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Silica analysis: XRD and FTIR · by direct-on-filter XRD and recent findings from workplace samples...
Transcript of Silica analysis: XRD and FTIR · by direct-on-filter XRD and recent findings from workplace samples...
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State-of-the-art analysis of respirable crystalline silica by direct-on-filter XRD and recent findings from workplace samples
Martin Mazereeuw, John Volpato, Akemi IchikawaTestSafe Australia – SafeWork NSW
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Silica analysis: XRD and FTIR
XRay Signal
Lamp Detector
Filter
Lamp Detector
IR Signal
XRD and FTIR used for RCS analysis
➢ Direct-on-filter approach
➢ Different technology
➢ Different performance
Diffraction
technique
Transmission
technique
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XRD Analysis
Method: NH&MRC (1984), HSE(2014)
Response factor: Peak intensity of Q (101) diffraction
Criteria: Q(101)/average*= 90-110%, Dust<2mg
Q (100), (112) when Q(101) interfered
Overload correction implemented when overloadedQ
(10
0)
Q(1
12)
Q(1
01)
Ag(1
11)
Ag(2
00)
Measurement area
(24mm diameter)
*average= {Q(100)+Q(101)+Q(112)}/3
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FT-IR Analysis
Method: HSE(2014)
Blank subtraction implemented
Response factor: Absorption peak height of Si-O vibration
Criteria: PH800/PH780 = 1-1.4, Dust<1mg
PV
C
Measurement area
(8mm diameter)
Q 8
00
Q 7
80
*
PV
C
PV
C
PV
C
PV
C
PH 800 PH 780
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Equipment
XRD
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a-quartz calibration curves
XRD r2=0.998 FT-IR r2=0.996
pure quartz = linear result
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XRD vs FT-IR (α-quartz samples)
r2=0.991n=43(valid results)
Pure α-quartz (No matrix)
Good agreement
r2=0.99
FT-IR values: XRD values
y=x
y=0.8x
y=1.2x
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Real workplace samples
n=253
Sampled 34 different workplaces
in Australia (2014-18)
Industry:
- Road construction/ Tunneling (47%)
- Coal mining (23%)
- Kitchen benchtop (25%)
- Others (5%)
Compositions depend on
individual samples
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XRD vs FT-IR (real workplace samples)
n=253(all measured
results: Included
invalid results)
y=x
y=0.8x
y=1.2x
Outliers
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XRD vs FT-IR (real workplace samples)
n=171(valid results)
y=x
y=0.8x
y=1.2x
32% of FT-IR data failed
(PH criteria, Dust >1mg)
r2=0.97
FT-IR values: ~10% higher
than XRD
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FT-IR Spectra (α-quartz vs Silicates)
Q(7
80
)
Q(8
00
)
Peak overlap on Quartz (800) Blank subtracted
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XRD Spectra (α-quartz vs Silicates)
Q(1
00
)
Q(1
12
)
Ag(1
11)
Q(1
01
)
Ag(2
00)
No major peak overlap on Quartz (101)
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Recovery of α-quartz (with Silicates)
FT-IR showed positive bias
w/ Kaolinite (>60%),
Albite (>90%)
Cristobalite(>10%)
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Cristobalite
α-Quartz Tridymite Cristobalite
T > 800 ºC T > 1100 ºC
Quartz transforms to Cristobalite (Tridymite) by heat process
>~800degC and influenced by alkalinity.
Pure Quartz transforms to Cristobalite at ~1400degC.
Quartz most commonly present (stones, soils).
Cristobalite (Tridymite) presence in nature related to volcanic activity.
Cristobalite (Tridymite) presence in engineered stones.
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Cristobalite
Engineered stone
Cristobalite found regularly
in dust samples
Sometimes at high %
10-15 % of cristobalite found in all jobs offered.
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SDS – engineering stones
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Quartz-Cristobalite
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Estimated LOD
For “Direct-on-filter” using XRD with old instrument
Major limitation: Signal to Noise Ratio (SNR)
XRD can achieve
2 µg LODwhen needed
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Estimated LOD
For “Direct-on-filter” using XRD with new instrument
XRD can achieve
800 ng LODwhen needed
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Blanks
Lowering exposure limit Lowering reporting limit
Analysis usually done
against a blank signal
When lowering detection limits,
quality of blank becomes important
Found: Not all blanks are blank
➢ Contamination control
➢ Blank variability
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Transfer/ Handling the sample
Do not use flat plastic bag Do not tape the sample
Dust came off from the filter
Dust came off when tape removed/
Interference from tape
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Recommended casePlace the sample and clip the edge,
collected surface (to be analysed) should be upside
Label on the top
Label on the top
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Chemical Analysis / TestSafe Australia
Level2, Bldg1, 9-15 Chilvers Rd,
Thornleigh, NSW 2120
P: 02 9473 4000
http://www.testsafe.com. au
Booth 48
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Questions/ Discussions
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Conclusion
Comparison between “Direct-on-filter” using XRD and
“Direct-on-filter” using FT-IR
“Direct-on-filter” using XRD showed better results:
1) Less interference from matrixes found in Australian
workplace samples.
2) 32% of workplace samples failed by FT-IR for valid
analysis
3) XRD could handle up to twice the sample loading
(2 mg) and could correct for overloading
4) XRD can achieve lower LOD
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Overloaded samples (Dust:1~3mg)- Pure α-quartz samples
- Simulated samples
XRD can handle
overloaded samples
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Crystalline silica
Chemical name CAS No.Current TWA
(mg/m3)
Quartz 14808-60-7 0.1Stone, cement,
soil
Cristobalite 14464-46-1 0.1
Engineering
stones, heated
condition
(>800degC)
Tridymite 15468-32-3 0.1heated condition
(>800degC)
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Quartz-Cristobalite-Tridymite
Quartz present in nature (stones, soils).
Cristobalite (Tridymite) presence in nature at volcanos.
Cristobalite (Tridymite) presence in engineer stones.
Quartz transforms to Cristobalite (Tridymite) by heat
process >~800degC with Alkaline elements (Li, Na, Mg,
Al, K, Ca) .
Pure Quartz transforms to Cristobalite at ~1400degC.
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Respirable crystalline silicaSamples from stone manufacturing
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Transfer/ Handring the sample
Do not use flat plastic bag Do not tape the sample
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Discussion: Possibility to achieve lower LOD
For “Direct-on-filter” using XRD
Major limitation: Signal to Noise Ratio (SNR)
XRD can achieve
lower LODWhen analyse with
slower scan or better
detector
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Respirable crystalline silica analysis
Method
Quick
analys
is
Precision(pure QTZ)
Interference
from matrixSensitivity
Effect of
PVC film
Effect of
Fe
“Direct on filter”
using FI-IR
“Direct on filter”
using XRD
“Indirect-KBr”
using FT-IR
“Indirect-filter”
using FT-IR -
“Indirect” using
XRD - -: Good or Not affected : Not good or Affected
Less likely
(Fe-oxide>90%)
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XRD Spectra (α-quartz vs non Silicates)Q
(10
0)
Q(1
12
)
Ag(1
11)
Q(1
01
)
Ag(2
00)
No peak overlap on Quartz (101) Noise increased slightly
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FT-IR Spectra (α-quartz vs non Silicates)
Q(7
80
)
Q(8
00
)
No peak
Broad absorption
For calcite& graphite, No peak but absorption observed at Quartz (800)
No peak at 800
Broad absorption
Blank subtracted
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Recovery of α-quartz (with non Silicates)
FT-IR showed negative bias
w/ Calcite (>95%)
XRD showed negative bias
w/ Fe-oxide (>90%)
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XRD vs FT-IR (real workplace samples)
n=171(valid results)
A
y=x
y=0.8x
y=1.2x
32% of FT-IR data failed
(PH criteria, Dust >1mg)
r2=0.97
FT-IR values: ~10% higher
than XRD
Z
B
C
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Spectra (Sample A) FT-IR = XRD
Q(1
00
)
Q(1
12)
Ag(1
11)
Q 8
00
Q(1
01
)
Ag(2
00)
No significant matrix
detected
α-quartz = 0.17mg
Blank subtracted
α-quartz: 82wt%, Matrix: 18wt%
Dust :0.21mg
No significant matrix
detected
I800/I780 = 1.2
α-quartz = 0.17 mg
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Spectra (Sample B) FT-IR > XRD
Q(1
00
)
Q(1
12)
Q 8
00
Kaolinite
Q(1
01
)
Ag(1
11)
Ag(2
00)
Blank subtracted
No interference
α-quartz = 0.26mg
Fe-oxide: 4wt% (XRF)
α-quartz: 36wt%, Matrix: 64wt%
Dust: <0.72mg
Kaolinite detected
Al4Si4O10(OH)8
I800/I780 = 1.4
α-quartz = 0.32 mg
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Q(1
00
)
Q(1
12)
Ag(1
11)
Q 8
00 Albite
Q(1
01
)
Ag(2
00)
Spectra (Sample C) FT-IR > XRD
Blank subtracted
Q(1
12) No interference
α-quartz = 0.14mg
Fe-oxide: 5wt% (XRF)
α-quartz: 16wt%, Matrix: 84wt%
Dust: <0.88mg
Albite detected
NaAlSi3O8
I800/I780 = 1.0
α-quartz = 0.32 mg
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Spectra (Sample Z) - FT-IR data failed
Q(1
00
)
Q(1
12)
Q 8
00Calcite
Q(1
01
)
Ag(1
11)
Ag(2
00)
Blank subtracted
No interference
α-quartz = 0.20mg
α-quartz: 10wt%, Matrix: 90wt%
Dust: 1.97mg
Quartz peaks deformed
Calcite detecte
Silicates detected
I800/I780 = 1.6
α-quartz = 0.28 mg
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Simulated respirable dust samples
- a-Quartz (0-100%) & common Matrix in Australian workplaces
(Known α-quartz & matrix, pre-weighted)
Silicates (Kaolinite: Al4Si4O10(OH)8,
Albite: NaAlSi3O8,
Cristobalite: SiO2 )
Non silicates (Calcite: CaCO3, Graphite: C)
Fe-oxide (Fe2O3)
=> Measured simulated samples
=> Calculated from spectrum for matrix
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a-quartz calibration curves
XRD r2=0.998
Linear to ZERO
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Standard deviation of α-quartz samples
LOD
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Respirable dust samples
1) Pure α-quartz samples (n=43), blanks (PVC filters)[Prepared with NIST SRM 1878a, A9950, WASP, LGC samples]
- Calibration curves
- Standard deviation/ LOD
- Relationship between both methods
2) Real workplace samples (n=253)
- Relationship between both methods
- Spectra analysis
3) Simulated samples (α-quartz with known matrix)
- Interference form Matrix
- Fe-effect
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PVC filters (Blanks)
- Suitable for gravimetry
(low moisture, light weight)
- Low cost
- Durable to water, acids, metals, oils
- Large differences : 4-8mg (25mm filter)
25mm filter weight
GLA-5000
Filter weightFT-IR Spectra of blanks
*before blank subtraction
Differences
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Respirable crystalline silica analysis
MethodPreparation for
specimen
film/pellet when
analised
Analysis
method
No. of
labs
“Direct on filter”
using FI-IR Not requiredPVC filter FT-IR 9(28%)
“Direct on filter”
using XRDPVC filter XRD 12(38%)
“Indirect-KBr”
using FT-IR Ashing/
Acid treatment/
Alkaline
treatment
if needed
KBr pellet FT-IR 7(22%)
“Indirect-filter”
using FT-IR
Re-deposited
(PVC) filterFT-IR 1(3%)
“Indirect” using
XRD
Re-deposited
(PVC) filterXRD 1(3%)
Other - - - 2(6%)
LGC (2017) AIR PT Scheme Report (Round 19) 2017
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Respirable crystalline silica analysis
Method
Quick
analys
is
Precision(pure QTZ)
Interference
from matrixSensitivity
Effect of
PVC film
Effect of
Fe
“Direct on filter”
using FI-IR ? ? ? ?
“Direct on filter”
using XRD ? ? ? ?
“Indirect-KBr”
using FT-IR
“Indirect-filter”
using FT-IR -
“Indirect” using
XRD - -: Good or Not affected : Not good or Affected
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Questions/ Discussions
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Crystalline silica information
http://www.safework.nsw.gov.au/silica
https://www.safework.nsw.gov.au/hazards-a-z/hazardous-
chemical
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Indirect method with FT-IR (3mm-KBr)
Ojima (2003)
Determining of Crystalline
Silica in Respirable Dust
Samples by Infrared
Spectrophotometry in the
Presence of Interferences
J Occup Health 2003; 45
94-103
Measurable range:
7-37 µg
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Indirect method with FT-IR
NMAM 7603
Quartz in Respirable Coal
Mine Dust, by IR
(Redeposition)
Measurable range:
10-500 µg
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Overload correction* (XRD)
*Overload correction by using
Ag-sheet
Altree-Williams (1977)
Quantitative X-ray
diffractometry on respirable
dust collected on nuclepore
filters
Ann Occup Hyg 1977; 20
109-126.
Able to handle
more than 2mg
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Bulk vs filter samples (XRD)
X-ray
Sample
Fe
X-ray
Bulk Filter
Absorbed Transmitted
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Simulated samples (Kaolinite)
FT-IR
XRD
Q(7
80
) Q
(80
0)
Acceptable range
Blank subtracted
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Simulated samples (Cristobalite)
FT-IR
XRD
Q(7
80
) Q
(80
0)
Acceptable range
Acceptable range
Blank subtracted
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Fe-effect (bulk samples, XRD)
Increase of
background noise
Decrease of peak intensity – Decrease of quartz amount
Increase of mass absorption
Fe effect
60% Fe-oxide
No Fe-oxide
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Fe-effect (filter samples, XRD)
Increase of background noise
Increase of mass absorption
Fe effect
60% Fe-oxide
No Fe-oxide
Workplace samples: 0-6%
Fe-effect negligible
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Respirable dust samples
Pure α-quartz samples (n=43)
- NIST SRM1878a, A9950
deposited onto a PVC filter (GLA5000) from a dust generator
through a cyclone sampler
- PT samples (WASP HSL, LGC UK)
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Standard deviation of blank filters (LOD)
ConditionXRD
(µg/filter)
FT-IR
(µg/filter)
Repeatability
(within day)
10 measurements of same
blank filter2.5 0.030
Intermediate precision
(between days)
10 measurements of same
blank filter over 3 months3.1 0.34
Variability between
filters
10 different blank filters2.8 3.45
Estimated LOD
from blanks (3 x s) 10 10
Major limitation to
determine standard
deviations
Signal to
noise ratio
(SNR)
Absorption &
difference of
blank filter
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XRD Spectra (α-quartz vs Silicates)
Q(1
00
)
Q(1
12
)
Ag(1
11)
Q(1
01
)
Ag(2
00)
No peak on Quartz (101)
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XRD Spectra (α-quartz vs Polymorphism)Q
(10
0)
Q(1
12
)
Ag(1
11)
Q(1
01
)
Ag(2
00)
No peak on Quartz (101)
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FT-IR Spectra (α-quartz vs Silicates)
Q(7
80
)
Q(8
00
)
Peak observed on Quartz (800) Blank subtracted
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FT-IR Spectra (α-quartz vs Polymorphism)
Q(7
80
)
Q(8
00
)
Strong peak observed on Quartz (800) Blank subtracted
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XRD vs FT-IR (real workplace samples)
n=171(valid results)
A
y=x
y=0.8x
y=1.2x
32% of FT-IR data failed
(PH criteria, Dust >1mg)
Almost all outlier excluded
r2=0.97
FT-IR values: ~10% higher
than XRDY
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Spectra (Sample Y) - FT-IR data excluded
- I800/I780 = 18
- Calcite detected
- Several silicates
detected
- Matrix/Dust :97 wt%
Q(1
00
)
Q(1
12)
Q 8
00
Calcite
Q(1
01
)
Ag(1
11)
Ag(2
00)
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