ARC-MET8000

Analizador y Seleccionador mvil de

aleaciones
Oxford Instruments Analytical
Oy
P.O. Box 85 (Nihtisillankuja 5)
I!"#$%& '(POO) inland
*el+ ,%58 - %#- .&&
ax+ ,%58 - %#-. &%""
'mail+ info/oxinst.0
111.oxford!instruments.com
5101 768-4E
Edi!ion "#10
Man$al de Cali%racion
C&'TE'()&
&. 2O BA(I3O 4'2 A53!6'* 7 2A '6I(ION OP*I3A......................&
*$e es el ARC-MET+########################################################################################################### 1
Modos de o,eracion########################################################################################################### 1
Carac!eris!icas del Arc-Me!################################################################################################# 1
Es,ec!rosco,ia de emision o,!ica###################################################################################### "
#. 3A2IB5A*IN8 A 3ON3'N*5A*ION 6O4'2.................................9
Concen!ra!ion models in Es,ec!rosco,ia de emision o,!ica##############################################7
-rinci,les o. cali%ra!in/ a concen!ra!ion model#################################################################8
-lannin/ !0e cali%ra!ion##################################################################################################### 8
Selec!in/ cali%ra!ion sam,les############################################################################################ 1
2o3 !0e concen!ra!ion model is %$il!#################################################################################1
S!ar!in/ !0e cali%ra!ion###################################################################################################### 1
Selec!in/ elemen!s########################################################################################################### 1"
Selec!in/ e4ci!a!ion ,arame!ers###################################################################################### 15
Addin/ and meas$rin/ cali%ra!ion sam,les#####################################################################15
Meas$rin/ sam,les########################################################################################################## 16
60a! does !0e Arc-Me! do 3i!0 cali%ra!ion meas$remen!s+############################################17
Addin/ s!andardiza!ion sam,les###################################################################################### 18
Some !erminolo/y######################################################################################################## 18
T0e %asics o. s!andardiza!ion###########################################################################################18
2o3 !o selec! s!andardiza!ion sam,les########################################################################11
Selec!in/ !0e %es! lines .or eac0 elemen!########################################################################""
7sin/ 8ine 6izard############################################################################################################# "5
1 1
7sin/ !3o lines .or cali%ra!ion########################################################################################## "6
Ma9in/ a re/ression model############################################################################################## "7
7nders!andin/ !0e Re/ression cali%ra!ion men$##########################################################"7
Addin/ an inde,enden!################################################################################################ "1
Selec!in/ an inde,enden!############################################################################################ 50
Removin/ sam,les .rom !0e cali%ra!ion#######################################################################51
Removin/ an inde,enden!########################################################################################### 55
:inis0in/ elemen! cali%ra!ion####################################################################################### 55
)e;nin/ a con!rol sam,le################################################################################################ 54
Acce,!in/ !0e model######################################################################################################## 55
APP'N4I: A. *;' '(('N*IA2( O 5'85'((ION..........................%9
Sim,le linear re/ression################################################################################################### 58
Eval$a!ion o. !0e re/ression############################################################################################ 51
M$l!ivaria!e linear re/ression########################################################################################### 4"
S!e,3ise re/ression######################################################################################################### 45
Some s,ecial cases########################################################################################################## 44
APP'N4I: B. 3ON3'N*5A*ION I2' O56A*.............................-
ii
&. 2O BA(I3O 4'2 A53!6'* 7 2A '6I(ION OP*I3A
<ue es el A53!6'*=
El Arc-Me! 8000 es $n Analizador y seleccionador mvil de aleaciones< el c$al $sa
la 's>ectrosco>ia de emision o>tica (O'(= como s$ ,rinci,io de !ra%a>o# El Arc-
Me! !iene $na am,lia area de a,licacions en aceros de %a>a aleacion< aceros de
al!a aleacion< y o!ras aleaciones como el al$minio< co%re< ni?$el< co%al!o<
ma/nesio< zirconi y !i!anio#
el Arc-Me! consis!s de dos mod$les ,rinci,ales< el sensor y la consola< connec!ados
,or $n ca%le @e4i%le# El sensor con!iene $na a camara de ?$emado con $n
elec!rodo< $n mod$lo de e4i!acion y $n es,ec!rome!ro# 8a consola con!iene la
$nidad ,rinci,al de ,roceso< !eclado y $na ,an!alla elec!ro l$minescen!e< %o!elln
de /as y la .$en!e de ener/ia#
8a es!r$c!$ra del Arc-Me! es!a descri!a en mas de!alle en el manual del usuario#
6odos de o>eracion
el Arc-Me! !iene dos modos %asicos de o,eracionA analisis e iden!i;cacion# Todas
las carac!erirs!icas es!an dis,oni%les ya sea en el modo de ar/on o modo de aire
Como $n analisador< el Arc-Me! le da valores de ensayo ,ara elemen!os es,eci;cos
en la m$es!ra Bassay mode=Bmodo de ensayo=#
Como $n iden!i;cador el Arc-Me! le oCreces al/o mas de dos Modos de o,eracionA
es!e le dice ya sea el /rado de la m$es!ra B?rade mode= Bmodo /rado= o lo
iden!i;ca com,arandolo con las m$es!ras de re.erencia ya medidas
BIdenti0cation mode< PA((@AI2 !mode=#
T0e Arc-Me! 3ill iden!i.y !0e /rade o. !0e sam,le a.!er i! 0as calc$la!ed !0e
concen!ra!ions o. !0e alloyin/ elemen!s# T0e Arc-Me! 3ill !0en com,are !0ese
concen!ra!ions !o !0e /rade li%rary#
(. no assay model .or !0e de!ermina!ion o. concen!ra!ions is availa%le< several
9no3n re.erence sam,les can %e ,$! !o/e!0er !o .orm a li%rary# T0e $n9no3n
sam,le is !0en com,ared 3i!0 !0e li%rary !o /e! an iden!i;ca!ion#
3aracteristicas del Arc!6et
T0e Arc-Me! 0as several $ni?$e .ea!$res !0a! /rea!ly sim,li.y i!s $se#
T0e es,ec!rome!ro i!sel. 0as %een minia!$rized %y $sin/ a ,0o!odiode array as a
li/0!-de!ec!in/ elemen!# T0is 0as made i! ,ossi%le !o ,lace !0e es,ec!rome!ro
inside el sensor< 30ic0 in !$rn elimina!es o,!ical ;%re lin9s %e!3een el sensor and
!0e main $ni! oCerin/ e4cellen! s!a%ili!y in car%on con!en! meas$rin/#
1 1
Deca$se !0e Arc-Me! $ses !0e ,0o!odiode array as a li/0!-de!ec!in/ $ni!< i! can
record !0e 30ole emission s,ec!r$m o. !0e sam,le and !0ere%y elimina!e ,ro;lin/
,roced$res and ,rovide !0e %es! analy!ical lines .or eac0 a,,lica!ion# T0ese
.ea!$res< co$,led 3i!0 ,o3er.$l so.!3are< oCer yo$ a 0i/0 de/ree o. a,,lica!ion
@e4i%ili!y#
(n every meas$remen! !0e Arc-Me! a$!oma!ically iden!i;es !0e ma!ri4
elemen!# T0is ens$res !0a! !0e Arc-Me! 3ill no! even !ry !o calc$la!e
assay val$es .or a sam,le i! canno! analyse#
's>ectrosco>ia de emision o>tica
T0e Arc-Me! is an o,!ical emission es,ec!rome!ro# To e4ci!e !0e o,!ical
s,ec!r$m o. !0e sam,le< Arc-Me! %$rns an in!err$,!ed )C-arc %e!3een
!0e sam,le and $n elec!rodo# T0e %$rn se?$ence consis!s o. !3o
,0asesA >re!Aurn and analysis Aurn# -re-%$rn mel!s !0e sam,lin/
area !o elimina!e any incl$sions and o!0er non-$ni.ormi!ies !0a! mi/0!
aCec! !0e res$l!s# (n A(R %$rn ,re-%$rn also cleans !0e elec!rode B0is!ory
eCec! elimina!ed=# )$rin/ !0e analysis %$rn !0e s,ec!r$m o. !0e sam,le
is recorded and s!ored in !0e Arc-Me!Es memory# T0e analy!ical res$l!s
are !0en calc$la!ed .rom !0e ac?$ired s,ec!r$m $sin/ a ,o3er.$l
micro,rocessor#
*o learn more aAout the Arc!6etBs excitation source
>arameters) read cha>ter Excitation sets.
To /e! an idea on 0o3 !0e s,ec!r$m is /enera!ed< consider !0e sam,le
a!oms in !0e sam,lin/ area Bsee ne4! ,ic!$re=# Dasically !0e ,rocess is
!0e same $nder ar/on a!mos,0ere or in air#
Electrode
Sampling area
Sample
Arc
60en !0e sam,le a!oms are /iven e4!ra ener/y in !0e .orm o. an
elec!rical c$rren!< !0ey ?$ic9ly va,orise and /e! e4ci!ed# Dy e4ci!a!ion<
!0e a!omEs o$!er s0ell elec!rons a%sor% ener/y and move $, !o 0i/0er
ener/y levels or s0ells#
1 1
8& DAS(C& )E8 ARC-MET F 8A EM(S(&' &-T(CA
External energy
Electrons
Nucleus
T0e e4ci!ed s!a!e las!s .or a very s0or! !ime ,eriod< !y,ically 1 Gs< a.!er
30ic0 !0e a!om loses i!s e4cess ener/y and emi!s li/0!# T0e e4ci!ed
elec!rons re!$rn !o !0eir ori/inal s0ells and !0e a!om is said !o %e in !0e
/ro$nd s!a!e a/ain#
Light
T0e emi!!ed li/0! 0as a c0arac!eris!ic 3avelen/!0< 30ic0 is !y,ical !o !0e
elemen!# T0ese emission lines da!a are ,$%lis0ed in re.erence %oo9s#
&ne elemen! may 0ave !0o$sands o. lines in !0e visi%le and 7-
s,ec!r$m#
3
Cali%ra!orEs man$al
This is the line
wavelength in
angstroms
This gives the
element for the
line
These numbers in-
dicate the intensity
of the line in difer-
ent excitations
T0e li/0! emi!!ed %y !0e va,orized a!oms o. !0e sam,le is collec!ed<
dis,ersed in!o a s,ec!r$m and recorded %y !0e es,ec!rome!ro o,!ics#
T0e %asic /eome!ry o. !0e o,!ics is ill$s!ra!ed in !0e .ollo3in/ ,ic!$re#
'o!e !0a! !0ere is a diCerence in !0e /eome!ry %e!3een !0e ARH&' and
!0e A(R sno$!s# T0e ARH&' sno$! con!ains a 3indo3 and a mirror and
!0e A(R sno$! con!ains lenses and an o,!ical ;%re#
4
8& DAS(C& )E8 ARC-MET F 8A EM(S(&' &-T(CA
T0e .ollo3in/ ;/$re s0o3s yo$ ,ar! o. !0e iron s,ec!r$m recorded %y
!0e Arc-Me!# Every ,ea9 in !0e s,ec!r$m re,resen!s one or more
emission lines emi!!ed %y !0e sam,le a!oms# T0e F-a4is dis,lays
in!ensi!y da!a and !0e I-a4is 3avelen/!0#
T0e s,ec!r$m is sen! !o !0e main $ni! 30ere !0e analysis so.!3are
iden!i;es !0e ma!ri4 elemen!< correc!s .or any !em,era!$re or s0oc9
ini!ia!ed s,ec!r$m s0i.!s< com,ensa!es .or losses in o,!ics !0ro$/0,$!
and ;nally calc$la!es !0e res$l!s accordin/ !o !0e $serEs ins!r$c!ions#
5
Cali%ra!in/ a Concen!ra!ion model
Cali%ra!in/ Concen!ra!ion model
#. 3aliAratin? a concentration model
T0is c0a,!er e4,lains !0e ,rinci,les o. !0e concen!ra!ion model
incl$din/ i!s cali%ra!ion# T0e !0eory %e0ind cali%ra!ion is e4,lained in
de!ail in A,,endi4 A Basics of regression#
3oncentration models in 's>ectrosco>ia de emision o>tica
T0e concen!ra!ion model may 3ell %e re/arded as !0e mos! im,or!an!
!y,e o. model# (! is ac!$ally !0e only model !0a! /ives yo$ an e4ac!
res$l! o. an $n9no3n sam,leEs concen!ra!ion val$es#
2o3ever< yo$ s0o$ld al3ays remem%er !0a! concen!ra!ion models in
Es,ec!rosco,ia de emision o,!ica< as in mos! cases in s,ec!rosco,y<
m$s! %e cali%ra!ed $sin/ relia%le re.erence s!andards#
5ememAer that the concentration model caliAration can neCer
Ae more accurate than the standards used for caliAratin? it. In
other 1ords) there are also errors in the certi0ed caliAration
s>ecimens. *his error (leCel of uncertainty) estimate should Ae
documented in the caliAration sam>le certi0cate.
(n Es,ec!rosco,ia de emision o,!ica< concen!ra!ion val$es are $s$ally
calc$la!ed $sin/ !0e internal standard >rinci>le# T0is means !0a! an
elemen!Es meas$remen! lineEs in!ensi!y is al3ays divided %y !0e
in!ensi!y o. a reference line# T0e re.erence line is a ma!ri4 elemen!
line# (n calc$la!in/ concen!ra!ion val$es !0e concen!ra!ion val$es ra!ios
B!0a! is elemen! concen!ra!ions divided %y ma!ri4 elemen!
concen!ra!ion= are calc$la!ed ;rs!#
T0e calc$la!ion o. concen!ra!ion val$es is !0en cond$c!ed %y ass$min/
!0a! !0e s$m o. meas$red elemen!sE concen!ra!ion val$es< incl$din/
ma!ri4 elemen!< is 100J#
60en doin/ !0e calc$la!ion !0e Arc-Me! does !0e .ollo3in/# (!A
&. OAtains intensities for all analysis lines and for all reference
lines.
#. 3alculates intensity ratios for all elements
Cali%ra!orEs man$al
%. 3alculates concentration ratios
T0e concen!ra!ion ra!ios are calc$la!ed accordin/ !o !0e model
.. OAtains matrix concentration
5. 3alculates element concentrations
Princi>les of caliAratin? a concentration model
Concen!ra!ion model cali%ra!ion is a len/!0y ,roced$re !0a! re?$ires
some ,reliminary ,lannin/#
As a 30ole< concen!ra!ion model cali%ra!ion can %e divided in!o
diCeren! ,0ases#
&. Plannin? of the caliArationD s>eci0cation of caliAration
ran?es.
#. (electin? necessary caliAration standards.
%. Pre>arin? the standards for caliAration.
.. *y>in? caliAration sam>lesB concentration Calues into the
Arc!6et (or loadin? them from an external com>uter).
5. (electin? a suitaAle excitation set.
$. 6easurin? caliAration sam>les.
9. 3han?in? analysis and reference lines) if necessary.
8. 6easurin? standardiEation or normalisation sam>le(s).
-. Buildin? models for each element to Ae caliArated.
&". 6easurin? test sam>les.
&&. Acce>tin? the model.
&#. Printin? caliAration re>ort (if needed).
Plannin? the caliAration
To ma9e !0e ac!$al cali%ra!ion easier yo$ s0o$ld !a9e eno$/0 !ime !o
,lan !0e cali%ra!ion# -lannin/ !0e cali%ra!ion means !0a! yo$ s0o$ld
decide onA
K T0e elemen!s yo$ 3is0 !o incl$de in !0e cali%ra!ion#
8
Cali%ra!in/ a Concen!ra!ion model
Cali%ra!in/ Concen!ra!ion model
K T0e concen!ra!ion ran/es .or eac0 elemen!#
K 60a! 9ind o. s!andards yo$ 3ill $se .or cali%ra!ion#
T0e in!ernal s!andard ,rinci,le $sed in Es,ec!rosco,ia de emision
o,!ica ass$mes !0a! !0e s$m o. all analysed concen!ra!ions is 100 ,er
cen!# T0is %asic ass$m,!ion im,lies !0a! all !0ose elemen!s !0a! 0ave
concen!ra!ions /rea!er !0an 0#5 ,er cen! s0o$ld %e incl$ded in !0e
model#
Al1ays make sure that all those elements that haCe
concentrations ?reater than ".5 >er cent are included in the
caliAration.
(electin? caliAration sam>les
T0e cali%ra!ion sam,les m$s! %e re,resen!a!ive sam,les# T0eir
elemen!al concen!ra!ions m$s! 0ave %een analysed $sin/ a relia%le
me!0od# -re.era%ly yo$ s0o$ld $se only !racea%le s!andards !0a! 0ave
%een analysed %y several la%ora!ories $sin/ diCeren! !ec0ni?$es# T0ese
s!andards can %e ordered .rom &4.ord (ns!r$men!s Analy!ical &F#
T0e !o!al n$m%er o. cali%ra!ion sam,les needed .or cali%ra!ion de,ends
on !0e concen!ra!ion ran/e o. individ$al elemen!s# (n /eneral< !0e more
cali%ra!ion sam,les yo$ $se< !0e %e!!er and more re,resen!a!ive 3ill %e
!0e cali%ra!ion# T0e Arc-Me! can $se $, !o 60 cali%ra!ion sam,les in one
model#
6ake sure that the caliAration sam>les you use re>resent the
sam>les to Ae analysed usin? the model.
Selec! !0e cali%ra!ion sam,les s$c0 !0a! !0e concen!ra!ions o. !0e
cali%ra!ion sam,les cover !0e 30ole concen!ra!ion ran/e re?$ired#
-re,are !0e cali%ra!ion sam,les %y /rindin/ as e4,lained in c0a,!er 5
L-re,arin/ sam,les .or meas$remen!E in !0e 7serEs man$al#
;o1 the concentration model is Auilt
T0e Arc-Me! 0as ,o3er.$l so.!3are !o 0el, yo$ cali%ra!e any !y,e o.
model yo$ need# Concen!ra!ion model cali%ra!ion 0as %een made as
easy as ,ossi%le %y $sin/ a ste>1ise re?ression calc$la!ion sc0eme#
T0e Arc-Me!Es a,,roac0 /ives yo$< as a cali%ra!or< many 3ays !o do a
cali%ra!ion# Fo$ can ei!0er selec! !0e varia%les yo$rsel. or leave !0e !as9
!o !0e ins!r$men! and ado,! !0e role o. an Lins,ec!orE# Fo$ !0en sim,ly
acce,! or re>ec! 30a!ever !0e ,ro/ram s$//es!s# T0e selec!ion s0o$ld
,re.era%ly %e %ased on ,0ysical %ases# (. !0e ,ro/ram s$//es!s
9
Cali%ra!orEs man$al
some!0in/ !0a! is in con!radic!ion 3i!0 ,0ysics !0e da!a is mos! li9ely
erroneo$s#
(tartin? the caliAration
To ma9e a ne3 concen!ra!ion model carry o$! !0e .ollo3in/ ins!r$c!ionsA
&. (tart your Arc!6et F the measurement menu 1ill a>>ear.
T0e Main men$ can %e iden!i;ed %y !0e solid in.orma!ion ;eld in !0e
$,,er ,ar! o. !0e screen# Ma9e s$re !0a! yo$ 0ave selec!ed !0e
cali%ra!or $ser mode#
C0ec9 also !0a! yo$ 0ave a mo$se connec!ed !o !0e Arc-Me!#
#. Press Menu button.
%. (elect confguration from the list.
T0e .ollo3in/ screen 3ill %e visi%le#
.. (elect Gne1 modelB and add a ne1 name for the model.
10
Cali%ra!in/ a Concen!ra!ion model
Cali%ra!in/ Concen!ra!ion model
Fo$ s0o$ld crea!e a dis!inc!ive name !0a! 0as no! %een $sed %e.ore# T0e
name m$s! no! con!ain any o. !0e .ollo3in/ c0arac!ersA M N A O + P Q R S
5. Press OK.
A.!er !0e s$ccess.$l ini!ializa!ion o. !0e ne3 model< a s!ar!-$, screen 3ill
a,,ear#
11
Cali%ra!orEs man$al
(electin? elements
:irs! yo$ 0ave !o decide 30ic0 elemen!s yo$ 3an! !o incl$de in !0e
model# T0is selec!ion is %ased on yo$r re?$iremen!s# 2o3ever< yo$
canno! .reely selec! !0e elemen!s# 6e 0ave ,revio$sly disc$ssed !0is in
!0e Principles of calibrating a concentration model#
Selec! LElemen!sE ,a/e .rom !0e main ,a/e< !0e .ollo3in/ in!er.ace 3ill
a,,earA

Matrix
element
Can be
selected here
List of available
Elements

Line selection
List of selected elements
+ information
Up and down
buttons
Pages
&. (elect matrix element
Selec! !0e ma!ri4 elemen! .rom !0e lis! in !0e $,,er le.!mos! corner#
'o!e !0a! in addi!ion !o selec!in/ !0e ma!ri4 elemen!< yo$ s0o$ld also
selec! !0e a!mos,0ereT ei!0er ARH&' or A(R#
#. (elect elements
A.!er selec!in/ !0e ma!ri4 elemen! and !0e a!mos,0ere< selec! !0e
availa%le elemen!s .rom !0e -ossi%le Elemen!s lis! %o4 accordin/ !o yo$r
cali%ra!ion ,lan# Clic9 !0e elemen! yo$ 3an! and veri.y i! %y ,ressin/
LAdd Ran/eE# A.!er selec!in/ an elemen! yo$ can also selec! analy!ical
lines .or i! B!0is can also %e done la!er=# Clic9 !0e elemen! in !0e
selec!ed elemen!s lis!# Selec! L8ineE and LRe.erence lineE and ,ress !0e
LA,,lyE %$!!on#
12
Cali%ra!in/ a Concen!ra!ion model
Cali%ra!in/ Concen!ra!ion model
To dele!e an elemen! .rom !0e lis!< clic9 !0e elemen! and ,ress
LRemoveE#
%. 3heck the order of the elements.
T0e c0osen order o. !0e elemen!s 3ill remain !0ro$/0o$! in !0is model#
(. yo$ 3an! !o c0an/e !0e order $se !0e $, and do3n %$!!ons in !0e
ri/0!mos! ,ar! o. !0e screen#
Clic9 !0e elemen! 30ose ,osi!ion in !0e lis! yo$ 3is0 !o c0an/e# -ress
L$,E and Ldo3nE %$!!ons accordin/ly !o selec! !0e re?$ired ,osi!ion#
If an element is not in either the >ossiAle elements or measure
elements list) then the Arc!6et cannot analyse it in the matrix
you haCe selected. 3heck that the matrix is correct. If the
missin? element is Cital for you) contact your Arc!6et
re>resentatiCe to 0nd out 1hether that element could Ae added
to the line dataAase of the Arc!6et.
(electin? excitation >arameters
T0e ne4! s!e, is !o se! !0e e4ci!a!ion ,arame!ers !o $se in !0is model#
De.ore yo$ s!ar! selec!in/ !0e ,arame!ers yo$ s0o$ld 9no3 some %asics
a%o$! !0e Arc-Me!Es e4ci!a!ion so$rce and 0o3 !o selec! !0e %es!
e4ci!a!ion .or yo$r a,,lica!ion#
T0ere are !0ree diCeren! !y,es o. e4ci!a!ion modes 30ic0 are availa%leT
con!in$o$s )C arc< in!err$,!ed )C arc and s,ar9#
T0e Arc-Me!Es e4ci!a!ion so$rce is .$lly so.!3are con!rolled# Fo$ can
.reely se! !0e e4ci!a!ion ,arame!ers 3i!0in !0e /iven limi!s# 2o3ever<
!0e mos! common e4ci!a!ion ,arame!ers are ,rese! in !0e .ac!ory# 6e
0i/0ly recommend !0a! yo$ $se !0ese ,arame!ers# T0ese s!andard
,arame!er se!s .orm excitation sets#
T0e Arc-Me! 0as several ,rese! e4ci!a!ion se!sA
K 8o3 alloys Bin ARH&' and in A(R=#
K 2i/0 alloys Bin ARH&' and in A(R=#
13
Cali%ra!orEs man$al
K Al alloys Bin ARH&' and in A(R=#
Fo$ s0o$ld $se !0ese se!s as e4,lained in !0e .ollo3in/ descri,!ion o.
!0eir a,,lica%ili!y#
If your a>>lication is not listed in the taAle or you 1ant more
s>eci0c information aAout the excitation system) >lease contact
your local Arc!6et re>resentatiCe for assistance.
&. (elect G'xcitation ParametersB >a?e.
T0is 3ill %rin/ yo$ !o !0e .ollo3in/ screen#
#. (elect a suitaAle excitation set for your a>>lication from the
list
C0ec9 !0e LAvaila%le E4ci!a!ion Se!sE lis! %o4 .or a s$i!a%le e4ci!a!ion se!
.or yo$r a,,lica!ion# (. one is no! ,resen!< cons$l! yo$r Arc-Me!
re,resen!a!ive .or assis!ance# (. a .ac!ory ,rese! se! is selec!ed i!s ,$lse
,arame!ers are ;4ed< only ar/on @$s0 and %$rn !ime ,arame!ers can %e
modi;ed#
%. Insert ar?on Hush and Aurn time >arameters
14
Cali%ra!in/ a Concen!ra!ion model
Cali%ra!in/ Concen!ra!ion model
Ar/on @$s0 ,arame!ers Bin A58ON mode= can %e se! 3i!0o$!
res!ric!ions# LDe.ore Meas$remen!E is $sed !o crea!e a ,ro,er
a!mos,0ere in !0e camara de ?$emado# T0e recommended LDe.ore
Meas$remen!E !ime is %e!3een 4000 and 6000 ms# T0e LA.!er
meas$remen!E ar/on @o3 is $sed !o clean !0e 3indo3 and cool !0e
elec!rode# T0e recommended val$e is 1000-4000 ms#
L-re%$rnE is $sed !o ,re,are !0e sam,le s$r.ace .or o,!im$m sam,lin/#
T0e recommended ,re%$rn !ime in ARH&' is "000-7000 ms and in A(R
100-1000 ms de,endin/ on !0e a,,lica!ion# T0e L-re%$rn Dac9/ro$ndE
!ime s0o$ld %e !0e same as !0e ,re%$rn !ime#
Ac!$al in!ensi!ies are collec!ed d$rin/ !0e %$rn se?$ence# T0e
recommended LD$rnE !ime in ARH&' is 1000-7000 ms and in A(R< 500-
5000 ms de,endin/ on !0e a,,lica!ion# T0e LD$rn Dac9/ro$ndE !ime
s0o$ld %e !0e same as !0e %$rn !ime#
(elect ;i?h lo1 if necessary
Selec! L2i/0 :lo3E i. yo$ 3an! !o meas$re s$l.$r or ,0os,0oro$s# T0e
2i/0 :lo3 o,!ion increases !0e sensi!ivi!y in !0e lo3 7 3avelen/!0s#
Addin? and measurin? caliAration sam>les
T0e ne4! s!e, is !o !y,e in !0e names and concen!ra!ion val$es o. !0e
cali%ra!ion sam,les# To do !0is< .ollo3 !0ese ins!r$c!ionsA
&. (elect standards >a?e.
T0is 3ill %rin/ .or3ard !0e cali%ra!ion sam,le men$ s0o3n 0ere#
15
Cali%ra!orEs man$al
#. Add ne1 sam>le(s).
T0ere are !3o 3ays !o add a sam,leBs= !o !0e model< ei!0er man$ally
one %y one< or %y do3nloadin/ a concen!ra!ion ;le# T0is concen!ra!ion
;le 0as !o 0ave %een crea!ed %y a s,reads0ee! ,ro/ram or !e4! edi!or#
T0e .orma! is descri%ed in a,,endi4 D#
To add sam,les one %y one $sin/ !0e in!er.ace< clic9 L'e3 sam,leE# T0is
o,ens a /$ided ,roced$re !o add a sam,le name and rela!ed
concen!ra!ions#
To do3nload a concen!ra!ion ;le< ,ress 8oad# 8oca!e !0e ,a!0 o. !0e
concen!ra!ion ;le# See %elo3A
16
Cali%ra!in/ a Concen!ra!ion model
Cali%ra!in/ Concen!ra!ion model

%. 3heck or calculate the matrix concentration
(. yo$ do no! 9no3 !0e ma!ri4 concen!ra!ion yo$ can as9 !0e Arc-Me! !o
calc$la!e i!# U$s! ,ress Calculate concentr# Remem%er !0a! yo$ s0o$ld
0ave added all o!0er elemen! concen!ra!ions %e.ore calc$la!in/ !0e
ma!ri4 concen!ra!ion#
6easurin? sam>les
De.ore meas$rin/ sam,les< c0ec9 !0e ins!r$men! as descri%ed in !0e
7serEs Man$al# Also< ,re,are !0e s!andards care.$lly .or meas$remen!s#
A.!er inser!in/ !0e sam,les names and concen!ra!ions i! is !ime !o
meas$re !0e sam,les#
&. 3lick the sam>le name (>ossiAly the 0rst one).
#. Push Burn Autton.
T0e .ollo3in/ dialo/ 3ill a,,ear 30ic0 as9s !0e $ser !o %$rn !0e ;rs!
sam,le#
17
Cali%ra!orEs man$al
%. Press the tri??er 1hile holdin? the camara de Iuemado
a?ainst the sam>le s>ecimen.
(. yo$ are no! s$re 30a! !o do re.er !o !0e 7serEs man$al 3i!0o$!
0esi!a!ion#
T0e %$rn se?$ence ,roceeds and a.!er ;nis0in/< !0e ,ro/ram as9s !0e
$ser !o %$rn a second !ime# (n s,ecial cases i! may re?$ire !0ree or even
.o$r %$rns !o /e! sa!is.ac!ory s,ec!ra# All s,ec!ra are analysed and
eval$a!ed so !0a! !0ey mee! !0e s!ric! cri!eria re?$ired in !0e cali%ra!ion
,rocess#
.. 3heck s>ectra
Fo$ can c0ec9 !0e ?$ali!y o. !0e %$rns %y ,ressin/ LS0o3 s,ec!r$mE
%$!!on# T0is .ea!$re /ives yo$ !0e o,,or!$ni!y !o see !0e s,ec!ra
o%!ained .rom !0e meas$remen!s# (! is recommended !o c0ec9 !0e
s,ec!ra a.!er !0e ;rs! sam,le 0as %een meas$red or i. !0ere 0as %een
diVc$l!ies /e!!in/ /ood s,ec!ra#
5. (elect next sam>le
T0e ,ro/ram a$!oma!ically selec!s !0e ne4! sam,le on !0e lis! Bmar9ed
3i!0 red in a !e4! %o4=< %$! yo$ can selec! any sam,le 30ic0 is on !0a!
lis!#
Jhat does the Arc!6et do 1ith caliAration measurements=
)$rin/ cali%ra!ion !0e Arc-Me! al3ays as9s yo$ !o ma9e a! leas! !3o
consec$!ive meas$remen!s .or eac0 cali%ra!ion sam,le# T0e !3o
18
Cali%ra!in/ a Concen!ra!ion model
Cali%ra!in/ Concen!ra!ion model
s,ec!ra are !0en analysed and i. !0ey diCer more !0an a ,re-se! limi! !0e
Arc-Me! 3ill as9 .or a !0ird %$rn#
:rom !0e meas$remen!s< !0e Arc-Me! selec!s !0ose !3o !0a! are closes!
!o eac0 o!0er and calc$la!es !0e avera/e o$! o. !0eir in!ensi!ies#
T0e Arc-Me! s!ores %o!0 s,ec!ra in!o !0e da!a%ase# T0a! ma9es i!
,ossi%le !o selec! meas$remen! and re.erence lines .reely and also !o
c0an/e !0em la!er 3i!0o$! meas$rin/ !0e cali%ra!ion sam,les a/ain#
Addin? standardiEation sam>les
T0e Arc-Me! oCers an eVcien! me!0od !o ens$re lon/-!erm s!a%ili!y o.
!0e ins!r$men! and res$l!s# T0is me!0od is called LS!andardiza!ionE# T0is
correc!ion 3ill com,ensa!e .or any small dri.!s in analy!ical res$l!s
ca$sed %y reasons !0a! are no! con!rolled or com,ensa!ed .or in any
o!0er 3ay# Fo$ 0ave !3o me!0ods availa%leA
As e4,lained earlier< !0e Arc-Me! $ses s!andardiza!ion !o com,ensa!e
.or any small dri.!s in analy!ical res$l!s ca$sed %y reasons !0a! are no!
con!rolled or com,ensa!ed .or in any o!0er 3ay# (! does no! correc! !0e
res,onse o. !0e 30ole de!ec!or %$! ins!ead< ma9es !0e in!ensi!ies o.
meas$red lines similar !o !0ose meas$red 30en !0e model 3as ;rs!
cali%ra!ed# T0e 9ey idea is !o meas$re some sam,les d$rin/ cali%ra!ion
and s!ore !0ose in!ensi!ies# A! a la!er !ime< 30en !0ose same sam,les
are meas$red a/ain< !0e Arc-Me! 3ill calc$la!e a correc!ion e?$a!ion !o
ma9e !0e ne3 in!ensi!ies !0e same as !0ey 3ere 30en !0e sam,les 3ere
;rs! meas$red#
(! is recommended !0a! yo$ al3ays $se s!andardiza!ion 30en yo$ 0ave
,ro,er s!andardiza!ion sam,les availa%le#
Some !erminolo/y
S!andardiza!ion is %ased on meas$rin/ sam,les near !0e lo3er and
0i/0er cali%ra!ions limi!s .or eac0 elemen!# T0e areas aro$nd !0e lo3er
and 0i/0er limi!s are called Llo3 ,oin!sE and L0i/0 ,oin!sE< res,ec!ively#
60en 3e say< W!0is s!andardiza!ion sam,le 0andles !0e car%on lo3
,oin! and silicon 0i/0 ,oin!X 3e mean !0a! !0e Arc-Me! 0as de!ec!ed
!0a! !0e sam,leEs car%on concen!ra!ion is near !0e lo3er limi! o. !0e
cali%ra!ion ran/e .or car%on and !0e siliconEs con!en! near !0e 0i/0er
limi! o. !0e cali%ra!ion ran/e .or silicon#
T0e s!andardiza!ion .$nc!ion is normally linear# (n some cases !0e Arc-
Me! may only $se an oCse! correc!ion< 30ic0 means !0a! !0e correc!ion
is a,,lied only !o !0e in!erce,!< no! !o !0e slo,e#
19
Cali%ra!orEs man$al
*he Aasics of standardiEation
S!andardiza!ion is %ased on re.erence meas$remen!s !0a! are made
d$rin/ cali%ra!ion# T0e in!ensi!ies o. !0ose meas$remen!s are s!ored
inside !0e Arc-Me!# 60en !0e same sam,les are meas$red a/ain< !0e
Arc-Me! calc$la!es a correc!ion e?$a!ion !o ma9e !0e ne3 in!ensi!ies !0e
same as !0ey 3ere 30en !0e sam,les 3ere ;rs! meas$red#
T0e in!ensi!ies are correc!ed $sin/ a linear e?$a!ion#
I
new
= a
0
+ a
1
I
old
60ere
I
old
is !0e ori/inal in!ensi!y as meas$red d$rin/ cali%ra!ion and
I
new
is !0e correc!ed BWrecali%ra!edX= in!ensi!y a.!er !0e o,era!or 0as
done !0e s!andardiza!ion meas$remen!#
T0e coeVcien!s a
0
and a
1
are calc$la!ed %ased on !0e s!andardiza!ion
meas$remen!s $sin/ !0e leas! s?$ares ,rinci,le#
*he >rinci>les of least sIuares is ex>lained in A>>endix A
Basics of re?ression.
To %e a%le !o ma9e a correc!ion !0e Arc-Me! re?$ires a! leas! !0ree
s!andardiza!ion sam,les# T0ey s0o$ld cover !0e minim$m and
ma4im$m concen!ra!ions o. all im,or!an! elemen!s in !0e model# (. !0e
s!andardiza!ion sam,les do no! con!ain !0e lo3 or 0i/0 ,oin! .or some
elemen! yo$ can ei!0er $se an oCse! correc!ion or .orce a linear
correc!ion#
'o!e !0a! !0e Arc-Me! 3ill a$!oma!ically >$d/e 30e!0er a sam,le is /ood
.or recali%ra!in/ any 0i/0 or lo3 ,oin!s# (. !0e in!ensi!y o. an elemen! is
3i!0in Y 50J .rom !0e in!ensi!y o. !0e cali%ra!ion ran/e lo3 or 0i/0
,oin!< !0e sam,le 3ill %e acce,!ed as a lo3 or 0i/0 ,oin! .or !0a!
elemen!< res,ec!ively#
2o3 !o selec! s!andardiza!ion sam,les
S!andardiza!ion sam,les s0o$ld %e 0omo/eneo$s sam,les o. !0e alloy
!0a! !0e model is %$il! .or# T0ere are< 0o3ever< some .$r!0er
re?$iremen!sA
&. *he sam>les should haCe hi?h and lo1 concentrations of all
major elements that are caliArated in the model.
E#/# (. Car%on is cali%ra!ed .rom 0#05J !o 1#"J yo$ s0o$ld 0ave a! leas!
one sam,le !0a! 0as aro$nd 0#05J Car%on and ano!0er !0a! 0as aro$nd
1#"J Car%on# T0e same a,,lies !o all cali%ra!ed elemen!s#
20
Cali%ra!in/ a Concen!ra!ion model
Cali%ra!in/ Concen!ra!ion model
7ou should recaliArate all im>ortant elements for the
concentration ran?e that is si?ni0cant. It may not Ae the same
as the caliAration ran?e.
See ne4! ;/$re#
#. If the concentration ran?e is Cery narro1 you should only
use an oKset correction.
(n some e4!reme cases !0is is no! !r$e# :or e4am,le< in 504 M 5048
se,ara!ion yo$ s0o$ld $se a normal linear correc!ion< i. ,ossi%le#
%. In the case of a t1o line caliAration rememAer to recaliArate
the middle >oint also.
See c0a,!er L7sin/ !3o lines .or cali%ra!ionE .or de!ails on !3o-line
cali%ra!ion#
21
Cali%ra!orEs man$al
Al1ays use standardiEation if you haCe the suitaAle
standardiEation sam>les aCailaAle. (ee cha>ter G6easurin?
standardiEation sam>lesB for details on ho1 to select
a>>ro>riate standardiEation sam>les. Basically you can use the
same sam>les 1hich are included in the caliAration.
22
Cali%ra!in/ a Concen!ra!ion model
Cali%ra!in/ Concen!ra!ion model
To ini!ialize !0e s!andardiza!ion do !0e .ollo3in/A
&. (elect G(tandardiEation (am>lesB >a?e.
Fo$ come !o a men$ li9e !0isA
#. Add the standardiEation sam>les.
-ress LAddE !o add !0e sam,les yo$ re?$ire#
.. Burn the sam>les.
T0e ,ro/ram as9s .or !0ree %$rns# T0ese %$rns are e4!remely im,or!an!
%eca$se !0e lon/-!erm s!a%ili!y is %ased on !0ese#
5. (elect correction ty>e.
Fo$ can selec! a correc!ion !y,e %e!3een none< slo,e< in!erce,! or slo,e
Z in!erce,!# :or more in.orma!ion see la!er ,ar! o. !0is c0a,!er#
T0e Arc-Me! $ses !0ree diCeren! sym%ols in 8o3 2i/0 ;elds# T0eir
meanin/ isA
(ymAol 6eanin?
o T0is ,oin! is de;ned %y some
sam,leBs= %$! no! %y !0e one
O T0is ,oin! is &'8F de;ned %y
!0e sam,le $nder !0e c$rsor
23
Cali%ra!orEs man$al
Z T0is ,oin! is de;ned %y !0e
sam,le $nder !0e c$rsor %$!
(electin? the Aest lines for each element
Since !0e Arc-Me! meas$res !0e 30ole s,ec!r$m< .rom 175 nm !o 410
nm Bin ARC-MET 8000 Mo%ile8a% S- mode=< i! can oCer yo$ a 3ide
varie!y o. diCeren! analy!ical emission lines .or eac0 elemen!#
(n !0e %asic lo3 alloy s!eel cali%ra!ion !0e lines !0a! !0e Arc-Me! selec!s
a$!oma!ically are s$i!a%le .or analy!ical $se# D$!< in !0e case o. o!0er
a,,lica!ions< yo$ need !o c0ec9 30ic0 lines !o $se .or a cali%ra!ion#
To c0ec9 !0e lines .ollo3 !0ese s!e,sA
&. (elect G'lementsB >a?e
T0e .ollo3in/ screen 3ill a,,ear Bsame as in !0e LSelec!in/ Elemen!sE
s!a/e=
Lines
Selected elements list

#. (elect element and set lines
To selec! an elemen!< clic9 !0e elemen! in !0e lis!# A.!er selec!in/ !0e
elemen! yo$ can selec! an analy!ical meas$remen! line and a re.erence
line .or i!# T0e lines can %e selec!ed .rom !0e lis! %o4es#
As an e4am,le< Doron 0as %een selec!ed and .rom !0e lis! %o4 3e can
see !0e meas$remen! lines 30ic0 are availa%le .or Doron in !0is ma!ri4
and a!mos,0ere#
24
Cali%ra!in/ a Concen!ra!ion model
Cali%ra!in/ Concen!ra!ion model

(n !0e same manner< yo$ can selec! a re.erence line .or !0e selec!ed
meas$remen! line# A.!er selec!in/ all !0e lines yo$ can s!ar! !o %$ild !0e
re/ression model#
Fo$ can also $!ilize !0e (n!ensi!y dis,lay o,!ion in order !o ;nd !0e %es!
line .or a ,ar!ic$lar analy!e# -ress !0e L(n!ensi!iesE %$!!on and !0e
.ollo3in/ men$ 3ill a,,earA

his graph shows the
relationship between
concentration ratio and
intensit! ratio" in this
case for carbon

he !#axis is the intensit!
ratio

he x#axis contains the
concentration ratios


he line and reference line
in $uestion are shown here
Fo$ s0o$ld ,ay s,ecial a!!en!ion !o ens$re !0a! !0e ,oin!s .orm a
s!rai/0! line or a c$rve# (. !0is line ,air does no! !0en yo$ s0o$ld !ry
ano!0er one#
25
Cali%ra!orEs man$al
2ere are some e4am,les o. /ood /ra,0sA
(. only one or a .e3 ,oin!Bs= are o$!side a line or a c$rve !0ey co$ld %e
o$!liers d$e !o errors in meas$remen! or concen!ra!ion val$es#
$. 5eturn to the lines menu and select another measurement
line (if aCailaAle).
9. 3heck the ?ra>h for that line >air.
8. 4o this for all measurement lines and select the Aest one.
-. or the Aest one try diKerent reference lines and select the
Aest >air of lines.
&". 8o to another element.
What to look for?
A /ood ,air o. lines 3ill .orm a nea! s!rai/0! line or a c$rve# T0ere are
some /$idelines yo$ s0o$ld .ollo3 30en selec!in/ lines !o $seA
K Selec! !0e line ,air !0a! /ives !0e %es! /ra,0#
K (. yo$ 0ave diVc$l!ies in >$d/in/ selec! !0e $,,er one in !0e lis!#
K Try !o avoid lines !0a! 0ave ne/a!ive n$m%ers in !0ey-a4is< i.
,ossi%le#
T0e .ollo3in/ e4am,le /ra,0s 3ill s0o3 some !y,ical cases#
26
Cali%ra!in/ a Concen!ra!ion model
Cali%ra!in/ Concen!ra!ion model
This graph shows a
poor sensitivity in low
concentrations (see
the scatter)
This line pair has a few
outliers but reasona-
bly good graph in
these low concentra-
tions
This graphs shows the
lack of sensitivity in
high concentrations
5ememAer that you can come Aack later and chan?e the lines if
the caliAration does not 1ork out 1ith the ones you haCe
selected.
Lsin? 2ine JiEard
:or some elemen!s !0ere are many line com%ina!ions< 30ose !es!in/
3o$ld re?$ire 10-50 min$!es# To s,eed $, !0is ,rocess yo$ can $!ilize
!0e eVcien! cali%ra!ion !ool named L8ine 6izardE< 30ic0 a$!oma!ically
,er.orms !0e !as9 !o ;nd !0e %es! analy!ical line com%ina!ion#
(n !0e in!ensi!ies men$< a.!er selec!in/ !0e elemen!< selec! !0e L:ind %es!
linesE %$!!on# T0e 8ine 6izard s!ar!s !o ;nd !0e %es! com%ina!ion# A
!y,ical o$!,$! is ,resen!ed %elo3A
A.!er !0e 6izard 0as .o$nd !0e %es! com%ina!ion yo$ can selec! !0e
lines and ,ress !0e LA,,ly linesE %$!!on B,revio$s ,ic!$re=#
27
Cali%ra!orEs man$al
Lsin? t1o lines for caliAration
60en !0e %es! line .or !0e lo3 concen!ra!ions s0o3s a lac9 o. sensi!ivi!y
a! !0e $,,er end o. !0e cali%ra!ion ran/e i! may %e %es! !o $se a
diCeren! line .or lo3 and .or 0i/0 concen!ra!ions#
To $se !3o lines .or cali%ra!ion do !0e .ollo3in/A
&. 3reate ne1 ran?e.
Selec! !0e elemen! .rom !0e ,ossi%le elemen!s lis!# -ress !0e LAdd
Ran/eE %$!!on# T0e elemen! 3ill no3 a,,ear in !0e )e;ned elemen!s
lis!#
(. yo$ 0ave added a second ran/e .or C0romi$m BCr=< .or e4am,le< !0is
second ran/e is la%elled 3i!0 LCr"E#
Clic9 ei!0er o. !0ese elemen!s on !0e )e;ned Ran/es lis! and ,ress !0e
LHra,0ic ie3E %$!!on !o de;ne !0e s,li!!in/ o. !0ese ran/es#
#. 4e0ne s>lit ran?es
A.!er yo$ 0ave ,$s0ed !0e Hra,0ic ie3 %$!!on yo$ 3ill see !0is 9ind o.
vie3A
%lue lines show the ranges
&ed bars show the sample
concentrations
'oom in(out
#. 4ra? the ran?e Aars around a data >oint 1here you 1ant to
diCide the ran?e.
Hri, ,oin!s are on !0e ed/es o. !0e %ars#
28
Cali%ra!in/ a Concen!ra!ion model
Cali%ra!in/ Concen!ra!ion model
T0e ran/e is no3 s,li!# Concen!ra!ions can %e seen on !0e le.! side o.
!0e ran/e %ars#
6akin? a re?ression model
'o3 3e are /oin/ !o ma9e !0e re/ression model# T0e Arc-Me! $!ilizes an
eVcien! m$l!i,le s!e,3ise re/ression me!0od# :or more in.orma!ion
,lease re.er !o A,,endi4 A 30ic0 covers !0e %asics o. re/ression# Fo$
m$s! ma9e a model .or eac0 elemen!# T0ese elemen! models calc$la!e
!0e concen!ra!ion val$e ra!ios o$! o. !0e meas$red in!ensi!y ra!ios#
7nders!andin/ !0e Re/ression cali%ra!ion men$
T0e elemen! cali%ra!ion men$ is divided in!o !3o 0alves# T0e le.! ,ar! o.
!0e men$ s0o3s mainly !0e re/ression modelEs s!a!is!ical ,arame!ers<
and !0e ri/0! ,ar! s0o3s a /ra,0 rela!in/ !0e es!ima!ed concen!ra!ion
val$e ra!ios 3i!0 c0emical concen!ra!ion val$e ra!ios#
Element to be
modelled
Statistical
information of the
regression
List of possible
independents
)utomatic addition
of first independent
Calibration curve
Sample b!
sample
information
29
Cali%ra!orEs man$al
Parameter area
T0e ,arame!er area s0o3s a .e3 essen!ial ,arame!ers .or %$ildin/ an
elemen! cali%ra!ion#
or a detailed descri>tion of model >arameters and their
meanin? refer to Appendix A, The Essentials of Regression.
A.!er addin/ !3o inde,enden!s !o !0e model !0e ,arame!er area 3ill
loo9 li9e !0e e4am,le %elo3#

he data of each
independent is in a
dedicated column
Statistical
data of each
independent
Eac0 added inde,enden! /e!s i!s o3n col$mn in elemen! model
s!a!is!ical ,arame!er area#
8ra>h area
T0e /ra,0 area s0o3s !0e rela!ions0i, %e!3een !0e es!ima!ed and !0e
c0emical concen!ra!ion val$e ra!ios .or !0e elemen! %ein/ cali%ra!ed#
Eac0 cali%ra!ion sam,le is s0o3n as a ,oin! in !0e /ra,0#
30
Cali%ra!in/ a Concen!ra!ion model
Cali%ra!in/ Concen!ra!ion model
The 45 degree line represents
cases when estimated and chemi-
cal values are the same
Vertical axis (y-axis) shows chemi-
cal assay value ratios
Horizontal axis (x-axis) shows esti-
mated assay value ratios
The element being calibrated is
shown below the graph
(n addi!ion< !0ere is a line re,resen!in/ !0e o,!imal ;!# T0e closer !0e
,oin!s are !o !0a! line !0e %e!!er is !0e ;!# 'o!e< !0a! a! !0e s!ar!< all !0e
,oin!s are on !0e 4-a4is %eca$se !0ere is no model< !0a! is< !0e
es!ima!ed concen!ra!ion val$e ra!ios are all zero#
Note how all the points lie
on the x-axis because their
estimated value is zero
As soon as !0e ;rs! inde,enden! 0as %een added !o !0e model !0e
,oin!s 3ill a,,roac0 !0e 45 de/ree line#
Addin/ an inde,enden!
To le! !0e Arc-Me! c0oose !0e %es! inde,enden!< one a! a !ime< ,ress
LAuto Add inde>endentB. B6e ass$me a$!oma!ic addin/ o. ;rs!
inde,enden! is no! selec!ed< see a%ove=
31
Cali%ra!orEs man$al

:irs! inde,enden!
BCr= 0as %een added
!o !0e model o.
c0romi$m
Eleent calibration enu after frst !Add"
T0e Arc-Me! 3ill c0oose !0e %es! inde,enden! !o add %ased on !0e leas!
s?$ares ,rinci,le#
If you are not familiar 1ith the least sIuares >rinci>le or other
Aasics of ste>1ise re?ression) read a>>endix A G*he 'ssentials
of re?ression.
Fo$ can con!in$e !o add inde,enden!s %y ,ressin/ LA$!o Add
inde,enden!E# Dasically yo$ can add almos! !0e same n$m%er o.
inde,enden!s as yo$ 0ave real sam,le da!a ,oin!s in !0e model#
2o3ever< i! is recommended !o add a ma4im$m o. 4 inde,enden!s# (.
yo$ 0ave very .e3 cali%ra!ion sam,les !0e addin/ o. inde,enden!s may
%e !ermina!ed even %e.ore !0a!# (n !0a! case !0ere 3ill %e an aler!A
WCanno! add ne3 inde,enden! d$e !o small n$m%er o. sam,lesX#
T0e Arc-Me! re?$ires a! leas! 'Z1 cali%ra!ion sam,les i. ' is !0e n$m%er
o. inde,enden!s in !0e model#
Selec!in/ an inde,enden!
Some!imes yo$ may 3is0 !o selec! an inde,enden! yo$rsel.# T0is is
es,ecially !r$e 30en !0e Arc-Me! c0ooses inde,enden!s o!0er !0an !0e
elemen! yo$ are cali%ra!in/#
32
Cali%ra!in/ a Concen!ra!ion model
Cali%ra!in/ Concen!ra!ion model
Fo$ can o.!en de!ec! ,ossi%le o$!liers %y selec!in/ !0e ;rs! ,o3er o. !0e
elemen! %ein/ cali%ra!ed !o %e !0e ;rs! inde,enden!#
To selec! an inde,enden! !o !0e model< selec! i! .rom !0e lis! %o4 $nder
!0e 0eader L(nde,enden!sE# T0ose inde,enden!s 30ic0 0ave %een
removed %e.ore are la%elled 3i!0 an as!eris9#
Removin/ sam,les .rom !0e cali%ra!ion
Some!imes yo$ may de!ec! an o$!lier !0a! yo$ 3an! !o remove .rom !0e
cali%ra!ion# T0ese o$!liers may %e d$e !o a meas$remen! error or
incorrec! concen!ra!ion val$es# &$!liers can %e de!ec!ed %y selec!in/
!0e ;rs! ,o3er o. !0e elemen! %ein/ cali%ra!ed as !0e ;rs! inde,enden!#
;o1 to identify an outlier=
An o$!lier can %e de!ec!ed as a ,oin! lyin/ 3ay oC !0e o,!im$m line# (n
!0e case o. a ,oor ;! iden!i.yin/ an o$!lier is more diVc$l!#
&ne s!a!is!ical de;ni!ion !o de!ec! an o$!lier is !0a! i. !0e o$!lier ,oin!
devia!es %y more !0an 5 s!andard devia!ions .rom !0e correc! val$e i! is
an o$!lier#
33
Cali%ra!orEs man$al
Note that other points form a
quite clear line or slightly
curved path which helps us
to fnd the outlier
In this case the actual re-
gression should go some-
where along this line
It means that this point is an
outlier
Jhat does remoCin? a sam>le mean=
As !0e model .or a ,ar!ic$lar elemen! is %ein/ %$il!< !0e Arc-Me! 3ill
calc$la!e a ;! %e!3een c0emical concen!ra!ion val$e ra!ios and
in!ensi!y ra!ios# A! !0is s!a/e !0e Arc-Me! 3ill !a9e in!o !0e calc$la!ion all
sam,les !0a! 0ave no! %een removed .rom !0e calc$la!ion#
(! means !0a! i. a sam,le !0a! does no! %elon/ !o a cali%ra!ion Ban
o$!lier .or e4am,le= 0as %een removed< !0e calc$la!ion is made as i.
!0a! sam,le did no! e4is! a! all# 2o3ever< !0e es!ima!ed concen!ra!ion
val$e ra!ios are calc$la!ed .or !0a! sam,le !oo< %$! !0e ac!$al model is
calc$la!ed 3i!0o$! i!#
;o1 to remoCe a sam>le
Fo$ can remove a sam,le %y $sin/ !0e LZM-L %$!!on on !0e le.! side o.
!0e men$ or< 3i!0 !0e le.! 0and mo$se %$!!on< 30ile ,$!!in/ !0e c$rsor
over !0e da!a ,oin! in !0e cali%ra!ion c$rve#
(. yo$ $se !0e ZM- %$!!on yo$ m$s! ;rs! selec! !0e sam,le .rom !0e lis!A
34
Cali%ra!in/ a Concen!ra!ion model
Cali%ra!in/ Concen!ra!ion model
5emoCin? sam>les from an element caliAration only aKects the
model for the element you are caliAratin?. It does not aKect any
other elements. If you 1ant to totally remoCe a sam>le from
the caliAration remoCe it from the caliAration sam>les.
Removin/ an inde,enden!
Some!imes yo$ may 3is0 !o remove an inde,enden! .rom a model# T0e
,roced$re is diCeren! .or an inde,enden! already in !0e model !0an .or
an inde,enden! no! ye! in !0e model#
5emoCin? an inde>endent already in the model
To remove one o. !0e inde,enden!s !0a! are already in !0e model selec!
!0a! inde,enden! 3i!0 a c$rsor and ,ress Reo#e independent#
(. yo$ remove an inde,enden! !0a! 3as no! !0e las! one added Bas in o$r
e4am,le a%ove=< yo$ 3ill no!ice !0a! all !0e inde,enden!s added a.!er
!0e one yo$ 0ave >$s! removed< disa,,ear# T0ey are no! removed .rom
!0e lis!< %$! are merely !a9en a3ay .rom !0e model# A.!er all< !0ose
inde,enden!s came !o !0e model a.!er !0e inde,enden! yo$ removed
3as already in !0e model# To ma9e s$re !0a! !0e %es! ,ossi%le
inde,enden!s are in !0e model !0ese inde,enden!s 0ave !o %e !a9en
a3ay#
T0e removed inde,enden! is added !o !0e inde,enden! lis! la%elled 3i!0
an as!eris9 BO=#
:inis0in/ elemen! cali%ra!ion
60en yo$ 0ave reac0ed a model !0a! sa!is;es yo$ ,ress $Esc%# T0is
3ill %rin/ yo$ %ac9 !o !0e Cali%ra!ion men$# 'o!e !0a! !3o ne3 ;elds
0ave a,,earedA
K A ;eld s0o3in/ !0e correla!ion coeVcien! (R) and !0e s!andard error
(stderror).
K A ;eld dis,layin/ model inde,enden!s#
T0ese !3o ;elds s$mmarize !0e mos! im,or!an! ,arame!ers o. !0e
model yo$ 0ave %$il!# T0ese val$es 3ill %e availa%le i. yo$ 3an! !o vie3
model ,arame!ers#
35
Cali%ra!orEs man$al
Fo$ can dis,lay a cali%ra!ion re,or! %y ,ressin/ LS0o3 Cali%ra!ion
Re,or!E or yo$ can save !0e da!a on a dis9e!!e .or .$r!0er ins,ec!ion#
T0e re,or! is saved %y ,ressin/ !0e LSave re,or! !o dis9e!!eE %$!!on#
4e0nin? a control sam>le
Eac0 concen!ra!ion model yo$ cali%ra!e s0o$ld 0ave a de;ned con!rol
sam,le# T0is sam,le is $sed !o c0ec9 !0e acc$racy o. !0a! ,ar!ic$lar
model on a day-!o-day %asis# T0e o,era!or is advised in !0e 7serEs
man$al< !o %$rn !0e con!rol sam,le a! leas! once a day# (. !0e res$l!s .or
!0e con!rol sam,le are o$!side !0e acce,!ance limi!s de;ned %y !0e
cali%ra!or B!0a! is< yo$ or &4.ord (ns!r$men!s Analy!ical &F= !0e o,era!or
3ill 0ave !o do a s!andardiza!ion !o correc! !0e res$l!s#
Fo$ s0o$ld $se a con!rol sam,le !0a! is in !0e middle o. !0e mos!
im,or!an! concen!ra!ion val$e ran/e .or !0e mos! im,or!an! elemen!s# (.
yo$ ,lan !o analyse lo3 alloy s!eels< 0avin/ car%on .rom 0#1 !o 0#6J<
silicon .rom 0#5 !o 0#5J and c0romi$m .rom 0#5 !o 1#5J< yo$ s0o$ld
;nd a con!rol sam,le 0avin/ a,,ro4ima!elyA C 0#55J< Si 0#4J and Cr
1J#
T0e con!rol sam,le does no! 0ave !o %e a s!andard %$! i! s0o$ld %e a
0omo/eneo$s sam,le !0a! can %e s!ored 3i!0 o!0er accessories and is
al3ays availa%le#
36
Cali%ra!in/ a Concen!ra!ion model
Cali%ra!in/ Concen!ra!ion model
To de;ne !0e acce,!ance limi!s .or eac0 elemen! yo$ s0o$ld .ollo3
!0ese s!e,sA
&. 6easure the control sam>le at least 0Ce times in GACera?eB
dis>lay.
Se! avera/e dis,lay as e4,lained in !0e c0a,!er LHe!!in/ avera/es o.
consec$!ive meas$remen!sE in !0e Users manual#
#. 3heck the aCera?e Calue and the standard deCiation.
%. 3alculate the acce>tance limits for all elements for instance
to Ae at least c
ave
+ 2
conc
1here c
ave
is the aCera?e and
conc
is
the standard deCiation of the re?ression model.
:or cer!ain elemen!s< .or e4am,le< yo$ s0o$ld allo3 limi!s .rom 0#55J !o
0#65J< i. !0e Wcorrec!X val$e is 0#51 J and !0e s!andard devia!ion o. !0e
re/ression model is ZM-0#0" J#
.. Jrite the acce>tance limits do1n for the o>eratorBs use.
Acce>tin? the model
Acce,!ance o. !0e model is !0e cali%ra!orEs !as9# (! is recommended !o
doc$men! !0e ,er.ormance o. !0e ins!r$men! s!rai/0! a.!er !0e
cali%ra!ion and !o s!ore all !0e cali%ra!ion in.orma!ion# (. any ,ar! o. !0e
cali%ra!ion is /oin/ !o %e c0an/ed !0e doc$men!a!ion s0o$ld also %e
$,da!ed#
37
Cali%ra!in/ a Concen!ra!ion model
Cali%ra!in/ Concen!ra!ion model
A>>endix A. *he essentials of re?ression
T0is a,,endi4 descri%es !0e .$ndamen!als o. concen!ra!ion model
cali%ra!ion# (. yo$ ,lan !o do yo$r o3n cali%ra!ions yo$ s0o$ld s!$dy !0is
c0a,!er in de!ail# -rac!ically< yo$ do no! 0ave !o remem%er all !0e
e?$a!ions %$! yo$ s0o$ld %e .amiliar a! leas! 3i!0 !0e %asic conce,!s
and ;/$res o. meri!#
Re/ression analysis is an eCec!ive ma!0ema!ical !ool 30ic0 is $sed !o
es!a%lis0 a rela!ions0i, in a se! o. varia%les so !0a! !0e val$e o. a
cer!ain varia%le can %e ,redic!ed on !0e %asis o. !0e o!0er varia%les#
(! is essen!ial !0a! !0e ori/inal da!a is o. a 0i/0 cali%re %eca$se invalid
da!a inevi!a%ly crea!es res$l!s o. a %ad ?$ali!y# (. !0e res$l! can %e
im,roved %y $sin/ ei!0er !0e 0ard3are or !0e so.!3are< e#/#< ma9e
si/nals more ,$re %e.ore a,,lyin/ re/ression< !0is is %e!!er< as i! ma9es
!0e re/ression more sim,le and more relia%le#
(n !0e Arc-me!< !0e ,$r,ose o. re/ression is !o ;nd !0e %es! 3ay !o
!rans.orm !0e in.orma!ion incl$ded in !0e in!ensi!ies< in!o
concen!ra!ions# (. !0is 0as %een done s$cces.$lly !0e res$l! is %o!0
acc$ra!e and ,recise< i#e# i! is close !o !0e !r$e val$e and is re,ea!a%le#
T0e res$l! may %e ?$i!e $se.$l even i. i! is only ,recise in s$c0 cases
30ere !0e ,$r,ose is !o com,are vario$s o%>ec!s< %eca$se !0en< !0e %ias
error does no! eC.ec! !0e decision # (.< on !0e o!0er 0and< i! is necessary
!o 9no3< .or e4am,le< 0o3 close !0e meas$rin/ res$l! is !o some
nominal val$e< !0en !0e acc$racy is !0e mos! im,or!an! .ac!oreven i.
one 0as !o allo3 a some30a! lo3er ,recision# (n many cases i! is
,ossi%le !o eCec! !0e cali%ra!ion !o some e4!en! !o em,a0isize ei!0er
.ea!$re< de,endin/ on !0e ;nal $se o. !0e ins!r$men!#
To in!rod$ce !0e commonly $sed c0arac!eris!ic ;/$res !0a! descri%e !0e
?$ali!y o. !0e re/ression 3e !a9e ;rs! !0e mos! sim,le case< namely
linear re/ression 3i!0 only one varia%le# T0en 3e /o over !o m$l!ilinear
re/ression and .$r!0er !o s!e,3ise re/ression !0a! is ac!$ally $sed in
Arc-me!#
Cali%ra!orEs man$al
(im>le linear re?ression
T0e s!e,3ise re/ression !0a! is $sed in Arc-me! is a s,ecial version o.
!0e m$l!ivaria!e linear re/ression#
8e! $s loo9 a! ;rs! !0e sim,le linear re/ression# T0e ;/$re %elo3
ill$s!ra!es !0e %asic ,ro%lem o. cali%ra!ion< namely< ;ndin/ !0e line !0a!
%es! ;!s !o !0e meas$remen! da!a accordin/ !o some cri!erion#
T0e ver!ical ,osi!ion o. eac0 ,oin! is /iven %y !0e e4,ression
i i i
e x a a y + + =
1 0
2ere< e
i
re.ers !o !0e devia!ion .rom !0e re/ression line# T0e mos!
common cri!erion .or !0e %es! ;! is !0a! !0e s$m o. !0e s?$ares o. !0e
devia!ions e
i
is minimized# T0$s !0e e4,ression !o %e minimized is
value x a a y e
i i i
min ) (
1 0
2
=

T0e minimiza!ion /ives val$es !o !0e ,arame!ers a
0
and a
1
# A.!er !0is !0e
es!ima!es
y
.or y val$es can %e calc$la!ed and com,ared !o !0e
re.erence val$es# T0e diCerence
y y
is called !0e resid$al#
40
T0e Essen!ials o. Re/ression
'Caluation of the re?ression
T0e re/ression ,ro/ram $s$ally /ives several ,arame!ers !0a! descri%e
!0e ?$ali!y o. !0e re/ression e?$a!ion# T0e mos! commonly $sed
c0arac!eris!ic ;/$res and !0eir $ses are %rie@y disc$ssed in !0e
.ollo3in/#
(tandard error of the estimate
T0e de;ni!ion o. !0e S!andard error o. !0e es!ima!e as in !0e ,resen!
case#
2 / 1 2
)) 2 /( ) (( =

n e s
i
2ere n is !0e n$m%er o. o%serva!ions and Bn-"= re.ers !o !0e so called
de/rees o. .reedom# '$m%er " means !0a! !3o de/rees 0ave %een $sed
30en ,arame!ers a
0
and a
1
3ere de!ermined#
5elatiCe standard error of estimate
T0e de;ni!ion is sim,le and direc!ly rela!ed !o s
y s s / ) 100 (
,
=
3oerrelation coeMcient
T0e de;ni!ion loo9s sim,le 30en i! is %ased on only vario$s y val$es

=
2
2
2
) (
) (
y y
y y
R
i
i
T0e ma4im$m val$e .or r" is o%!ained 30en !0e es!ma!ed and !r$e
val$es o. y coincide# (n !0a! case R is 1# (. R 0as ne/a!ive val$es i!
means !0a! y decreases 30en 4 is increasin/# (. !0e a%sol$!e val$e o. R
is lo3< li9e 0#6< or even lo3er< !0en !0e re/ression e?$a!ion is no!
s!a!is!ically si/ni;can!#
41
Cali%ra!orEs man$al
!test
7sin/ !0e a%ove no!a!ions !0e : val$e .or :is0erEs !es! is de;ned as

=
2 / ) (
) (
2
2
n e
y y
F
i
i
(! is o%vio$s !0a! 30en !0e error /oes do3n !0e : val$e /oes $,# (. :
remains small< e#/# %elo3 4 < i! means !0a! !0e re/ression e?$a!ion is
no! a%le !o ,redic! y on !0e %asis o. x#
t!test for the slo>e Calue
T0e de!ermina!ion o. !0e slo,e can only %e made 3i!0 a cer!ain
acc$racy# T0e inacc$racy can %e eval$a!ed on !0e %asis o. !0e same
da!a on 30ic0 all !0e calc$la!ions are done# (. !0e s!andard error o.
es!ima!e o. slo,e EaE is mar9ed %y s !0e !r$e val$e o. EaE is 3i!0 !0e
cer!ain!y o. 68 J 3i!0in !0e limi!s
1 1
1 1 1

a a
s a a s a + < <
Hra,0ically !0e si!$a!ion loo9s as in !0e ;/$re %elo3
42
T0e Essen!ials o. Re/ression
-arame!er S
a1
can also %e $sed !o !es! 30e!0er a[1 diCers .rom some
o!0er val$e aE1 $sin/ e?$a!ion
1

1 1 a
s t a a =
:ac!or t in .ron! o. s is !0e s!$den!Es !es! .ac!or# (nser!in/ !0e 9no3n
val$es in!o !0e a%ove e?$a!ion !0e n$meric val$e o. ! can %e calc$la!ed#
'e4! !0is can %e com,ared !o !0e val$es /iven in s!a!is!ical !a%les !o
see 30a! is !0e ,ro%a%ili!y !0a! !0e diCerence is s!a!is!ically si/ni;can!#
(n ordinary cali%ra!ion 3or9 !0e only reasona%le val$e !o com,are 3i!0
is zero %eca$se i! 3o$ld mean !0a! varia%le x is no! si/ni;can! and can
%e i/nored# Se!!in/

1
a e?$al !o zero !0e e4,ression .or ! %ecomes#
1
1

a
s
a
t =
(! is o%vio$s !0a! !0e smaller !0e inacc$racy in !0e slo,e de!ermina!ion<
!0e 0i/0er ! 3ill %e# (n ,rac!ice< 3e can se! a limi! .or !0e minim$m
acce,!a%le val$e .or !0e a%sol$!e val$e o. ! and 3ri!e#
5 . 2 t
T0e limi! val$e means !0a! slo,e EaE is diCeren! .rom zero 3i!0 a
,ro%a%ili!y o. a%o$! 11 J#
(tandard residual
43
Cali%ra!orEs man$al
T0is is !0e ra!io o. !0e resid$als and !0e s!andard error o. es!ima!e# (!
0el,s in ;ndin/ !0e ,oin!s !0a! do no! ;! 3ell !o !0e line#
3on0dence limits for the sin?le oAserCations
As a conse?$ence o. !0e $ncer!ain!y in !0e slo,e val$e< !0e s!andard
resid$als do no! !ell !0e 30ole !r$!0 30en %ad ,oin!s in !0e da!a are
loo9ed .or# (n .ac!< .or a /iven 4 val$e 3e can say !0a! !0e es!ima!ed y
val$e 3ill %e 3i!0 a ,reselec!ed con;dence 3i!0in !0e ran/e#
( )
( )

+ +
2
2
1
1
x x
x x
n
s t y
i
T0e val$e .or ! is selec!ed on !0e %asis o. !0e desired con;dence $sin/
n! as !0e de/ree o. .reedom# Hra,0ically !0e si!$a!ion loo9s in ,rinci,le
as in !0e ;/$re %elo3# T0e ran/e is a! i!s minim$m in !0e middle ,oin!
o. !0e da!a and increases !o3ards %o!0 ends# T0$s i! is clear !0a! i. !0e
%ad ,oin! 0a,,ens !o %e close !o ei!0er end a %i//er devia!ion m$s! %e
!olera!ed#
T0e s val$e /iven in !0e re/ression ,ro/ram re.ers !o !0e middle ,oin!
o. !0e da!a# (n ,rac!ice a rela!ive s!andard resid$al %i//er !0an 5 means
!0a! !0e ,oin! is li9ely some0o3 !o %e in error even i. i! is .ar .rom !0e
middle#
44
T0e Essen!ials o. Re/ression
(! s0o$ld %e no!ed !0a! none o. !0e a%ove men!ioned c0arac!eris!ic
;/$res are alone s$Vcien! !o descri%e !0e ?$ali!y o. !0e ;!# T0e
a%sol$!e error may %e small %$! !0a! may %e d$e !o !0e small varia!ion
o. varia%le y i!sel.# T0e rela!ive error may %e small %eca$se o. a 0i/0
mean val$e o. y# T0e correla!ion coeVcien! can %e made 0i/0 in a
cali%ra!ion >$s! %y ma9in/ !0e cali%ra!ion ran/e %road< %$! i. !0e !r$e
varia!ion in ,rac!ice is narro3 !0e ac!$al correla!ion may %e modes!# &n
!0e o!0er 0and< i. !0e cali%ra!ion da!a is re,resen!a!ive< %o!0 correla!ion
coeVcien! and : and ! !es! val$es are /ood meas$res !o !ell 30e!0er
!0ere is any si/ni;can! ,redic!a%ili!y#
6ultiCariate linear re?ression
60en !0e sim,le linear re/ression model is no! s$Vcien! .or !0e ac!$al
needs and more in.orma!ion a%o$! !0e meas$remen! is availa%le< more
!erms can %e added !o !0e e?$a!ion# T0e /eneral .orm o. !0is !y,e o.
e?$a!ion is
i
m
i
i
x a a y

=
+ =
1
0
2ere x can %e any varia%le $ as s$c0 or some .$nc!ion o. i! as e#/# i!s
s?$are# 8inear 0ere means !0a! !0e e?$a!ion is linear as .ara as !0e
re/ression coeVcien!s are concnerned# T0e de!ermina!ion o. !0e
coeVcien!s o. !0e e?$a!ion 0a,,ens in !0e same 3ay as in !0e sim,le
re/ression# Also !0e de;ni!ions o. !0e c0arac!eris!ics ;/$res descri%in/
!0e ?$ali!y o. !0e ;! remain essen!ially !0e same al!0o$/0 !0e
calc$la!ions %ecome more com,lica!ed# T0e main diCerence 0ere is !0a!
!0e de/rees o. .reedom %ecome a .$nc!ion o. !0e n$m%er o. !0e
varia%les !a9en in!o !0e e?$a!ion# T0a! eCec!s mos!< varia%les s and :#
T0eir e4,ressions c0an/e as .ollo3s#
S %ecomes
) 1 /( ) (
2
=

m n e s
i
: %ecomes

=
1 / ) (
/ ) ( (
2
2
m n e
m y y
F
i
i
45
Cali%ra!orEs man$al
T0e e4,ression o. !0e con;dence limi!s .or a sin/le o%serva!ion
%ecomes clearly more com,lica!ed and i! is no! /iven 0ere# 2o3ever<
!0e r$le !0a! %i//er resid$als o$/0! !o %e !olera!ed 30en !0e ,oin!s are
.ar .rom !0e cen!er re/ion remains valid#
T0e eCec! o. m in !0e e4,ressions .or s and : is s$c0 !0a! i. !0e las!
varia%les 0ave no! im,roved !0e ;! %o!0 val$es /e! 3orse# T0is is
es,ecially !r$e .or : %eca$se !0e n$mera!or is inversely ,ro,or!ional !o
!0e s?a$re roo! o. m# To 9ee, : a! leas! a! !0e same level as %e.ore<
addin/ a ne3 varia%le< !0e s$m o. !0e diCerneces e m$s! decrease
corres,ondin/ly#
(te>1ise re?ression
T0e s!e,3ise re/ression !0a! is $sed in !0e Arc-Me! is a s,ecial version
o. !0e m$l!ivaria!e linear re/ression# T0e im,or!an! addi!ional .ea!$re is
!0a! !0e ,ro/ram !ries !o add varia%les in!o !0e e?$a!ion in s$c0 a
se?$ence !0a! !0e ?$ali!y o. !0e ;! im,roves %y ma4im$m s!e,s# T0e
$n.or!$na!e !0in/ 0ere is !0a! !0is ,ro/ram< li9e all commonly $sed
s!e,3ise re/ression ,ro/rams< is no! a%le !o /$aran!ee !0a! !0e ;nal
selec!ion is 3i!0 100 J cer!ain!y !0e %es! one# 2o3ever< i! /ives a /rea!
0el, 30en !0e n$m%er o. ,ossi%le varia%les is 0i/0# T0e ,ro/ram also
/ives cer!ain ne3 ;/$res !o .acili!a!e !0e eval$a!ion o. !0e m$!$al
im,or!ance o. diCeren! varia%les in !0e e?$a!ion# (. !0ere is some /ood
reason 30y a cer!ain varia%le s0o$ld %e in !0e e?$a!ion i! can %e .orced
!0ere %y sim,ly c0oosin/ i! man$ally< ,re.era%ly a! !0e %e/innin/#T0e
$ncer!ain!y< as !o 30e!0er !0e c0osen se! o. varia%les really is !0e %es!
,ossi%le< comes .rom !0e .ac! !0a! a.!er !a9in/ a ne3 varia%le in!o !0e
e?$a!ion one or more o. !0e earlier c0osen varia%les may %ecome
insi/ni;can!# &.!en !0is is d$e !o !0e correla!ion %e!3een varia%les< and
in com,lica!ed cases< some .alse correla!ions may %e s!ron/er !0an !0e
!r$e ones# To c0ec9 .or s$c0 si!$a!ions !0e Arc-Me! s!e,3ise ,ro/ram
/ives< a.!er eac0 s!e,< Be4ce,! .or !0e c0arac!eris!ic ;/$res !0a!
descri%e !0e ;! as a 30ole= .or eac0 varia%le< !0e ! !es! val$e and !3o :
!es! val$es# &ne o. !0ese< :-!o \En!er< descri%es !0e si/ni;cance o. !0e
la!es! added varia%le# T0e o!0er< :-!o-remove< descri%es !0e si/ni;cance
o. eac0 varia%le as i. i! 0ad %een added as !0e las! varia%le !o !0e se!#
T0e :-!o-en!er val$e does no! c0an/e in !0e co$rse o. !0e selec!ion
,rocess and i! sim,ly s0o3s 0o3 im,or!an! !0e varia%le 3as 30en i!
3as !a9en !o !0e e?$a!ion# T0is val$e can %e ?$i!e diCeren! .rom !0e :-
!o-remove val$e a! some la!er s!e,# :or !0e la!es! varia%le !0e !3o :
val$es are al3ays !0e same#
46
T0e Essen!ials o. Re/ression
(n mos! cases !0e selec!ion ,rocess can %e con!in$ed so .ar !0a! a! leas!
one varia%le %ecomes insi/ni;can!# A varia%le can %e considered
insi/ni;can! i. i!s :-!o-remove val$e is %elo3 4# S$c0 a varia%le o$/0! !o
%e removed .rom !0e e?$a!ion %eca$se i! is ca$sin/ mainly e4!ra noise#
(. !0ere 0a,,en !o %e more !0an one si/ni;can! varia%le in !0e
e?$a!ion!0ey s0o$ld only %e removed one %y one %eca$se a.!er
removin/ one !0e o!0er may %ecome im,or!an!#
T0$s< !0e $se o. !0e ,ro/ram means !0a! i. may %e necessary !o !ry
several diCeren! selec!ions even 30en !0e da!a is ,er.ec!ly .ree o.
errors# T0e selec!ion ,rocess %ecomes essen!ially easier i. a! leas! some
o. !0e varia%les can %e c0osen on e#/# a so$nd ,0ysical %asis# S$c0
varia%les can %e .orced !o !0e e?$a!ion as men!ioned %e.ore#
(ome s>ecial cases
(. !0e sam,les 0ave %een ,re,ared care.$lly< !0e meas$remen!s 0ave
%een made 3ell and !0e concen!ra!ion da!a is valid< !0e da!a 3ill li9ely
/ive /ood res$l!s 3i!0 sim,le loo9in/ e?$a!ions and 3i!0 very li!!le
3or9# T0e c0arac!eris!ic ;/$res 3ill 0ave reasona%le val$es and !0e
resid$als 3ill no! s0o3 any oddi!ies#
2o3ever< 30en !0e da!a are e4!ensive !0ey may easily incl$de some
real errors or mis!a9es or some s,ecial .ea!$res# T0e .ollo3in/ e4am,les
ill$s!ra!e some cases#
Outliers
T0e ,lo! y vs 4 may loo9 as .ollo3s#
47
Cali%ra!orEs man$al
(! is easy !o ;nd o$! !0a! !0ere is one ,oin! !0a! %e0aves diCeren!ly.rom
!0e o!0ers# T0is ,oin! can also %e easily .o$nd on !0e %asis o. s!andard
resid$als# A.!er ;ndin/ s$c0 a ,oin!< i! is %es! ;rs! !o !ry !o ;nd o$! !0e
reason .or !0e devia!ion and< i. !0ere is an error< !o remove !0e error#
Even i. no reason is .o$nd< i! may %e %es! !o leave !0e ,oin! o$! o. !0e
da!a< %eca$se some error is a very very ,ro%a%le reason !o s$c0 a %i/
devia!ion# (. !0is ,oin! is no! removed< and in .ac! is erroneo$s< !0e
eCec! is a %ias error# T0e slo,e 3ill no! c0an/e and !0$s !0e sensi!ivi!y
remains !0e same#
T0e devia!ion may %e ca$sed %y some e4ce,!ional com,osi!ion and d$e
!o some in!erac!ion# (. so< !0e ,oin! m$s! no! %e removed< %$! a ne3
varia%le co$ld %e !ried !o see i. i! 3o$ld elimina!e !0e diCerence# (n !0/e
case o. 3idely varyin/ com,osi!ion i! is 3ise !o c0ec9 30e!0er some
o!0er analy!ical or re.erence line 3o$ld /ive a %e!!er ;!#
(. !0e devia!in/ ,oin! is no! in !0e middle< %$! a! !0e end< !0e reason can
%e !0a! !0e sensi!ivi!y c0an/es and a linear rela!ions0i, is no! s$Vcien!#
Even i. only !0e mos! sim,le linear e?$a!ion is $sed i! is no! clear !0a!
!0is ,oin! co$ld %e dele!ed %eca$se errors are easily %i///er a! !0e end
o. !0e ran/e as e4,lained earlier# (. !0is concen!ra!ion area is im,or!an!
i! 3o$ld %e %es! !o !ry !o /e! a co$,le o. addi!ional sam,les .rom !0a!
area !o see 0o3 !0ey %e0ave#
(e>arate caliAration eIuation
48
T0e Essen!ials o. Re/ression
60en !0e ran/e o. meas$remen! is 3ide< !0e real!ions0i, easily
%ecomes c$rved< %$! also< !0e .ollo3in/ !y,e o. si!$a!ion is ?$i!e
,ossi%le i. e#/# !0ere are no alloys 0avin/ concen!ra!ions in a ,ar!ic$lar
ran/e#
(n s$c0 cases i! is ,ossi%le !o $se ins!ead an e?$a!ion 0avin/ s?$are or
c$%ic !erms< sim,ly " se,ara!e linear e?$a!ions< %eca$se !0ey may /ive
lo/ically %e!!er ;!s !0an an overall ;!#
'xtra>olation error
Es,ecially 30en !0e e?$a!ion incl$des s?a$res or c$%es o. varia%les i!
is dan/ero$s !o e4!ra,ola!e o$!side !0e ran/e o. cali%ra!ionT !0is is
ill$s!ra!ed in !0e .ollo3in/ ;/$re#
49
Cali%ra!orEs man$al
(. 4 is .ar o$!side !0e ran/e y may %ecome even ne/a!ive#
Interferin? element
(! may also 0a,,en !0a! !0e ,oin!s seem !o .orm !3o /ro$,s< eac0 ;!!in/
a line< %$! !0e lines are on eac0 o!0er li9e in ne4! ;/$re#
T0is 9ind o. si!$a!ion may %e d$e !o some ,ar!ic$lar elemen! !0a! e#/#
eCec!s %$rnin/# (! may 3ell 0a,,en !0a! %y c0an/in/ !0e meas$rin/
,arame!ers !0e ,oin!s ;! on !0e same line# (. !0e a,,lica!ion is ne3< !0e
reason .or /ro$,in/ may also %e s$c0 !0a! !0ere is an in!er.erin/ line
!0a! 0as no! %een no!ed 30en !0e ini!ial ,re,ara!ions 0ave %een made#
(.< 0o3ever< a.!er all c0ec9s !0e si!$a!ion ,ersis!s !0e /ro$,s can li9ely
%e %ro$/0! !o/e!0er %y addin/ !0e in!ensi!y o. !0e dis!$r%in/ elemen!
in!o !0e e?$a!ion# T0is si!$a!ion is an e4am,le o. a case 30ere i!
cer!ainly 3o$ld %e %e!!er !o ;nd a 0ard3are or so.!3are sol$!ion !o !0e
,ro%lem %eca$se !0e consis!ency o. !0e re/ression sol$!ion is no!
cer!ain#
50
Cali%ra!in/ a Concen!ra!ion model
Cali%ra!in/ Concen!ra!ion model
A>>endix B. 3oncentration 0le format
Concen!ra!ion ;le is a !a% delimi!ed !e4! ;le# Fo$ can crea!e i! %y a
s,reads0ee! ,ro/ram Bli9e E4cel= or a !e4! edi!or#X
Sam,le names are lis!ed in !0e ;rs! col$mn s!ar!in/ .rom !0e second
ro3# Elemen!s are lis!ed in !0e ;rs! ro3 s!ar!in/ .rom !0e second
col$mn# Elemen! concen!ra!ions can %e .o$nd in eac0 ro3 a.!er !0e
sam,le name#X
An e4am,le o. a ;le< crea!ed in 'o!e,ad< is s0o3n %elo3#