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7/26/2019 Provencher 2015
1/22
1Claisse,2015.AllRightsReserved/TousDroitsRservs.
Chara
cterization
ofCoal
andIt
sBy-prod
ucts
Using
BorateFu
sions
andIC
P-OESAnalyses
ByMarie-veProvenc
her,M.Sc.
Che
mist
USASa
les
Manager
Claisse,
2015
.AllRightsReserve
d/Tous
Dro
its
Rserv
s.
7/26/2019 Provencher 2015
2/22
2Claisse,2015.AllRightsReserved/TousDroitsRservs.
Solidwas
te
Filter
Coalash
SamplesfromCoalInd
ustry
Coa
lismos
tlyuse
dby
powerp
lan
tstoge
nera
tee
lec
tricity
Emiss
ions
frompower
plan
ts:
o
Gas
(flyas
h)
o
So
lidwas
te(ash)
Why
istraceana
lys
isimportan
t?
o
Ithe
lps
toknowt
hecon
ten
to
fthecoa
lby-pro
duc
ts(coalas
han
dcoa
lflyas
h)
o
Ita
llows
toknow
thecon
ten
to
fthewa
stefrompowerp
lants
(coa
las
han
dcoalf
ly
as
h)foraneco-fr
ien
dlydisposa
l
Coalflyash
Coal
7/26/2019 Provencher 2015
3/22
3Claisse,2015.AllRightsReserved/TousDroitsRservs.
Ce
rtifiedReferenceMaterials(C
RMs)
Coal
Coalash
Coalflya
sh
NCSFC28127
VS-7177-95
EOP12-1-02
China
Ru
ss
ia
Czec
hRepu
blic
Al
3.4
7
14
.3
16
.1
Si
5.6
1
27
.4
22
.9
3
CRMs
from
coa
lindus
try
H
ighs
ilicaan
da
lum
inac
on
ten
t
S
amp
leprep
ara
tionmet
ho
d
Ac
iddiges
tion
(no
te
fficien
t)
Hars
hac
id(HF)(no
ten
tire
lysa
fe)
Fus
ion
7/26/2019 Provencher 2015
4/22
4Claisse,2015.AllRightsReserved/TousDroitsRservs.
No
rms
AS
TMD6349
o
Samplepreparation:
Boratefus
ion
Aciddiges
tion
(HF/HNO
3/HCl)
o
ICP-OES
o
Al,Ba,Ca,Fe,K
,Mg,
Mn,Na,
P,S
,Si,Srand
Ti
AS1038.14.1
o
Sample
preparation:
borat
efusion
o
AA
o
Al,Ba,
Ca,Fe,K
,Mg
,
Mn,Na
,P,
S,Si,Sr,T
i
andZn
7/26/2019 Provencher 2015
5/22
5Claisse,2015.AllRightsReserved/TousDroitsRservs.
Coal
Coalash
Coalfly
ash
NCSFC28127
VS
-7177-95
EOP12-1-02
China
Russ
ia
Czec
h
Repu
blic
LOI
74
.3%
0.4
2%
0.29
%
R
ampup
to500Cfor1
hour
R
ampup
to750Cfor2
hours
H
olda
t750Cfor
2hours
Pretreatmen
tofSamples
7/26/2019 Provencher 2015
6/22
6Claisse,2015.AllRightsReserved/TousDroitsRservs.
SamplePrep
arationby
BorateFusion
XRF
Analys
is
ICP
and
AA
Ana
lysis
7/26/2019 Provencher 2015
7/22
7Claisse,2015.AllRightsReserved/TousDroitsRservs.
Sa
mplePrep
arationbyBorateF
usion
Ina
Pt/Au(95%/5%)
crucible:
o
0.1
00go
fas
hed
samp
le
o
0.1
50g
LiNO
3
o
1.0
00g
LiM/1
.5%
LiBr
Kee
pinmind:
o
Lowsamp
le/fluxra
tio
(1/10)foranopt
imize
dsamp
le
disso
lution
o
Thenon-we
ttingagen
ta
llowsacomp
letepouring
o
Silicaan
da
lum
inaareveryso
lubleinlithium
me
tabora
te
7/26/2019 Provencher 2015
8/22
8Claisse,2015.AllRightsReserved/TousDroitsRservs.
1.
Manual
Meekerburn
erandrisingstand
Mufflefurnac
e
Homemade
2.Automatic
Gasfired
Electric
Fu
sionTechniqueInst
ruments
7/26/2019 Provencher 2015
9/22
9Claisse,2015.AllRightsReserved/TousDroitsRservs.
ClaisseAutomaticFluxers
GASELECTRICM4TMClaisse
fluxe
r
LeNeo
Claisse
fluxer
Eagon2Claisse
fluxer
The
Ox
Claisse
fluxe
r
Propane
&N
atura
lGas
7/26/2019 Provencher 2015
10/22
10
Claisse,2015.AllRightsReserved/TousDroitsRservs.
Au
tomatedF
usion
L
eNeo
fusionins
trument
O
nefusionpositio
n
P
rogrammablepa
rameters(tempera
ture,
dura
tionan
dag
ita
tion
):
o
Ox
ida
tions
tepat
800C
o
Fas
ttempera
ture
ramp-up
(up
to1200
C)
o
The
fus
ions
teps
arecomp
letedin7m
inu
tes
Steps
Duration(m
in)
Rockingangle
Rockingspeed
Temperature(C)
O
xidation
2
0
0
800
Fusion
1
0
0
1000
Fusion
1
0
0
1050
Fusion
1
20
15
1050
Fusion
1
30
20
1050
Fusion
1
40
30
1050
P
ouring
Stirring
6
7/26/2019 Provencher 2015
11/22
11
Claisse,2015.AllRightsReserved/TousDroitsRservs.
Au
tomatedD
issolution
The
disso
lution
iscomp
lete
din6m
inutes:
o
Completepo
uring
o
90mLof10%
HNO
3
o
Magneticagitation
Steps
Duration(m
in)
Rockingangle
Rockingspeed
Temperature(C)
O
xidation
2
0
0
800
Fusion
1
0
0
1000
Fusion
1
0
0
1050
Fusion
1
20
15
1050
Fusion
1
30
20
1050
Fusion
1
40
30
1050
P
ouring
Stirring
6
7/26/2019 Provencher 2015
12/22
12
Claisse,2015.AllRightsReserved/TousDroitsRservs.
Ma
nualDilution
C
omp
leteto
100m
L
A
ddthe
interna
ls
tan
dar
d
D
ilution
1in2
F
ina
lvo
lume
at200m
L
0.5
%oftotald
issolvedsa
lt
7/26/2019 Provencher 2015
13/22
13
Claisse,2015.AllRightsReserved/TousDroitsRservs.
Instrumentation
o
PerkinElmer
Optima
7300D
VICP-OES
Analysis
o
Matrix-matchedcalibrationcur
ve
o
Internalstand
ardsadded
Nebulizer
Gem
TipCross
flow
Spraychamber
Sco
tt
Injector
Alum
ina
2mm
i.d
.
RF
1500W
Argonflow
Plasma:
16L/min
Ne
bu
lizer:
0.8
L/min
Aux
iliary:
0.4
L/min
Sampleflowrate
1.0
mL/min
An
alysisby
ICP-OES
7/26/2019 Provencher 2015
14/22
14
Claisse,2015.AllRightsReserved/TousDroitsRservs.
Elementsofinteres
t
Associatedinternalstandards
Both
Elem
ents
Wavelength
Io
nization
p
otential
Internal
standards
Wavelength
Ionization
potential
Ionization
state
View
ing
mode
A
l
237.3
13
6.0
Ga
294.3
64
6.0
I
Axial
Ca
422.6
73
6.1
Eu
381.9
67
5.7
II
Ra
dial
Fe
238.8
63
7.9
Re
197.2
48
7.9
II
Axial
K
766.4
90
4.3
Rb
780.0
23
4.2
I
Axial
Mg
279.0
77
7.6
Re
197.2
48
7.9
II
Axial
Na
589.5
92
5.1
Ga
294.3
64
6.0
I
Ra
dial
S
i
252.8
51
8.2
Te
214.2
81
9.0
I
Axial
T
i
337.2
79
6.8
Eu
381.9
67
5.7
II
Axial
Inte
rnalstandard
associatedwiththeelement:
Similar
ion
izatio
npo
ten
tia
l
Similar
ion
izatio
ns
tate
Int
ernalStan
dards
7/26/2019 Provencher 2015
15/22
15
Claisse,2015.AllRightsReserved/TousDroitsRservs.
Ca
libration,MethodDetectionLimits
(M
DLs)andLinearity
Elem
ents
Wavelength
(nm)
View
MDL
(mg/L)
Calibrationrange
Correlationcoefficient
(pts=5)
(Min)
(Max)
A
l
237
.313
Ax
ial
0.0
7
13
.8
275
1.0
000
B
a
413
.065
Ax
ial
0.0
06
0.2
5
5.0
0
1.0
000
C
a
422
.673
Ra
dial
0.1
6.0
0
115
1.0
000
F
e
238
.863
Ax
ial
0.0
2
6.2
5
125
1.0
000
K
766
.490
Ax
ial
0.0
02
0.9
00
18
.0
0.9
997
M
g
279
.077
Ax
ial
0.0
07
0.8
80
17
.5
1.0
000
M
n
293
.305
Ax
ial
0.0
01
0.1
38
2.7
6
1.0
000
N
a
589
.592
Ra
dial
0.0
5
0.2
80
5.5
0
1.0
000
P
177
.434
Ax
ial
0.0
3
1.6
0
30
.0
0.9
995
S
181
.975
Ax
ial
0.0
6
2.8
0
55
.0
1.0
000
S
i
252
.851
Ra
dial
0.0
7
15
.0
300
1.0
000
S
r
460
.733
Ax
ial
0.0
02
0.3
30
6.5
0
0.9
999
Ti
337
.279
Ax
ial
0.0
02
2.8
0
55
.0
1.0
000
Z
n
213
.857
Ax
ial
0.0
03
0.1
50
3.0
0
1.0
000
7/26/2019 Provencher 2015
16/22
16
Claisse,2015.AllRightsReserved/TousDroitsRservs.
T
hemethodhas
beentestedwith3differentty
pesofsamples
:
o
Flyas
h
o
Coa
las
h
o
Coa
l
A
ccuracyandprecisionwerecalculatedbased
onthecertified
r
eferencevalue
ofeachCRM(Al,Ca,
Fe,
K,M
g,
Na,
SiandT
i)
R
ecoverywasc
alculatedwiths
amplesspiked
beforefusion(B
a,
K
,Mn,
P,
S,
Sra
ndZn)
Re
sults
Fly
ash
Coalash
Co
al
7/26/2019 Provencher 2015
17/22
17
Claisse,2015.AllRightsReserved/TousDroitsRservs.
PrecisionandAccuracy
inBrown
CoalFlyAsh
EOP12
-1-02
Elements
Certifiedvalues
(%)
Experimentalvalues
(%)n=10
MDL
(%)
Precisiont0
,975;9
(%)
Accuracy
(%)
RS
D
(%
)
Al
16.1
16.3
0.0
1
0.1
98.7
0.5
Ca
1.4
9
1.4
4
0.0
2
0.0
4
96.5
3.9
Fe
5.1
7
5.2
1
0.0
03
0.0
2
99.2
0.5
K
0.6
51
0.6
30
0.0
004
0.0
11
96.7
2.4
Mg
0.5
81
0.6
23
0.0
01
0.0
02
93.0
0.5
Na
0.3
61
0.3
7
0.0
1
0.0
1
97.6
3.5
Si
22.9
23.8
0.0
1
0.4
96.3
3.7
Ti
3.6
1
3.4
4
0.0
003
0.0
1
95.3
0.5
Dilution
fac
tor:
1994
n=
10
7/26/2019 Provencher 2015
18/22
18
Claisse,2015.AllRightsReserved/TousDroitsRservs.
Precisionan
dAccurac
yinCoal
NCSFC28127
Elements
Certifiedvalues
(%)
Experimentalvalues
(%)n=10
MDL
(%)
Precisiont0
,975;9
(%)
Accuracy
(%)
RS
D
(%
)
Al
3.4
7
3.3
7
0.0
03
0.0
3
97.1
1.2
Ca
1.8
8
1.8
9
0.0
06
0.0
4
99.3
2.8
Fe
1.0
2
1.0
5
0.0
008
0.0
1
97.4
1.0
K
0.2
9
0.2
81
0.0
001
0.0
05
97.0
2.5
Mg
0.2
8
0.2
94
0.0
004
0.0
02
94.7
0.8
Na
0.0
52
0.0
52
0.0
02
0.0
01
99.6
2.2
Si
5.6
1
6.0
5
0.0
04
0.0
6
92.2
1.3
Ti
0.1
8
0.1
73
0.0
0008
0.0
02
96.4
1.4
Dilution
fac
tor:
513
n=
10
7/26/2019 Provencher 2015
19/22
19
Claisse,2015.AllRightsReserved/TousDroitsRservs.
Precisionan
dAccurac
yinCoal
Ash
VS717
795
Elements
Certifiedvalues
(%)*
Experimentalvalues
(%)n=10
MDL
(%)
Precisiont0
,975;9
(%)
Accuracy
(%)
RS
D
(%
)
Al
14.3
3
14.0
0.0
1
0.1
97.7
1.3
Ca
3.4
9
3.7
0
0.0
2
0.0
6
94.0
2.4
Fe
3.8
3
3.7
3
0.0
03
0.0
3
97.3
1.0
K
0.4
9
0.4
46
0.0
004
0.0
06
91.0
1.9
Mg
0.8
93
0.8
74
0.0
01
0.0
09
97.9
1.5
Na
0.1
0
0.1
1
0.0
1
0.0
1
97.6
3.1
Si
27.4
3
28.6
0.0
14
0.4
95.7
2.1
Ti
0.3
6
0.3
57
0.0
003
0.0
03
99.3
1.2
*MeasuredasAlbutreportedasAl2O
3onthecertificateofanalysisprovided
withmaterial
Dilution
fac
tor:
1992
n=
10
7/26/2019 Provencher 2015
20/22
20
Claisse,2015.AllRightsReserved/TousDroitsRservs.
Re
coveryforthe3CRMs
EOP12-1-02
(browncoal
flyash)
NCSFC28127
(coalash)
VS7177-95
(coal)
Elem
ents
Spiked
values
Recovery
RSD
Spiked
values
Recovery
RSD
S
piked
values
RecoveryR
SD
mg/L
%
%
mg/L
%
%
mg/L
%
%
Ba
1
102
0.4
1
102
1
1
103
0.2
K
3
91
3
5
102
2
3
91
4
Mn
1
102
1
2
100
0.7
1
104
0.6
P
1
99
1
1
103
1
1
101
3
S
1
97
3
5
100
1
1
96
3
Sr
1
96
1
1
100
0.9
1
98
3
Zn
1
100
0.7
1
101
0.9
1
101
1
n=
5
7/26/2019 Provencher 2015
21/22
21
Claisse,2015.AllRightsReserved/TousDroitsRservs.
Co
nclusion
G
reatoveralla
ccuracy:
o
Minimum(smallervalue)91.0%
forK
o
Average96.6
2.3
%
G
reatoverallrecovery:
o
Minimum91%
forK
o
Average99.5
3.6
%
I
tisappropriatetouseLeNeoinstrumenttopreparecoal
s
amplesforICP-OESanalys
isinaccordan
cewithindustry
n
orms
7/26/2019 Provencher 2015
22/22
22
Claisse,2015.AllRightsReserved/TousDroitsRservs.
Questions?
maprovencher@
claisse
.com
Booth#722
cla
isse.com