Quantum Cascade Laser Infrared Spectroscopy for Online Monitoring of Hydroxylamine Nitrate

We describe a new approach for high sensitivity and real-time online measurements to monitor the kinetics in the processing of nuclear materials and other chemical reactions. Mid infrared (Mid-IR) quantum cascade laser (QCL) high-resolution spectroscopy was used for rapid and continuous sampling of nitrates in aqueous and organic reactive systems, using pattern recognition analysis and high sensitivity to detect and identify chemical species. In this standoff or off-set method, the collection of a sample for analysis is not required. To perform the analysis, a flow cell was used for in situ sampling of a liquid slipstream. A prototype was designed based on attenuated total reflection (ATR) coupled with the QCL beam to detect and identify chemical changes and be deployed in hostile environments, either radiological or chemical. The limit of detection (LOD) and the limit of quantification (LOQ) at 3σ for hydroxylamine nitrate ranged from 0.3 to 3 and from 3.5 to 10 g·L−1, respectively, for the nitrate system at three peaks with wavelengths between 3.8 and 9.8 μm.

[1]  B. Lendl,et al.  High-performance liquid chromatography with diamond ATR–FTIR detection for the determination of carbohydrates, alcohols and organic acids in red wine , 2003, Analytical and bioanalytical chemistry.

[2]  R. Compton,et al.  Detection and determination of nitrate and nitrite: a review. , 2001, Talanta.

[3]  D. Armbruster,et al.  Limit of blank, limit of detection and limit of quantitation. , 2008, The Clinical biochemist. Reviews.

[4]  Boris Mizaikoff,et al.  Waveguide-enhanced mid-infrared chem/bio sensors. , 2013, Chemical Society reviews.

[5]  G. Norwitz,et al.  Spectrophotometric determination of nitrite with composite reagents containing sulphanilamide, sulphanilic acid or 4-nitroaniline as the diazotisable aromatic amine and N-(1-naphthyl)ethylenediamine as the coupling agent , 1984 .

[6]  M. W. Chase,et al.  NIST-JANAF Thermochemical Tables, 4th Edition , 1998 .

[7]  H. Naveau,et al.  ATR-FTIR sensor development for continuous on-line monitoring of chlorinated aliphatic hydrocarbons in a fixed-bed bioreactor. , 2000, Biotechnology and bioengineering.

[8]  C. W. van Neste,et al.  Quartz crystal tuning fork photoacoustic point sensing , 2010 .

[9]  Jennifer D. Schuttlefield,et al.  ATR FTIR Spectroscopy in the Undergraduate Chemistry Laboratory. Part I: Fundamentals and Examples. , 2008 .

[10]  C. W. van Neste,et al.  Standoff photoacoustic spectroscopy , 2008 .

[11]  Yuanyuan Xu,et al.  A novel hydroxylamine ionic liquid salt resulting from the stabilization of NH2OH by a SO3H-functionalized ionic liquid. , 2015, Chemical communications.

[12]  Bernhard Lendl,et al.  External-Cavity Quantum Cascade Laser Spectroscopy for Mid-IR Transmission Measurements of Proteins in Aqueous Solution. , 2015, Analytical chemistry.

[13]  Yun‐Hong Zhang,et al.  ATR-FTIR spectroscopic studies on aqueous LiClO4, NaClO4, and Mg(ClO4)2 solutions , 2004 .

[14]  Philip R. Bingham,et al.  Multi-spectral Infrared Computed Tomography , 2016, Computational Imaging.

[15]  S. M. Eid,et al.  Attenuated Total Reflectance Fourier Transformation Infrared spectroscopy fingerprinted online monitoring of the kinetics of circulating Butyrylcholinesterase enzyme during metabolism of bambuterol. , 2018, Analytica chimica acta.

[16]  A. T. Kowal.  Anharmonic vibrational spectra of hydroxylamine and its 15N, 18O, and deuterium substituted analogs. , 2002, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[17]  A. Erbe,et al.  Attenuated total reflection mid-IR-spectroscopy for electrochemical applications using a QCL , 2012 .

[18]  C. Tait,et al.  Raman Spectroscopic Study of the Aging and Nitration of Actinide Processing Anion-Exchange Resins in Concentrated Nitric Acid , 1999 .

[19]  Infrared microcalorimetric spectroscopy using quantum cascade lasers. , 2013, Optics letters.

[20]  Benjamin D. Roach,et al.  Hydroxylamine Nitrate Decomposition under Non-radiological Conditions , 2015 .

[21]  F. Theil,et al.  Surface-enhanced Raman spectroscopy (SERS): progress and trends , 2012, Analytical and Bioanalytical Chemistry.

[22]  Y. Long,et al.  Recent progress in surface enhanced Raman spectroscopy for the detection of environmental pollutants , 2013, Microchimica Acta.

[23]  Paul A. Giguère,et al.  INFRARED SPECTRUM, MOLECULAR STRUCTURE, AND THERMODYNAMIC FUNCTIONS OF HYDROXYLAMINE , 1952 .

[24]  Douglas B. Leviton,et al.  Temperature-dependent refractive index of silicon and germanium , 2006, SPIE Astronomical Telescopes + Instrumentation.

[25]  Bernhard Lendl,et al.  Tunable external cavity quantum cascade laser for the simultaneous determination of glucose and lactate in aqueous phase. , 2010, The Analyst.

[26]  J. M. Price,et al.  Vibrational spectroscopy of the ammoniated ammonium ions NH4+(NH3)n (n=1-10) , 1991 .

[27]  A. J. Moses.  REFRACTIVE INDEX OF OPTICAL MATERIALS IN THE INFRARED REGION , 1970 .

[28]  J. V. van Staden,et al.  Kinetic Study of the Decomposition of Nitrite to Nitrate in Acid Samples Using Raman Spectroscopy , 1996 .

[29]  J. D. Winefordner,et al.  Limit of detection. A closer look at the IUPAC definition , 1983 .

[30]  S. Radel,et al.  Ultrasound-Enhanced Attenuated Total Reflection Mid-infrared Spectroscopy In-Line Probe: Acquisition of Cell Spectra in a Bioreactor , 2015, Analytical chemistry.

[31]  C. W. van Neste,et al.  Standoff spectroscopy of surface adsorbed chemicals. , 2009, Analytical chemistry.

[32]  Yu-Chi Chang,et al.  Mid-infrared spectroscopy for gases and liquids based on quantum cascade technologies. , 2014, The Analyst.

[33]  S. Massie,et al.  HITRAN 2012 refractive indices , 2013 .

[34]  S. Asher,et al.  UV resonance raman spectroscopic detection of nitrate and nitrite in wastewater treatment processes. , 2002, Analytical chemistry.

[35]  G. Stedman,et al.  Kinetic and product studies on the decomposition of hydroxylamine in nitric acid , 1981 .