Wavelength dependence of laser induced breakdown spectroscopy (LIBS) on questioned document investigation.

The fast and nearly non-destructive criteria of laser induced breakdown spectroscopy (LIBS) technique has been exploited for forensic purposes, specifically, document investigation. The dependence of the optical emission spectra of different black gel ink samples on the excitation laser wavelength, namely the visible wavelength at λ=532 nm and the IR wavelength at λ=1064 nm, was studied. The inks of thirty black gel-ink pens comprising ten brands were analyzed to determine the variation of the chemical composition of ink and to discriminate among them with minimum mass removal and minimum damage to the document's paper. Under the adopted experimental conditions, the ability of the visible LIBS to differentiate among the different ink samples was successful compared to IR LIBS at the same laser pulse energy (~25 mJ/pulse, laser fluence is ~1400J·cm(-2) for visible laser and ~1100J·cm(-2) for IR laser) which could be attributed to the IR absorption effects by the black ink. However, the visible LIBS produces deeper crater with respect to that produced by IR LIBS. Applying IR LIBS with higher pulse energy of ~87mJ (laser fluence is ~4100J·cm(-2)), identification and differentiation of the adopted samples was performed with producing a larger-diameter but superficial crater. The plasma parameters are discussed at the adopted experimental conditions. The results support the potential of LIBS technique using both the visible and IR lasers to be commercially developed for forensic document examination.

[1]  Janina Zieba-Palus,et al.  Application of the micro-FTIR spectroscopy, Raman spectroscopy and XRF method examination of inks. , 2006, Forensic science international.

[2]  H. Griem Principles of Plasma Spectroscopy , 1997 .

[3]  W. Mazzella,et al.  A study to investigate the evidential value of blue gel pen inks. , 2003, Journal of forensic sciences.

[4]  Differentiation of black gel inks using optical and chemical techniques. , 2004, Journal of forensic sciences.

[5]  N. P. Evmiridis,et al.  Multivariate chemometrics for the forensic discrimination of blue ball-point pen inks based on their Vis spectra. , 2003, Forensic science international.

[6]  M. Mulholland,et al.  Forensic classification of ballpoint pen inks using high performance liquid chromatography and infrared spectroscopy with principal components analysis and linear discriminant analysis , 2006 .

[7]  M. Xie,et al.  Classification and dating of black gel pen ink by ion-pairing high-performance liquid chromatography. , 2006, Journal of chromatography. A.

[8]  José R. Almirall,et al.  Characterization of toners and inkjets by laser ablation spectrochemical methods and Scanning Electron Microscopy-Energy Dispersive X-ray Spectroscopy , 2014 .

[9]  Sargur N. Srihari,et al.  Role of automation in the examination of handwritten items , 2014, Pattern Recognit..

[10]  Israel Schechter,et al.  Use of LIBS for rapid characterization of parchment , 2006, Analytical and bioanalytical chemistry.

[11]  Nicoló Omenetto,et al.  Laser-Induced Breakdown Spectroscopy (LIBS), Part II: Review of Instrumental and Methodological Approaches to Material Analysis and Applications to Different Fields , 2012, Applied spectroscopy.

[12]  H. Furth,et al.  Plasma diagnostic techniques , 1965 .

[13]  Differentiation and dating of gel pen ink entries on paper by laser desorption ionization- and quadruple-time of flight mass spectrometry , 2012 .

[14]  D. Djozan,et al.  Forensic discrimination of blue ballpoint pen inks based on thin layer chromatography and image analysis. , 2008, Forensic science international.

[15]  H. Ahmed,et al.  From Ptolemaic to modern inked linen via Laser Induced Breakdown Spectroscopy (LIBS) , 2013 .

[16]  L. Yao,et al.  Dating the writing age of black roller and gel inks by gas chromatography and UV-vis spectrophotometer. , 2006, Forensic science international.

[17]  Leon J. Radziemski,et al.  Handbook of Laser-Induced Breakdown Spectroscopy , 2006 .

[18]  José R. Almirall,et al.  Micro-spectrochemical analysis of document paper and gel inks by laser ablation inductively coupled plasma mass spectrometry and laser induced breakdown spectroscopy , 2010 .

[19]  C. Ng,et al.  Spectrochemical Analysis of Liquids Using Laser-Induced Plasma Emissions: Effects of Laser Wavelength , 1997 .

[20]  Y. Iida Effects of atmosphere on laser vaporization and excitation processes of solid samples , 1990 .

[21]  Vincenzo Palleschi,et al.  Quantitative micro-analysis by laser-induced breakdown spectroscopy: a review of the experimental approaches☆ , 2002 .

[22]  Maria Fernanda Pimentel,et al.  Classification of blue pen ink using infrared spectroscopy and linear discriminant analysis , 2013 .

[23]  C. Adam,et al.  In situ luminescence spectroscopy with multivariate analysis for the discrimination of black ballpoint pen ink-lines on paper. , 2008, Forensic science international.

[24]  Ulrich Panne,et al.  Multivariate classification of pigments and inks using combined Raman spectroscopy and LIBS , 2012, Analytical and Bioanalytical Chemistry.

[25]  W. F. Ho,et al.  Spectrochemical Analysis of Liquids Using Laser-Induced Plasma Emissions: Effects of Laser Wavelength on Plasma Properties , 1997 .

[26]  Jagdish P. Singh,et al.  Laser-induced breakdown spectroscopy (LIBS) , 2011, Analytical and bioanalytical chemistry.

[27]  Systematic analysis of bulk blue ballpoint pen ink by FTIR spectrometry. , 2001, Journal of forensic sciences.

[28]  Mohamed Oujja,et al.  Identification of inks and structural characterization of contemporary artistic prints by laser-induced breakdown spectroscopy ☆ , 2005 .

[29]  Janina Zięba-Palus,et al.  PRAXIS—combined μ-Raman and μ-XRF spectrometers in the examination of forensic samples , 2008 .

[30]  Paweł Kościelniak,et al.  Application of laser induced breakdown spectroscopy to examination of writing inks for forensic purposes. , 2014, Science & justice : journal of the Forensic Science Society.

[31]  Joseph Almog,et al.  Minimum requirements for application of ink dating methods based on solvent analysis in casework. , 2011, Forensic science international.

[32]  V. Zholobenko,et al.  Classification and individualization of black ballpoint pen inks using principal component analysis of UV-vis absorption spectra. , 2008, Forensic science international.

[33]  V. Causin,et al.  The Discrimination Potential of Ultraviolet‐Visible Spectrophotometry, Thin Layer Chromatography, and Fourier Transform Infrared Spectroscopy for the Forensic Analysis of Black and Blue Ballpoint Inks , 2008, Journal of forensic sciences.

[34]  A comparative analysis of dichroic filter viewing, reflected infrared and infrared luminescence applied to ink differentiation problems. , 1970 .

[35]  André Braz,et al.  Raman spectroscopy for forensic analysis of inks in questioned documents. , 2013, Forensic science international.

[36]  Kristalia Melessanaki,et al.  Laser induced breakdown spectroscopy and hyper-spectral imaging analysis of pigments on an illuminated manuscript , 2001 .