Applied Laser Spark Spectroscopy: The Evolution of LIBS into Real- - - PowerPoint PPT Presentation
Applied Laser Spark Spectroscopy: The Evolution of LIBS into Real- World Applications Presented by: APPLIE D Technical Group Leadership SPE CTROSCOPY TE CHNICAL GROUP Chair: Elina A. Vitol, Staff Scientist, ECOLAB Advisor: Samuel
Chair: Elina A. Vitol, Staff Scientist, ECOLAB Advisor: Samuel Achilefu, Professor, Washington University in St. Louis Education Lead: Matthias Fischer, Project Manager, -4H- JENA Engineering Publications Lead: Frank Kuo, Project Manager, Mettler Toledo AutoChem Technical Meetings Lead: Prasoon Diwakar, Sr. Research Associate, Purdue University
APPLIE D SPE CTROSCOPY TE CHNICAL GROUP
Educational events. Contact us if you want to present to the group! We are targeting to have 2-3 webinars per year.
Monthly collection of papers concerning various topics in applied spectroscopy from OSA suite of journals. Sent out to all group members by email.
Look out for future announcements!
APPLIE D SPE CTROSCOPY TE CHNICAL GROUP
Contact us at OSA.AppliedSpectroscopy.TG@gmail.com Questions? Ideas? Suggestions?
APPLIE D SPE CTROSCOPY TE CHNICAL GROUP
http://www.osa.org/AppliedSpectroscopyTG
members
interest to you Facebook page: Coming soon!
APPLIE D SPE CTROSCOPY TE CHNICAL GROUP
We are looking for a Social Media Lead! Let us know if you are interested in serving on the Executive Committee of the group
Contact us at OSA.AppliedSpectroscopy.TG@gmail.com Questions? Ideas? Suggestions?
“Applied Laser Spark Spectroscopy: The Evolution of LIBS into Real-World Applications”
M ay 17, 2016 ▪10 am EDT
APPLIE D SPE CTROSCOPY TE CHNICAL GROUP
Nd:Y AG laser (1064 nm, 8 ns) spectrometer Laser-Induced Breakdown Spectroscopy
beam with sufficient energy to atomize/ ionize/ excite the target material => exceed the breakdown threshold
separates the wavelengths and detects the light energy
Nd:Y AG laser (1064 nm, 8 ns) spectrometer Laser-Induced Breakdown Spectroscopy
beam with sufficient energy to atomize/ ionize/ excite the target material => exceed the breakdown threshold
separates the wavelengths and detects the light energy
Nd:Y AG laser (1064 nm, 8 ns) spectrometer Laser-Induced Breakdown Spectroscopy
* “I enjoy the LIBS community more than all others, it ’s a great family, so to speak.” … from a prominent LIBS scientist in academia…
Sample Papers of Real-World Applications Presented at the LIBS 2014 Conference in Beijing, China
ewelry M icroanalysis using LIBS
Launched November 2011- arrived August 2012 (http:/ / www.msl-chemcam.com/ )
* Collaboration between NASA and CNES (French space agency)
ChemCam
Mast Unit (contains LIBS)
Standoff Range: 1.5-7 meters M ars Science Laboratory Rover “Curiosity”
radiation areas at the Sellafield nuclear plant and also at various nuclear power stations.
makeup of highly radioactive material.
capabilities in this area.
components of various nuclear plant and equipment where physical access is severely restricted (eg. steam tubes and other components inside a steam generator at a nuclear power station).
the operators of Sellafield to use APL ’s proprietary submersible LIBS probe to characterise radioactive waste submerged in water and sludge at several storage ponds which date back to the 1950s.
for 50 years and so is in a highly corroded state. Very few records were maintained on the inventory of this waste and so it must be characterised before it can be removed from the ponds and processed for long-term storage
waste via its elemental signature, for example being able to identify fragment
tubes, pieces of concrete, pieces of graphite, M agnox fuel cladding, etc.
Applied Geochemistry, 2009 Analytical and Bioanalytical Chemistry, 2011 Chemical and Engineering News, 2012
Richard Hark at Juniata and Prof. M atthieu Baudelet at UCF , have been advancing the application of LIBS to forensics
residue (GSR), biomaterials/ fingerprint, and nuclear forensics analyses.
attempted bank robbery.
Pathak, Awadhesh Kumar Rai, and Gyanendra Kumar Rai, Food Biophysics (2011) 6:527–533.
(2010) 727–733.
M enezes, E.A., M atos, W.O., M ilori, D.M .B.P ., Nogueira, A.R.A., and M artin-Neto, L.: Food Control, 2010, 21, pp. 1327–1330.
ablation/ ICP-OES spectrometry”, N. Gilon, J. El-Haddad, A. Stankova,W. Lei, Q. M a, V. M otto-Ros, and J. Y u, Anal Bioanal Chem (2011) 401:2681–2689.
Cleon Barnett, Courtneé Bell, Komal Vig, A. C. Akpovo, Lewis Johnson, Shreekumar Pillai, and Shree Singh, Anal Bioanal Chem (2011) 400:3323–3330.
M artelli, François Brygo, Philippe Delaporte, Xavier Rouau, and Cécile Barron, Food Biophysics (2011) 6:433–439.
Kumar Rai, Devendra Kumar Rai, Nilesh Kumar Rai, A. K. Rai, Dane Bicanic, Bechan Sharma and Geeta Watal, Food Biophysics, published online: 20 April 2010.
sorbent (mainly Cu and Co) from synthetic wastewater.
(XRF) analysis technique
verified the feasibility of using LIBS to detect traces of heavy metals adsorbed from wastewater by fish bones.
applications. * Citations directly from the Abstract and Conclusion
mechanically separated poultry meat (M SM ).
requested by the industry.
fast and potentially enables direct detection of minerals in a sample with minimal sample preparation.
measured by LIBS using sample preparation suitable for an industrial at-line monitoring setting.
were determined.
line method for measurement of fresh M SM samples in a production setting.
investigated and can be offered as an alternative to the wet methods of analysis.
alcohol performances and to payment systems.
combined with a Partial Least Squares (PLS) chemometric tool that can achieve the best model to predict fiber content in sugar cane.
predict fiber content in raw sugar cane bagasse, in the presence of impurities and moisture, without pre-treatment of samples and as close as possible to the nature of the samples.
for various materials.
products (e.g. coffee, spices) are in fact legitimate due to the variation of quality from different source locations world-wide. Another example is to identify the source country for imported commodities going through Customs so as to assess the correct tariff which varies depending on the source country.
for rapid identification of the country of origin of various materials.
can not only be created with 100% separation between the 4 countries of origin (China, India, Syria, and Turkey), but also when tested they show 100% correct matching to the country of origin.
elemental fingerprinting for provenance determinations.
“Spectroscopy M ethods for Identifying the Country of Origin”, Ellen Hondrogiannis, Erin Ehrlinger, and Andrzej W. M iziolek, Next-Generation Spectroscopic Technologies VI, edited by M ark A. Druy, Richard A. Crocombe, Proc. of SPIE Vol. 8726, 87260Q.
Spectrum
M g, Si Ca, Al Sr, Ca, M n Sr, Al, Fe
Discriminant Functions Plot by Origin Df1 (72.33%) Origin China Syria Turkey India Df2 (19.20%)
1.5 3.5
1 2 3 4
Centroid
The model correctly predicted the geographic origin of all test samples 100.0% during validation testing. Data captured by the benchtop LIBSCAN 100 system The intensities from the lines due to Al, Ba, Ca, Cr, Fe, M g and Sr were ratioed to K and entered into the discriminant analysis.
http:/ / www.oliveoiltimes.com/ tag/ olive-oil-adulteration
“Some reports… have shown that 80 percent of olive oil in grocery stores is either mislabeled — making the claim that it's extra virgin when it isn't — or what he called "counterfeit," mixed with seed
lorraine.mirabella@baltsun.com, M ay 10, 1016, http:/ / www.baltimoresun.com/ business/ bs-bz-olive-oil-fda-testing-20160509-story.html
identification, quality control, traceability, and adulteration detection of extra virgin olive oils.
certainty of more than 95%.
samples.
robust measurements, and the system can be packed into portable form for non-specialist users.
(RGC) are intrinsically related to its quality.
tasters.
prohibitive.
however it demands an accurate coupled-model for pattern recognition.
design of dedicated equipment with low-cost devices.
methodology for investigating elemental accumulation in different layers within plant leaves, with in-situ spatial resolution mapping, exploiting the technique of LIBS.
to develop a real time identification procedure in order to complement
analysis.
transportation and storage of some nutrition elements is changed.
processing the leaves of various plants of the genus Nicotiana tabacum.
a recent report from the United Nations Food and Agriculture Organization
cigars, which for some third-world countries is an important source of income.
that occurs, for example, when authentic high-quality leaves are replaced by lower quality leaves.
identification of handmade cigars that measures the M g/ Ca ratios in the tobacco leaves and wrappers of the cigars using laser-induced breakdown spectroscopy.
based solid sampling technique that has many potential forensic applications.
coupled plasma mass spectrometry (ICP-M S), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-M S) and X-ray microfluorescence (mXRF), was evaluated for the ability to conduct elemental analyses on Cannabis plant material, with a specific investigation of the possible links between hydroponic nutrients and elemental profiles from associated plant material.
concentrations or peak areas of the elements of interest were monitored.
could be related to the use of particular commercial nutrients.
techniques for the comparison of Cannabis samples from different sources, with high discriminating powers being achieved.
Jana Bockováa,d, Y e Tiana,b, Hualiang Yina, Nicole Delepine-Gilonc, Qianli M ae, Y anping Chene, Pavel Veisd and Jin Y ua,e,
aInstitut Lumière M atière, Université Lyon 1-CNRS, Université de Lyon, France bOptics and Optoelectronics Laboratory, Ocean University of China, 266100, Qingdao, R. P
. China
cInstitut des Sciences Analytiques, Université Lyon 1-CNRS, Université de Lyon,France dDepartment of Experimental Physics, Comenius University in Bratislava, M lynská dolina, 842 48, Bratislava, Slovakia eKey Laboratory for Laser Plasmas, Department of Physics and Astronomy, Shanghai Jiao T
* Work in progress
“Our results with wine are already quite significant with a LoD of 100 ppb for Ti and ~ 20 elements detected in commercial available wines, which opens many perspectives in wine analysis:
production region,
Calcified Tissues
Soft Tissues
M edical Specimens
Bacteria/ Pathogens
Laser guided surgery
Sampling locations
Concentration
5 9
A
C
Ratio of Mg/Ca
Sampling locations
1 2 4 5 3
B
Calcium-normalized strontium LIBS intensity (false color grayscale) A rb itra ry in ten sity u n its
D
Calcified Tissues
Soft Tissues
V.K. Singh and A.K. Rai, Lasers Med. Sci. 26, 307 (2011) F.C. Alvira et al., Appl. Spectrosc. 64, 313 (2010)
N o r m a lize d LIB S In t e n sity (A .U .)A breast cancer
N o r m a lize d LIB S In t e n sit y (A .U .)B colorectal cancer
Breast Cancer GradeC calcium emission D
Breast Cancer Grademagnesium emission E
Colorectal Cancer Gradecalcium emission F
Colorectal Cancer Grademagnesium emission
495 (2010)
Tooth 1D and 2D M apping
Au Nanoparticles in Rat Kidney (20 micron res.)
M alignant vs. Healthy Tissue
http:/ / www.spectroscopyonline .com/ biological-mapping-libs
Ros, Lyon 1 University
Journal of M edical Eng & Tech, 2012, 36(2): 77-89
Bacteria/ Pathogens
(a)
Escherichia Enterobacter Staphylococcus Streptococcus Mycobacterium
(b)
Q.I. Mohaidat et al., Appl. Opt. 51, B99 (2012)
Bacterial Strain Differentiation
R.A. Putnam et al., Spectrochim. Acta B 87, 161-167 (2013).
Laser guided surgery
D.C. Jeong et al., Curr. Opin. Neurobiol. 22, 24 (2012) B.-M. Kim et al., Appl. Surface Sci. 127– 129, 857 (1998)
LIBS-Feedback-Guided Laser Surgery
Background
Billion dollars market for online/fast coal proximate and ultimate analysis in
China for pricing, coal blending, and combustion optimization
Traditional chemical processing method takes 14~24 hours
Thirstily require online/fast coal property analyzer LIBS: a promising technology
Challenges
Precision
Reproducibility: Very little work has been done to improved measurement-to-measurement reproducibility
Normally much higher than national standard for coal analyze (RSD less than 1%) Accuracy
Affected by ash content, moisture content, and volatile content greatly
Increasing pulse number does not effectively decrease sample-to-sample RSD to satisfactory levels
Univariate model: Worse calibration results, better reproducibility Multi-variate model: Better calibration results, worse reproducibility
Current Model does not work for coal analysis
Lifetime cooperation between TSI and Tsinghua University
Methods
Using standardization method to reduce the RSD of each spectral line
Using dominant factor based PLS method to improve measurement accuracy
Using self-adoptive spectra database and spectrum identification technology to greatly improve reproducibility and accuracy
Special consideration for coal analysis
Rely more on major coal elements such as C, H, O, N
Classification before prediction
Results
Meet the national standard using chemical processing method using LIBS and prove the feasibility of LIBS for quantitative coal analysis
Develop a method that enable precise and accurate measurement for
Method Flow-chart
PLS model Proposed model National standard Error of C measurement 4.9% 0.42% <1% Error of H measurement 0.30% 0.05% <0.25% Error of ash measurement 1.1 %( ash<15%) 1.8 %( 15 %< ash<30%) 1.9 %( ash>30%) 0.07 % (ash<15%) 0.17% (15 %< ash<30%) 0.23% (ash>30%) <0.3% (ash<15%) <0.5% (15 %< ash<30%) <0.7% ( ash>30%) Error of volatile measurement 0.93 %( volatile <20%) 1.69 %( 20 %< volatile <40%) (No sample for volatile >40%) 0.03 %( volatile <20%) 0.11 %( 20 %< volatile <40%) (No sample for volatile >40%) <0.5% ( volatile <20%) <1% (20%<volatile <40%) <1.5% (volatile >40%) Error of heat value measurement 1.1 MJ/kg 0.07 MJ/kg <0.3 MJ/kg
Results list Carbon Measurement Heat value Measurement
wear metals in oils has been evaluated in this work with a specific ablation configuration
Ni, Pb, Si, Sn, and Ti) was prepared.
the determination coefficient, R2, of all the calibration curves are superior to 0.99.
Pb excluded)… (M g, Cu and Ag) are determined lower than μg/ g, i.e. in the sub-ppm level.
introduced ablation configuration as one of the most suitable methods for highly sensitive and precise wear metal analysis in oils.
magnetic plugs allows the machinery maintainer to assess the health of the engine or gearbox and identify specific component damage.
induced breakdown spectroscopy (LIBS) and Xray fluorescence (XRF) instruments. Both techniques can be utilized in various industries including aviation, marine, railways, heavy diesel and other industrial machinery.
measurements of a wide range of typical aerospace alloys including steels, titanium, aluminum and nickel alloys.
alloys comprising lighter elements as compared to that of the portable XRF system, and reveals a significant reduction in the analysis time over XRF.
5 1
Large Scale Deployable/Mobile Systems - Least sensitive to system size, cost, & power
– Facilities; Installed large system infrastructure, water and sewer treatment – Power Production Industry; Windmills, Turbine Engines, Transmissions, Generators – Transportation; Ocean Going Vessels, Cargo Shipping, Military, Cruise Ships – Manufacturing process fluids and effluent stream monitoring
Intermediate Scale Fieldable/Installed Platform Systems - Reducing size, weight & cost
– Transportation Industry - Commercial Long Haul; Trucking, Locomotives, Planes – Construction Equipment; Bulldozers, Quarry equipment, Mining and Tunneling – Scientific studies and long-term monitoring (e.g. waterways, streams and effluent)
Small Scale Integrated Analysis Systems Market - More sensitive to system size & cost
– Planes, Trains, and Automobiles (e.g. oil, cooling steering, and transmission fluids) – Medial monitoring and diagnostics (e.g. cell, bacterial, and wound monitoring)
Commercial Scale Transparent Monitoring Systems - Large quantities, small & cheap
– Home and commercial appliances (e.g. HVAC and refrigeration systems) – Ubiquitous installed monitoring applications
Ron Pivarnik, Director of Programs, Ron@sbmicrosystems.us
5 2
Large Scale Deployable/Mobile Systems (1-5 Years)
– Reasonable, not overly sensitive to, size or constrained requirements – Ruggedized Deployable analysis system for very expensive equipment – Installed base of systems in the hundreds of units – Level of detection (LOD) – parts per million (PPM)
Intermediate Scale Fieldable Systems (5-15 Year)
– Installable system platform, size and cost reduction – Size reduction due to custom component integrations – Installed base growing into the hundreds of thousands – Level of detection (LOD) – parts per billion (PPB)
Small Scale Integrated Analysis Systems (15+ Years)
– Size, weight, power, and cost constraints are important – Transparently installation base in the millions units annually – Integrated with other commercial and home analytics system sensors – Level of detection (LOD) – parts per trillion (PPT)
Installation of small, cost effective in-situ fluidic analysis system in high value machinery. Data becomes the product, not the system itself. Enablers
Small size : Unobtrusive installation
Requires new thinking in source and detection components
Lower duty cycle, rugged environment
Unattended monitoring, seamless integration
Low cost relative to monitored equipment/system
Cost reduces as monitoring is pushed closer to consumer & volume increases
Industrial machinery (Power generator transmissions, manufacturing equipment, cargo vessels)
Consumer machinery (Automotive [~15M units/annum], household appliances)
Heavy machinery (Trucks, ships, trains, planes)
Product qualification & safety (HALT, HASS)
Drilling platforms (Oil, water)
On-the-fly monitoring of machine health
Reduces the downtime of machinery
Measured in $M/hr
Environmentally conscious
Reduces consumption of lubricants, coolants, other hazards 5 3
Two models: Z-200: Spectral range 190 – 615 nm Z-300: Spectral range 190 – 950 nm Extended range of Z-300 adds lines for 10 additional elements: H, O, N, Cl, Br, F , Rb, K, Ce, S
There are 7 companies that are selling handheld (HH) LIBS systems
56
alloy verification and scrap sorting,
major metal producers for quantitative alloy chemistry and grade verification. (key elements Li, Be, M g, Si, Cr, Cu, Zn, Zr).
for flow-accelerated corrosion (power plants),
scrap.
technology that can measure several critical elements and base metals: Li, Be, B, Na, M g, Al,
transition/ heavy metals,
complementary technology,
due to sampling effects not LIBS precision/ bias.
measure S lines in 920- 930 nm.
The effect of the coupling between the laser electromagnetic field and the surface plasmons of the NPs deposited
1) Production of seed electrons by electron emission field (tunneling) instead of multiphoton ionization and consequent generation of multipoint plasma ignition (i.e. more efficient ablation) 2) More efficient electron excitation 3) Increasing of the emitters concentration inside the confining SW wall 4) Increasing of the emission lines up to 2 orders of magnitude
Microdrop of metal NPs solution (0.5 µl, 0.02 mg/ml, surface concentration 32 ng cm-2) Laser @1064 nm Laser @1064 nm
Signal enhancement about 200 times in conductive samples
50 100 150 200 50 100 150 200 250 300
Intensity Pb I405.78 nm (a.u.) PbCl2 Pb concentration (ppb)
NELIBS LIBS y = 1.54*x + 5.87, R
2 = 0.992
y = 0.28*x + 42.46, R
2 = 0.999
Comparison between NELIBS and LIBS Li signal in a solution of the protein Reaction Center (RC) from the purple bacterium Rhodobacter sphaeroides at concentration 10-5 M. Comparison between NELIBS and LIBS Mn I calibration curves in bronze alloys Comparison between NELIBS and LIBS Pb I calibration curves in PbCl2 water solution
Recent results: 1) Application to biological samples (enhancement of the signal up to 1-2 order of magnitude) Detection of metals in proteins and tagged proteins (collaboration with DSU). 2) LOD below hundreds of parts-per-trillion (ppt) for metallic cations in 1 µl of liquid solution. 3) Non destructive analysis of transparent sample. 4) Enhancement of the molecular emission up to 1 order of magnitude (collaboration with LBNL). Work in progress: 1) Applying NELIBS to animal tissue (collaboration with University of Lyon) 2) Push the spatial resolution of LIBS to nm scale exploiting the different ablation threshold
Chapter Content for the LIBS Section 7.7 Laser-Induced Breakdown Spectroscopy 7.7.1 Principle of Operation 7.7.2 Instrumentation 7.7.3 Applications of LIBS 7.7.3.1 Qualitative Analysis 7.7.3.2 Quantitative Analysis 7.7.3.3 Remote Analysis 7.7.4 Commercial LIBS S ystems
7th Edition contains new topics-
Example of a handheld LIBS unit, 5-7 mJ/ pulse, battery-operated. There are currently 7 companies selling handheld LIBS systems. Example of Person- Portable LIBS unit, 45-50 mJ/ pulse, battery operated Example of Trans- Portable LIBS unit, 150 mJ/ pulse A number of LIBS M anufacturers make benchtop systems. Generally, the greater the laser pulse energy up to 100-150 mJ/ pulse, the better the performance in “elemental fingerprinting/ provenance”