Enabling Microscale Processing: Combined Raman and Absorbance Spectroscopy for Microfluidic On-Line Monitoring

Nelson, Gilbert L.; Lackey, Hope E.; Bello, Job M.; Felmy, Heather M.; Bryan, Hannah B.; Lamadie, Fabrice; Bryan, Samuel A.; Lines, Amanda M.

doi:10.1021/acs.analchem.0c04225

Enabling Microscale Processing: Combined Raman and Absorbance Spectroscopy for Microfluidic On-Line Monitoring

Journal Article · Fri Dec 18 04:00:00 EST 2020 · Analytical Chemistry

DOI:https://doi.org/10.1021/acs.analchem.0c04225· OSTI ID:1783814

Nelson, Gilbert L. ^[1]; Lackey, Hope E. ^[2]; Bello, Job M. ^[3]; Felmy, Heather M. ^[2]; Bryan, Hannah B. ^[2]; ^[4]; ^[2]; Lines, Amanda M. ^[2]

College of Idaho, Caldwell, ID (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Spectra Solutions Incorporated, 1502 Providence Highway, Norwood, Massachusetts 02062-4643, United States
Montpellier Univ. 2 (France)

Microfluidics have many potential applications including characterization of chemical processes on a reduced scale, spanning the study of reaction kinetics using on-chip liquid–liquid extractions, sample pretreatment to simplify off-chip analysis, and for portable spectroscopic analyses. The use of in situ characterization of process streams from laboratory-scale and microscale experiments on the same chemical system can provide comprehensive understanding and in-depth analysis of any similarities or differences between process conditions at different scales. A well-characterized extraction of Nd(NO₃)₃ from an aqueous phase of varying NO_3– _(aq) concentration with tributyl phosphate (TBP) in dodecane was the focus of this microscale study and was compared to an earlier laboratory-scale study utilizing counter current extraction equipment. Here, we verify that this same extraction process can be followed on the microscale using spectroscopic methods adapted for microfluidic measurement. Concentration of Nd (based on UV–vis) and nitrate (based on Raman) was chemometrically measured during the flow experiment, and resulting data were used to determine the distribution ratio for Nd. Extraction distributions measured on the microscale were compared favorably with those determined on the laboratory scale in the earlier study. Both micro-Raman and micro-UV–vis spectroscopy can be used to determine fundamental parameters with significantly reduced sample size as compared to traditional laboratory-scale approaches. This leads naturally to time, cost, and waste reductions.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1783814

Report Number(s):: PNNL-SA--156894

Journal Information:: Analytical Chemistry, Journal Name: Analytical Chemistry Journal Issue: 3 Vol. 93; ISSN 0003-2700

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (40)

Microreactors: New Technology for Modern Chemistry Ehrfeld, Wolfgang; Hessel, Volker; Löwe, Holger https://doi.org/10.1002/3527601953		April 2000
Liquid-liquid two-phase flow patterns in a rectangular microchannel Zhao, Yuchao; Chen, Guangwen; Yuan, Quan AIChE Journal, Vol. 52, Issue 12 https://doi.org/10.1002/aic.11029	journal	January 2006
Oil-water two-phase flow in microchannels: Flow patterns and pressure drop measurements Salim, Abdelkader; Fourar, Mostafa; Pironon, Jacques The Canadian Journal of Chemical Engineering, Vol. 86, Issue 6 https://doi.org/10.1002/cjce.20108	journal	December 2008
Surface molecular property modifications for poly(dimethylsiloxane) (PDMS) based microfluidic devices Wong, Ieong; Ho, Chih-Ming Microfluidics and Nanofluidics, Vol. 7, Issue 3 https://doi.org/10.1007/s10404-009-0443-4	journal	April 2009
Photonic Lab-on-a-Chip analytical systems for nuclear applications: optical performance and UV–Vis–IR material characterization after chemical exposure and gamma irradiation Mattio, Elodie; Lamadie, Fabrice; Rodriguez-Ruiz, Isaac Journal of Radioanalytical and Nuclear Chemistry, Vol. 323, Issue 2 https://doi.org/10.1007/s10967-019-06992-x	journal	December 2019
Complex formation in the neodymium nitrate-tributyl phosphate-water system Bostian, H.; Smutz, M. Journal of Inorganic and Nuclear Chemistry, Vol. 26, Issue 5 https://doi.org/10.1016/0022-1902(64)80329-8	journal	May 1964
A versatile and low-cost chip-to-world interface: Enabling ICP-MS characterization of isotachophoretically separated lanthanides on a microfluidic device Lackey, Hope; Bottenus, Danny; Liezers, Martin Analytica Chimica Acta, Vol. 1137 https://doi.org/10.1016/j.aca.2020.08.049	journal	November 2020
Hydrodynamics of liquid–liquid slug flow capillary microreactor: Flow regimes, slug size and pressure drop Kashid, Madhvanand N.; Agar, David W. Chemical Engineering Journal, Vol. 131, Issue 1-3 https://doi.org/10.1016/j.cej.2006.11.020	journal	July 2007
Flow patterns of liquid–liquid two-phase flow in non-Newtonian fluids in rectangular microchannels Fu, Taotao; Wei, Lijuan; Zhu, Chunying Chemical Engineering and Processing: Process Intensification, Vol. 91 https://doi.org/10.1016/j.cep.2015.03.020	journal	May 2015
Liquid–liquid two-phase flow patterns and mass transfer characteristics in rectangular glass microreactors Dessimoz, Anne-Laure; Cavin, Laurent; Renken, Albert Chemical Engineering Science, Vol. 63, Issue 16 https://doi.org/10.1016/j.ces.2008.05.005	journal	August 2008
Effect of surface properties on the flow characteristics and mass transfer performance in microchannels Zhao, Yuchao; Su, Yuanhai; Chen, Guangwen Chemical Engineering Science, Vol. 65, Issue 5 https://doi.org/10.1016/j.ces.2009.10.027	journal	March 2010
Spectroscopic properties of Eu3+/Nd3+ co-doped phosphate glasses and opaque glass–ceramics Narro-García, R.; Desirena, H.; López-Luke, T. Optical Materials, Vol. 46 https://doi.org/10.1016/j.optmat.2015.03.051	journal	August 2015
Spectroscopic properties of neodymium(III)-containing polyoxometalates in aqueous solution But, Slawomir; Lis, Stefan; Deun, Rik Van Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 62, Issue 1-3 https://doi.org/10.1016/j.saa.2005.01.019	journal	November 2005
Microreaction engineering — is small better? Jensen, Klavs F. Chemical Engineering Science, Vol. 56, Issue 2, p. 293-303 https://doi.org/10.1016/s0009-2509(00)00230-x	journal	January 2001
Development of Online Spectroscopic pH Monitoring for Nuclear Fuel Reprocessing Plants: Weak Acid Schemes Casella, Amanda J.; Ahlers, Laura R. H.; Campbell, Emily L. Analytical Chemistry, Vol. 87, Issue 10 https://doi.org/10.1021/ac504578t	journal	April 2015
Multivariate Analysis for Quantification of Plutonium(IV) in Nitric Acid Based on Absorption Spectra Lines, Amanda M.; Adami, Susan R.; Sinkov, Sergey I. Analytical Chemistry, Vol. 89, Issue 17 https://doi.org/10.1021/acs.analchem.7b02161	journal	August 2017
Multivariate Analysis To Quantify Species in the Presence of Direct Interferents: Micro-Raman Analysis of HNO ₃ in Microfluidic Devices Lines, Amanda M.; Nelson, Gilbert L.; Casella, Amanda J. Analytical Chemistry, Vol. 90, Issue 4 https://doi.org/10.1021/acs.analchem.7b03833	journal	January 2018
Micro-Raman Technology to Interrogate Two-Phase Extraction on a Microfluidic Device Nelson, Gilbert L.; Asmussen, Susan E.; Lines, Amanda M. Analytical Chemistry, Vol. 90, Issue 14 https://doi.org/10.1021/acs.analchem.7b04330	journal	May 2018
Uranium(VI) On-Chip Microliter Concentration Measurements in a Highly Extended UV–Visible Absorbance Linearity Range Rodríguez-Ruiz, Isaac; Lamadie, Fabrice; Charton, Sophie Analytical Chemistry, Vol. 90, Issue 4 https://doi.org/10.1021/acs.analchem.7b05162	journal	January 2018
Microfluidic Device for the Determination of Water Chlorination Levels Combining a Fluorescent meso -Enamine Boron Dipyrromethene Probe and a Microhydrocyclone for Gas Bubble Separation Tillo, Adam; Bartelmess, Juergen; Chauhan, Vraj P. Analytical Chemistry, Vol. 91, Issue 20 https://doi.org/10.1021/acs.analchem.9b03039	journal	September 2019
Reimagining pH Measurement: Utilizing Raman Spectroscopy for Enhanced Accuracy in Phosphoric Acid Systems Lackey, Hope E.; Nelson, Gilbert L.; Lines, Amanda M. Analytical Chemistry, Vol. 92, Issue 8 https://doi.org/10.1021/acs.analchem.9b05708	journal	March 2020
High Precision Droplet-Based Microfluidic Determination of Americium(III) and Lanthanide(III) Solvent Extraction Separation Kinetics Launiere, C. A.; Gelis, A. V. Industrial & Engineering Chemistry Research, Vol. 55, Issue 7 https://doi.org/10.1021/acs.iecr.5b04691	journal	February 2016
Liquid–Liquid Two-Phase Flow Patterns in Y-Junction Microchannels Darekar, Mayur; Singh, Krishna Kumar; Mukhopadhyay, Sulekha Industrial & Engineering Chemistry Research, Vol. 56, Issue 42 https://doi.org/10.1021/acs.iecr.7b03164	journal	October 2017
Online, Real-Time Analysis of Highly Complex Processing Streams: Quantification of Analytes in Hanford Tank Sample Lines, A. M.; Tse, P.; Felmy, H. M. Industrial & Engineering Chemistry Research, Vol. 58, Issue 47 https://doi.org/10.1021/acs.iecr.9b03636	journal	October 2019
Overcoming Oxidation State-Dependent Spectral Interferences: Online Monitoring of U(VI) Reduction to U(IV) via Raman and UV–vis Spectroscopy Lines, Amanda M.; Hall, Gabriel B.; Sinkov, Sergey Industrial & Engineering Chemistry Research, Vol. 59, Issue 19 https://doi.org/10.1021/acs.iecr.9b06706	journal	April 2020
Online Monitoring of Solutions Within Microfluidic Chips: Simultaneous Raman and UV–Vis Absorption Spectroscopies Nelson, Gilbert L.; Lines, Amanda M.; Bello, Job M. ACS Sensors, Vol. 4, Issue 9 https://doi.org/10.1021/acssensors.9b00736	journal	August 2019
Liquid–Liquid Two-Phase Flow Patterns in a Serpentine Microchannel Sarkar, P. S.; Singh, K. K.; Shenoy, K. T. Industrial & Engineering Chemistry Research, Vol. 51, Issue 13 https://doi.org/10.1021/ie201590f	journal	March 2012
Experimental and Numerical Investigations of Two-Phase (Liquid−Liquid) Flow Behavior in Rectangular Microchannels Cherlo, Siva Kumar Reddy; Kariveti, Sreenath; Pushpavanam, S. Industrial & Engineering Chemistry Research, Vol. 49, Issue 2 https://doi.org/10.1021/ie900555e	journal	January 2010
Characterization of Mixing in Micromixers by a Test Reaction: Single Mixing Units and Mixer Arrays Ehrfeld, Wolfgang; Golbig, Klaus; Hessel, Volker Industrial & Engineering Chemistry Research, Vol. 38, Issue 3 https://doi.org/10.1021/ie980128d	journal	March 1999
Focusing analytes from 50 μL into 500 pL: On-chip focusing from large sample volumes using isotachophoresis van Kooten, Xander F.; Truman-Rosentsvit, Marianna; Kaigala, Govind V. Scientific Reports, Vol. 7, Issue 1 https://doi.org/10.1038/s41598-017-10579-5	journal	September 2017
Nonlinear decrease of background fluorescence in polymer thin-films – a survey of materials and how they can complicate fluorescence detection in μTAS Hawkins, Kenneth R.; Yager, Paul Lab Chip, Vol. 3, Issue 4 https://doi.org/10.1039/b307772c	journal	January 2003
The autofluorescence of plastic materials and chips measured under laser irradiation Piruska, Aigars; Nikcevic, Irena; Lee, Se Hwan Lab on a Chip, Vol. 5, Issue 12 https://doi.org/10.1039/b508288a	journal	January 2005
Miniaturized system for isotachophoresis assays Kaigala, G. V.; Bercovici, M.; Behnam, M. Lab on a Chip, Vol. 10, Issue 17 https://doi.org/10.1039/c004120c	journal	January 2010
Development and testing of a novel micro-Raman probe and application of calibration method for the quantitative analysis of microfluidic nitric acid streams Nelson, Gilbert L.; Lines, Amanda M.; Casella, Amanda J. The Analyst, Vol. 143, Issue 5 https://doi.org/10.1039/c7an01761h	journal	January 2018
Theoretical assessment of wettability on silane coatings: from hydrophilic to hydrophobic Huang, Haiming; Wang, Weiliang; Wang, Liming Physical Chemistry Chemical Physics, Vol. 21, Issue 16 https://doi.org/10.1039/c9cp01232j	journal	January 2019
A microfluidic study of synergic liquid–liquid extraction of rare earth elements El Maangar, Asmae; Theisen, Johannes; Penisson, Christophe Physical Chemistry Chemical Physics, Vol. 22, Issue 10 https://doi.org/10.1039/c9cp06569e	journal	January 2020
Simulant testing of a co-decontamination (CoDCon) flowsheet for a product with a controlled uranium-to-plutonium ratio Lumetta, Gregg J.; Allred, Jarrod R.; Bryan, Samuel A. Separation Science and Technology, Vol. 54, Issue 12 https://doi.org/10.1080/01496395.2019.1594899	journal	March 2019
Photoluminescence response of acrylic (PMMA) and polytetrafluoroethylene (PTFE) to ultraviolet light: Limits on low-intensity photoluminescence in support materials of rare-event search experiments Araujo, G. R.; Pollmann, T.; Ulrich, A. The European Physical Journal C, Vol. 79, Issue 8 https://doi.org/10.1140/epjc/s10052-019-7152-2	journal	August 2019
Controllable energy transfer in fluorescence upconversion of NdF_3 and NaNdF_4 nanocrystals Li, M.; Hao, Z. -H.; Peng, X. -N. Optics Express, Vol. 18, Issue 4 https://doi.org/10.1364/oe.18.003364	journal	January 2010
Spectroscopic monitoring of spent nuclear fuel reprocessing streams: an evaluation of spent fuel solutions via Raman, visible, and near-infrared spectroscopy Bryan, S. A.; Levitskaia, Tatiana G.; Johnsen, A. M. Radiochimica Acta, Vol. 99, Issue 9 https://doi.org/10.1524/ract.2011.1865	journal	September 2011

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Enabling Microscale Processing: Combined Raman and Absorbance Spectroscopy for Microfluidic On-Line Monitoring

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