments7 $lass3are7 and met1ods 1a8e limits on si$ni+icant +i$ures 31ic1 must /e ta!en into consideration 31en reportin$ results. <um/ers t1at are not si$ni+icant must /e dropped /y roundin$ o++. I+ t1e di$it 57 7 "7 &7 or ) is dropped7 round up one unit. I+ t1e di$it *7 17 27 37 or 4 is dropped7 do not c1an$e t1e precedin$ di$it. ,or e(ample7 11.443 is rounded o++ to 11.447 31ile 11.44" is rounded o++ to 11.45. Se!tion 1$" LABO ATO Y ;O 2 S4EETS 51e plant operator 1as t3o $oals in usin$ a la/oratory note/oo! and 3or! s1eets :or /enc1 s1eets;: +irst7 to record data7 and second7 to arran$e t1e data in an orderly manner. Days o+ 3or! can /e 3asted i+ data are 3ritten do3n on scrap paper 31ic1 is misplaced or t1ro3n a3ay. 0or! s1eets and note/oo!s 1elp pre8ent error and pro8ide a record o+ t1e 3or! per+ormed. 51e routine use o+ 3or! s1eets and note/oo!s is t1e only 3ay an operator can /e sure t1at all important in+ormation +or a test is properly recorded.

C1apter 1* - 5

51ere is no standard la/oratory +orm. 4ost treatment plants usually de8elop t1eir o3n 3or! s1eets +or recordin$ la/oratory results and ot1er important plant data. 51e 3or! s1eets are prepared in a manner t1at ma!es it easy to record t1e data7 re8ie3 it7 and reco8er it 31en necessary. 51ese s1eets pro8ide t1e in+ormation needed to complete <9D'S permit reportin$ +orms. 'ac1 plant may 1a8e di++erent needs +or collectin$ and recordin$ data. At a minimum7 3or! s1eets s1ould include t1e +ollo3in$ in+ormation: 1. 2. 3. 4. 5. . ". Date and time o+ sample collection 9erson 31o collected t1e sample Sample preser8ation Analyte tested #a3 data Calculations Section +or recordin$ a/normal conditions

Se!tion 1," QUALITY CONT OL ;O 2 S4EETS 'ac1 la/oratory is also re6uired to document proper care o+ e6uipment and 1andlin$ o+ la/ c1emicals. An e6uipment maintenance s1eet s1ould /e !ept up to date reportin$ all maintenance per+ormed on la/ instruments. 51e s1eet s1ould include t1e date7 time and tec1nician 31o per+ormed t1e 3or!. #epairs to e6uipment7 c1an$ed mem/ranes7 cleanin$s7 pre8entati8e maintenance c1ec!s and o/ser8ed pro/lems s1ould /e recorded. '8ery re+ri$erator7 o8en7 3ater /at1 and incu/ator must 1a8e a temperature record indicatin$ on a daily /asis /ot1 t1e re6uired temperature and t1e actual temperature. A c1emical in8entory must /e maintained t1at documents date o+ purc1ase7 e(piration date7 date o+ openin$7 and date 31en t1e c1emical is used up or discarded. It is also 1elp+ul to record 31ere t1e c1emical 3as purc1ased. A rea$ent preparation lo$ must /e maintained +or analysts to record t1e date o+ preparation o+ standards and rea$ents. 51is 1elps to maintain control o8er rea$ent preparation and pro8ides a met1od to trace t1e source o+ error 31en pro/lems are encountered. Sample QC /enc1 s1eets are included in Appendi( %. Qui< 10=1 1. 2. 3. Calculate t1e percent di++erence /et3een t1e resultsF 1.)1 and 2.*3. 01y s1ould QC samples /e purc1ased +rom outside sources and /e tested periodicallyG At a minimum7 31at in+ormation s1ould /e included on la/ 3or! s1eetsG

C1apter 1* -

An&3er& to Qui< 10=1 1. Calculate t1e percent di++erence /et3een t1e resultsF 1.)1 and 2.*3. 5 )i**eren!e > ?@ 0 yA B ??@ C yAB$A @ 1005 > ?$=0, 0 1=:1AB?$=0, C 1=:1AB$ @ 1005 > 0=1$B1=:7 @ 1005 > 65 2. 01y s1ould 6uality control samples /e purc1ased +rom outside sources and /e tested periodicallyG They are u&e) to )e+on&trate that !ali'ration !ur1e& are a!!urateD that the analy&i& i& 'eing properly runD that !ali'ration &tan)ar)& are a!!urateD an) to 1eri*y the re&ult& o* analy&e& on plant &a+ple&= 3. At a minimum7 31at in+ormation s1ould /e included on la/ 3or! s1eetsG 1= $= ,= -= .= 6= 7= #ate an) ti+e o* &a+ple !olle!tion Per&on 3ho !olle!te) the &a+ple Sa+ple pre&er1ation Analyte te&te) a3 )ata Cal!ulation& Se!tion *or re!or)ing a'nor+al !on)ition&

C1apter 1* - "

APPEN#I9 A e*eren!e& Standard 4et1ods +or t1e '(amination o+ 0ater and 0aste3ater7 1&t1t1 'dition7 A00A7 A9EA7 09C,F 0ater 9ollution Control ,ederation7 0as1in$ton7 DC7 1))2. -peration o+ 0aste3ater 5reatment 9lants7 Holume II7 Cali+ornia State Ini8ersity7 Sacramento +or t1e I.S. '.9.A. NOTES"

C1apter 1* > Appendi( A > 9a$e 1

APPEN#I9 B

Sa+ple Ben!h Sheet&

La' #upli!ate Analy&e& #ate Sa+ple Analy&i& Te!h= Fir&t&t re&ult Se!on)n) re&ult 5 )i**eren!e

Spi(e) Sa+ple Analy&i& #ate Sa+ple !on!= Sa+ple 1ol= Spi(e !on!= Spi(e 1ol= Spi(e re&ult Cal!= 5 e!o1ery

C1apter 1* > Appendi( % > 9a$e 1

In&tru+ent /aintenan!e Log #ate Te!h In&tru+ent /o)el E /aintenan!e Per*or+e) ea&on

C1apter 1* > Appendi( % > 9a$e 2

La' Che+i!al In1entory Che+i!al Na+e FFFFFFFFFFFFFFFFFFFFFFF #ate e!ei1e) Quantity Lo!ation FFFFFFFFFFFFF #ate Opene) #ate E+ptie)

Supplier

C1apter 1* > Appendi( % > 9a$e 3

La'

eagent Preparation Log #ate eagent Te&t Te!h=

C1apter 1* > Appendi( % > 9a$e 4