A prototype laser-induced breakdown spectroscopy (LIBS) sensor is tested for the determination of rare earth elements (Eu and Yb) in liquid and solid samples. The sensor head, built using a monolithic passively Q-switched (PQSW) Nd:YAG laser, produced a 1064 nm laser beam with ns pulses and an energy of 4.2 mJ. The measurements show good calibration linearity for both Eu and Yb with R2 values above 0.99 for all analyzed spectral lines in liquid and solid samples. Limits of detection (LODs) obtained were as low as 1 ppm, which are comparable to or better than those reported previously by using table top actively Q-switched systems. This study aims to develop a high sensitivity, field deployable sensor for characterizing existing and new sources of rare earth elements.

References

References
1.
U.S. DOE
,
2011
, “
Critical Materials Strategy
,” U.S. Department of Energy, Washington, DC.
2.
Ganguli
,
R.
, and
Cook
,
D. R.
,
2018
, “
Rare Earths: A Review of the Landscape
,”
MRS Energy Sustainability
,
5
, pp. 1–16.
3.
Cornell
,
D.
,
1993
, “
Rare Earths From Supernova to Superconductor
,”
Pure Appl. Chem.
,
65
(
12
), pp.
2453
2464
.
4.
Noack
,
C. W.
,
Dzombak
,
D. A.
, and
Karamalidis
,
A. K.
,
2014
, “
Rare Earth Element Distributions and Trends in Natural Waters With a Focus on Groundwater
,”
Environ. Sci. Technol.
,
48
(
8
), pp.
4317
4326
.
5.
Haas
,
J. R.
,
Shock
,
E. L.
, and
Sassani
,
D. C.
,
1995
, “
Rare Earth Elements in Hydrothermal Systems: Estimates of Standard Partial Molal Thermodynamic Properties of Aqueous Complexes of the Rare Earth Elements at High Pressures and Temperatures
,”
Geochim. Cosmochim. Acta
,
59
(
21
), pp.
4329
4350
.
6.
Douville
,
E.
,
Bienvenu
,
P.
,
Charlou
,
J. L.
,
Donval
,
J. P.
,
Fouquet
,
Y.
,
Appriou
,
P.
, and
Gamo
,
T.
,
1999
, “
Yttrium and Rare Earth Elements in Fluids From Various Deep-Sea Hydrothermal Systems
,”
Geochim. Cosmochim. Acta
,
63
(
5
), pp.
627
643
.
7.
Michard
,
A.
,
1989
, “
Rare Earth Element Systematics in Hydrothermal Fluids
,”
Geochim. Cosmochim. Acta
,
53
(
3
), pp.
745
750
.
8.
Cravotta
,
C. A.
, III.
,
2008
, “
Dissolved Metals and Associated Constituents in Abandoned Coal-Mine Discharges, Pennsylvania, USA—Part 1: Constituent Quantities and Correlations
,”
Appl. Geochem.
,
23
(
2
), pp.
166
202
.
9.
Da Silva
,
E. F.
,
Bobos
,
I.
,
Matos
,
J. X.
,
Patinha
,
C.
,
Reis
,
A.
, and
Fonseca
,
E. C.
,
2009
, “
Mineralogy and Geochemistry of Trace Metals and REE in Volcanic Massive Sulfide Host Rocks, Stream Sediments, Stream Waters and Acid Mine Drainage From the Lousal Mine Area (Iberian Pyrite Belt, Portugal)
,”
Appl. Geochem.
,
24
(
3
), pp.
383
401
.
10.
Ayora
,
C.
,
Macias
,
F.
,
Torres
,
E.
,
Lozano
,
A.
,
Carrero
,
S.
,
Nieto
,
J.-M.
,
Pérez-López
,
R.
,
Fernandez- Martfnez
,
A.
, and
Castillo-Michel
,
H.
,
2016
, “
Recovery of Rare Earth Elements and Yttrium From Passive- Remediation Systems of Acid Mine Drainage
,”
Environ. Sci. Technol.
,
50
(
15
), pp.
8255
8262
.
11.
Laudal
,
D. A.
,
Benson
,
S. A.
,
Palo
,
D.
, and
Addleman
,
R. S.
,
2018
, “
Rare Earth Elements in North Dakota Lignite Coal and Lignite-Related Materials
,”
ASME J. Energy Resour. Technol.
,
140
(
6
), p.
062205
.
12.
NETL
, U.S. DOE, 2018, “
Rare Earth Element Database
,” National Energy Technology Laboratory, Pittsburgh, PA, accessed July 2018, https://edx.netl.doe.gov/ree/
13.
Taggart
,
R. K.
,
Hower
,
J. C.
,
Dwyer
,
G. S.
, and
Hsu-Kim
,
H.
,
2016
, “
Trends in the Rare Earth Element Content of US-Based Coal Combustion Fly Ashes
,”
Environ. Sci. Technol.
,
50
(
11
), pp.
5919
5926
.
14.
Franus
,
W.
,
Wiatros-Motyka
,
M. M.
, and
Wdowin
,
M.
,
2015
, “
Coal Fly Ash as a Resource for Rare Earth Elements
,”
Environ. Sci. Pollut. Res.
,
22
(
12
), pp.
9464
9474
.
15.
Zawisza
,
B.
,
Pytlakowska
,
K.
,
Feist
,
B.
,
Polowniak
,
M.
,
Kita
,
A.
, and
Sitko
,
R.
,
2011
, “
Determination of Rare Earth Elements by Spectroscopic Techniques: A Review
,”
J. Anal. At. Spectrom.
,
26
(
12
), pp.
2373
2390
.
16.
Jain
,
J. C.
,
Neal
,
C. R.
, and
Hanchar
,
J. M.
,
2001
, “
Problems Associated With the Determination of Rare Earth Elements of a ‘Gem’ Quality Zircon by Inductively Coupled Plasma-Mass Spectrometry
,”
Geostand. Newsl.
,
25
(
2–3
), pp.
229
237
.
17.
Musazzi
,
S.
, and
Perini
,
U.
,
2014
,
Laser-Induced Breakdown Spectroscopy
, (Springer Series in Optical Sciences), Springer, Berlin, p. 182.
18.
Singh
,
J. P.
,
Almirall
,
J. R.
,
Sabsabi
,
M.
, and
Miziolek
,
A. W.
,
2011
, “
Laser-Induced Breakdown Spectroscopy (LIBS)
,”
Anal. Bioanal. Chem.
,
400
(10), pp. 3191–3192
19.
Unnikrishnan
,
V.
,
Nayak
,
R.
,
Devangad
,
P.
,
Tamboli
,
M.
,
Santhosh
,
C.
,
Kumar
,
G.
, and
Sardar
,
D.
,
2013
, “
Calibration Based Laser-Induced Breakdown Spectroscopy (LIBS) for Quantitative Analysis of Doped Rare Earth Elements in Phosphors
,”
Mater. Lett.
,
107
, pp.
322
324
.
20.
Martin
,
M.
,
Martin
,
R. C.
,
Allman
,
S.
,
Brice
,
D.
,
Wymore
,
A.
, and
Andre
,
N.
,
2015
, “
Quantification of Rare Earth Elements Using Laser-Induced Breakdown Spectroscopy
,”
Spectrochim. Acta, Part B
,
114
, pp.
65
73
.
21.
Bhatt
,
C. R.
,
Jain
,
J. C.
,
Goueguel
,
C. L.
,
McIntyre
,
D. L.
, and
Singh
,
J. P.
,
2018
, “
Determination of Rare Earth Elements in Geological Samples Using Laser-Induced Breakdown Spectroscopy (LIBS)
,”
Appl. Spectrosc.
,
72
(
1
), pp.
114
121
.
22.
Abedin
,
K.
,
Haider
,
A.
,
Rony
,
M.
, and
Khan
,
Z.
,
2011
, “
Identification of Multiple Rare Earths and Associated Elements in Raw Monazite Sands by Laser-Induced Breakdown Spectroscopy
,”
Opt. Laser Technol.
,
43
(
1
), pp.
45
49
.
23.
Bhatt
,
C. R.
,
Jain
,
J. C.
,
Goueguel
,
C. L.
,
McIntyre
,
D. L.
, and
Singh
,
J. P.
,
2017
, “
Measurement of Eu and Yb in Aqueous Solutions by Underwater Laser Induced Breakdown Spectroscopy
,”
Spectrochim. Acta, Part B
,
137
, pp.
8
12
.
24.
Yun
,
J.-I.
,
Bundschuh
,
T.
,
Neck
,
V.
, and
Kim
,
J.-I.
,
2001
, “
Selective Determination of Europium (III) Oxide and Hydroxide Colloids in Aqueous Solution by Laser-Induced Breakdown Spectroscopy
,”
Appl. Spectrosc.
,
55
(
3
), pp.
273
278
.
25.
Alamelu
,
D.
,
Sarkar
,
A.
, and
Aggarwal
,
S.
,
2008
, “
Laser-Induced Breakdown Spectroscopy for Simultaneous Determination of Sm, Eu and Gd in Aqueous Solution
,”
Talanta
,
77
(
1
), pp.
256
261
.
26.
Bhatt
,
C. R.
,
Yueh
,
F. Y.
, and
Singh
,
J. P.
,
2017
, “
Univariate and Multivariate Analyses of Rare Earth Elements by Laser-Induced Breakdown Spectroscopy
,”
Appl. Opt.
,
56
(
8
), pp.
2280
2287
.
27.
Jung
,
E.
,
Lee
,
D.-H.
,
Yun
,
J.-I.
,
Kim
,
J.
,
Yeon
,
J.
, and
Song
,
K.
,
2011
, “
Quantitative Determination of Uranium and Europium in Glass Matrix by Laser-Induced Breakdown Spectroscopy
,”
Spectrochim. Acta, Part B
,
66
(
9–10
), pp.
761
764
.
28.
Manard
,
B. T.
,
Wylie
,
E. M.
, and
Willson
,
S. P.
,
2018
, “
Analysis of Rare Earth Elements in Uranium Using Handheld Laser-Induced Breakdown Spectroscopy (HH LIBS
),”
Appl. Spectrosc.
,
72
(11), pp. 1653–1660.
29.
Myhre
,
K. G.
,
Mehta
,
M. J.
,
Martin
,
M. Z.
, and
Du
,
M.
,
2018
, “
Laser Induced Breakdown Spectroscopy Analysis of Europium and Samarium in Aluminum Oxide
,”
Spectrochim. Acta Part B
,
149
, pp.
30
34
.
30.
Hartzler
,
D. A.
,
Jain
,
J. C.
, and
McIntyre
,
D. L.
,
2019
, “
Development of a Subsurface LIBS Sensor for In Situ Groundwater Quality Monitoring With Applications in CO2 Leak Sensing in Carbon Sequestration
,”
Sci. Rep.
(submitted).
31.
Allan
,
D. W.
,
1966
, “
Statistics of Atomic Frequency Standards
,”
Proc. IEEE
,
54
(
2
), pp.
221
230
.
32.
Witt
,
T.
, and
Reymann
,
D.
,
2000
, “
Using Power Spectra and Allan Variances to Characterise the Noise of Zener-Diode Voltage Standards
,”
IEE Proc. Sci., Meas. Technol.
,
147
(
4
), pp.
177
182
.
33.
Zhang
,
N. F.
,
2008
, “
Allan Variance of Time Series Models for Measurement Data
,”
Metrologia
,
45
(
5
), p.
549
.
34.
Carson
,
C. G.
,
Goueguel
,
C. L.
,
Sanghapi
,
H.
,
Jain
,
J.
, and
McIntyre
,
D.
,
2016
, “
Evaluation of a Commercially Available Passively Q-Switched Nd: YAG Laser With LiF: Saturable Absorber for Laser-Induced Breakdown Spectroscopy
,”
Opt. Laser Technol.
,
79
, pp.
146
152
.
35.
Kramida
,
A.
,
Ralchenko
,
Y.
,
Reader
,
J.
, and
Team
,
N. A.
,
2018
, “
NIST Atomic Spectra Database (Ver. 5.5.6)
,” National Institute of Standards and Technology, Gaithersburg, MD.
36.
Kennedy
,
P. K.
,
Hammer
,
D. X.
, and
Rockwell
,
B. A.
,
1997
, “
Laser-Induced Breakdown in Aqueous Media
,”
Prog. Quant. Electron.
,
21
(
3
), pp.
155
248
.
37.
Anabitarte
,
F.
,
Cobo
,
A.
, and
Lopez-Higuera
,
J. M.
,
2012
, “
Laser-Induced Breakdown Spectroscopy: Fundamentals, Applications, and Challenges
,”
ISRN Spectrosc.
,
2012
, p. 285240.
38.
Singh
,
J. P.
, and
Thakur
,
S. N.
,
2007
,
Laser-induced Breakdown Spectroscopy
,
Elsevier
, Amsterdam, The Netherlands.
39.
Griem
,
H.
,
1974
,
Spectral Line Broadening by Plasmas
,
Academic Press
,
New York
.
40.
Sakka
,
T.
,
Tamura
,
A.
,
Matsumoto
,
A.
,
Fukami
,
K.
,
Nishi
,
N.
, and
Thornton
,
B.
,
2014
, “
Effects of Pulse Width on Nascent Laser-Induced Bubbles for Underwater Laser-Induced Breakdown Spectroscopy
,”
Spectrochim. Acta Part B
,
97
, pp.
94
98
.
41.
Thornton
,
B.
,
Sakka
,
T.
,
Masamura
,
T.
,
Tamura
,
A.
,
Takahashi
,
T.
, and
Matsumoto
,
A.
,
2014
, “
Long-Duration Nano-Second Single Pulse Lasers for Observation of Spectra From Bulk Liquids at High Hydrostatic Pressures
,”
Spectrochim. Acta Part B
,
97
, pp.
7
12
.
42.
Lam
,
J.
,
Lombard
,
J.
,
Dujardin
,
C.
,
Ledoux
,
G.
,
Merabia
,
S.
, and
Amans
,
D.
,
2016
, “
Dynamical Study of Bubble Expansion Following Laser Ablation in Liquids
,”
Appl. Phys. Lett.
,
108
(
7
), p.
074104
.
43.
Angel
,
S. M.
,
Bonvallet
,
J.
,
Lawrence-Snyder
,
M.
,
Pearman
,
W. F.
, and
Register
,
J.
,
2016
, “
Underwater Measurements Using Laser Induced Breakdown Spectroscopy
,”
J. Anal. At. Spectrom.
,
31
(
1
), pp.
328
336
.
44.
Xu
,
H.
,
Mejean
,
G.
,
Liu
,
W.
,
Kamali
,
Y.
,
Daigle
,
J.-F.
,
Azarm
,
A.
,
Simard
,
P.
,
Mathieu
,
P.
,
Roy
,
G.
, and
Simard
,
J.-R.
,
2007
, “
Remote Detection of Similar Biological Materials Using Femtosecond Filament-Induced Breakdown Spectroscopy
,”
Appl. Phys. B
,
87
(
1
), pp.
151
156
.
45.
Rai
,
S.
, and
Rai
,
A. K.
,
2011
, “
Characterization of Organic Materials by LIBS for Exploration of Correlation Between Molecular and Elemental LIBS Signals
,”
AIP Adv.
,
1
(
4
), p.
042103
.
46.
Rao
,
E. N.
,
Mathi
,
P.
,
Kalam
,
S. A.
,
Sreedhar
,
S.
,
Singh
,
A. K.
,
Jagatap
,
B.
, and
Rao
,
S. V.
,
2016
, “
Femtosecond and Nanosecond LIBS Studies of Nitroimidazoles: Correlation Between Molecular Structure and LIBS Data
,”
J. Anal. At. Spectrom.
,
31
(
3
), pp.
737
750
.
47.
El Haddad
,
J.
,
Canioni
,
L.
, and
Bousquet
,
B.
,
2014
, “
Good Practices in LIBS Analysis: Review and Advices
,”
Spectrochim. Acta Part B
,
101
, pp.
171
182
.
You do not currently have access to this content.