2.
Materials and Methods
2.1. Sample Preparation
The biomass pellets were provided by different bioenergy companies, and they are
representative of the most commonly used varieties found on the biofuel market in China. They mainly
included rice husks, pine wood, rubber wood, and red wood. The distance between the sample
surface and the lens for laser focusing will affect the intensity of the spectral signals. Besides, uneven
samples will also cause interference in the spectral signals. Thus, a uniform and regularly shaped
sample is of great importance. In order to obtain accurate and reliable experimental data, the biomass
pellets were first milled and then compressed into a circle tablet using a pressing machine (FY-24,
SCJS, Tianjin, China) for 30 s and under a pressure of 10 MPa. The resulting side length and
thickness were 10 mm and 2 mm, respectively. The tablets were then dried at 60 °C for 6 h in an
oven. A total of 128 tablets samples were prepared. They were divided into calibration and prediction
sets in a ratio of 3:1 by joint x–y distances (SPXY) methods [25]. Thus, 96 samples and 32 samples
were obtained for calibration and prediction, respectively. Besides, the four kinds of biomass pellets
were distributed in both calibration and prediction sets to make the analyses more reliable.
2.2. Determination of Quality Indexes
In this study, industrial analysis components were also determined according to the traditional
methods. Ash content (Ash) and volatile matter (VM) were measured according to ASTM D1102-84
and ASTM E872-82 [26]. The gross calorific value (CV) (MJ·kg −1) was determined in accordance with
the China national standards GB/T30727-2014 using an oxygen bomb calorimeter (5E-AC, Chansha
Kaiyuan Instrument Co., Ltd., Changsha, China). Fixed carbon (FC) was calculated after determining
the Ash and VM content according to the following equation:
FC% = 100% − Ash% − VM%
(1)
The values of Ash, VM, and FC were dry basis.
2.3. Experimental Apparatus and LIBS Measurement
A self-built LIBS system (Figure 1) was used in this work. It mainly comprised of a Q-switched
Nd:YAG pulsed laser (Vlite-200, Beamtech Optronics, Beijing, China) with the maximal energy of 200
mJ @532 nm for generating laser pulse to ablate samples, an Echelle spectrograph (ME5000, Andor
Technology, Belfast, UK) equipped with an (intensified charge coupled device) ICCD camera (iStar
DH340T, Andor Technology, Belfast, UK) for collecting spectral signals, and a digital delay pulse
generator (DG645, Stanford Research Systems, San Jose, CA, USA) for controlling the delay time
between the laser and the ICCD camera. In addition, lens, mirrors and X-Y-Z stage were used for
laser transmission and sample placement. A Hg: Ar lamp (HG-1, Ocean Optics, Winter Park, FL,
USA) and a Deuterium Halogen light source (DH-2000-BAL-CAL, Ocean Optics, Winter Park, FL,
USA) were used for the calibration of the wavelength and intensity. Experimental parameters were
optimized by the response surface methodology (RSM) to obtain a best signal to noise ratio (SNR)
and relative standard deviation (RSD). Based on the optimization, the energy of laser pulse was 60
mJ with 1 Hz repetition rate, the delay time was 1.5 μs, and the gate width of ICCD was 10 μs.
Besides, the distance between the lens and sample surface was optimized to 98 mm when a good
spectral signal was obtained.
Figure 1. Schematic diagram of the LIBS system.
LIBS measurements were conducted after setting the parameters. First, the laser beam was
adjusted to be focused 2 mm below the sample surface to avoid any interference caused by an
uneven sample surface. The signal detector was then adjusted to ensure that the spectral signal could
be collected. After that, a total of 80 spectra of each sample were obtained by controlling the moving
path of the X-Y-Z stage. 16 position of each tablet sample were ablated with five successive
accumulations. At last, the average of 80 spectra was used to be the spectrum of the sample.
2.4. Data Pretreatment and Analyze
In order to eliminate the impact caused by experimental instruments and radiation generated by
plasma formation, and further to improve the precision and repeatability of LIBS detection, several
pre-processing methods were introduced, including baseline correction, wavelet transform,
normalization, and outlier discarding. Baseline correction could eliminate background signals, and
wavelet transform could reduce any noise. Normalization could effectively reduce the fluctuation of
each shot and improve signal stability. Detailed information of these methods were mentioned in our
previous work [27]. Outlier discarding could improve the reliability and accuracy of the data. A self-
developed outlier removing algorithm based on median absolute deviation (MAD) was used in this
work. In order to meet our particular demands, a relatively stable spectral line of CN 388.29 nm was
applied to identify outliers. Once the difference between the intensity and median of CN 388.29 nm
exceeded 2.5 times the MAD, the spectrum would be considered as an outlier and be removed.
Outliers removing was repeated until there were no outliers or a maximum of 25% of the original
spectra were removed.
2.5. Chemometrics for Data Analyze
Several chemometric methods were conducted after data pretreatment, including partial least
squares regression (PLSR), least squares-support vector machines (LS-SVM), extreme learning
machines (ELM). The specific procedure of LIBS data analysis is shown in Figure 2.
