Chapter 10

TABLE OF CONTENTS
Quality Control
Page
Section 1: Introduction to Quality Control........................................................................................... 2
Section 2: Glossary............................................................................................................................. 2
Section 3: Quality Assurance.............................................................................................................. 3
Section 4: Quality Control................................................................................................................... 3
Section 5: Duplicate Samples............................................................................................................. 3-4
Section : Spi!e Samples................................................................................................................... 4
Section ": #ea$ent %lan!s.................................................................................................................. 4
Section &: '(ternal Standards............................................................................................................ 5
Section ): Data Quality....................................................................................................................... 5
Section 1*: Si$ni+icant ,i$ures........................................................................................................... 5
Section 11: #oundin$ -++.................................................................................................................... 5
Section 12: .a/oratory 0or! S1eets.................................................................................................. 5-
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
C1apter 1* - 1
Chapter 10
QUALITY CONTOL
Se!tion 1" INTO#UCTION TO QUALITY CONTOL
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 $" %LOSSAY
A!!ura!y" 51e com/ination o+ /ias and precision o+ an analytical procedure 31ic1 re+lects 1o3 close
t1e measured 8alue is to t1e true 8alue.
Bia&" Consistent de8iation o+ measured 8alues +rom true 8alues caused /y systematic errors in a
procedure.
Cali'ration !he!( &tan)ar)" 51e standard used to determine 31et1er or not an instrument is properly
cali/rated.
Chain o* !u&to)y" 9rocedures and associated documents desi$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 ASSUANCE
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 CONTOL
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*); > ::*.115 B *.1*);>2; ( 1**@
A :*.** > *.112; ( 1**@
A 5@
%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* Pre!i&ion o* Pre!i&ion o*
2no3n Lo3 Le1el 4igh Le1el
A))ition& #upli!ate& #upli!ate&
5 5 5 Analy&i&
<utrients &* - 12* 25 1*
4etals &* - 12* 25 1*
Inor$anics &* - 12* 25 1*
Se!tion 6" SPI2E SA/PLES
Spi!e sample analysis :or !no3n addition; is used to test t1e met1od at 8aryin$ 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" E9TENAL 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$1 precision.
Se!tion 10" SI%NIFICANT FI%UES
5o a8oid reportin$ 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$it. ,or e(ample7
11.443 is rounded o++ to 11.447 31ile 11.44" is rounded o++ to 11.45.
Se!tion 1$" LABOATOY ;O2 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. Date and time o+ sample collection
2. 9erson 31o collected t1e sample
3. Sample preser8ation
4. Analyte tested
5. #a3 data
. Calculations
". Section +or recordin$ a/normal conditions
Se!tion 1," QUALITY CONTOL ;O2 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. Calculate t1e percent di++erence /et3een t1e resultsF 1.)1 and 2.*3.
2. 01y s1ould QC samples /e purc1ased +rom outside sources and /e tested
periodicallyG
3. 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= #ate an) ti+e o* &a+ple !olle!tion
$= Per&on 3ho !olle!te) the &a+ple
,= Sa+ple pre&er1ation
-= Analyte te&te)
.= a3 )ata
6= Cal!ulation&
7= Se!tion *or re!or)ing a'nor+al !on)ition&
C1apter 1* - "
APPEN#I9 A
e*eren!e&
Standard 4et1ods +or t1e '(amination o+ 0ater and 0aste3ater7 1&t1t1 'dition7 A00A7 A9EA7 09C,F
0ater 9ollution Control ,ederation7 0as1in$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$e 2
La' Che+i!al In1entory
Che+i!al Na+e FFFFFFFFFFFFFFFFFFFFFFF Lo!ation FFFFFFFFFFFFF
#ate e!ei1e) Quantity Supplier #ate Opene) #ate E+ptie)
C1apter 1* > Appendi( % > 9a$e 3
La' eagent Preparation Log
#ate eagent Te&t Te!h=
C1apter 1* > Appendi( % > 9a$e 4