Trends in Analytical Chemistry 85 (2016) 260–272

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Trends in Analytical Chemistry

j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / t r a c

Challenging applications for multi-element analysis by laser-induced

breakdown spectroscopy in agriculture: A review
Jiyu Peng, Fei Liu *, Fei Zhou, Kunlin Song, Chu Zhang, Lanhan Ye, Yong He *
College of Biosystems Engineering and Food Science, Zhejiang University, 866 Yuhangtang Road, Hangzhou 310058, China

A R T I C L E I N F O A B S T R A C T

Keywords:
Toxic metal contamination and nutritious elements detection are two main issues in agriculture, as these
Agriculture
relate to the development of agriculture and human health. Among the investigated techniques, laser-
Agricultural products and food
Instruments
induced breakdown spectroscopy (LIBS) has the potential to become a fast and effective analytical tool
Laser-induced breakdown spectroscopy for the application in agriculture. Herein is a review of the recent developments and applications of LIBS
Nutrient elements in the field of agriculture. We discussed the LIBS instruments and quantitative analytical methods, and
Plants introduced signal enhancement methods for expanding the elements detection capability. For detailed
Precision agriculture aspects of applications, we reviewed the recent progress in soil, plants, agricultural products and food.
Soil To solve the severe “matrix effect” problem and to meet high demands in agriculture, we recommended
Toxic metals the development of robust and practical LIBS instruments, exploiting the chemometric methods and signal
enhancement methods for quantitative analysis.
© 2016 Elsevier B.V. All rights reserved.

Contents

1. Introduction ........................................................................................................................................................................................................................................................ 261

2. Instruments ......................................................................................................................................................................................................................................................... 261
2.1. Laboratory and fieldable LIBS system ........................................................................................................................................................................................... 261
2.2. Commercial LIBS system ................................................................................................................................................................................................................... 262
3. Relevant techniques for signal enhancement ......................................................................................................................................................................................... 263
3.1. Dual-pulse LIBS .................................................................................................................................................................................................................................... 263
3.2. Spatial-confinement LIBS ................................................................................................................................................................................................................. 263
3.3. Resonance-enhanced LIBS ................................................................................................................................................................................................................ 264
3.4. Nanoparticle-enhanced LIBS ........................................................................................................................................................................................................... 264
4. Methodological approaches for quantitative analysis .......................................................................................................................................................................... 264
4.1. Univariate analysis .............................................................................................................................................................................................................................. 265
4.2. Multivariate analysis .......................................................................................................................................................................................................................... 265
4.3. Calibration-free analysis ................................................................................................................................................................................................................... 265
5. Applications in agriculture ............................................................................................................................................................................................................................ 265
5.1. Soil ............................................................................................................................................................................................................................................................ 266
5.2. Plants ....................................................................................................................................................................................................................................................... 267
5.3. Agricultural products and food ...................................................................................................................................................................................................... 268

Abbreviations: AAS, atomic absorption spectroscopy; ANN, artificial neural network; CF, calibration-free; CRM, certified reference material; C-T, Czerny–Turner; DPLIBS,
dual-pulse LIBS; ICP-OES, inductively coupled plasma optical emission spectroscopy; ICP-MS, inductively coupled plasma atomic emission spectrometry; LA-ICP-MS, laser
ablation inductively coupled plasma mass spectrometry; LIBS, laser-induced breakdown spectroscopy; LIF, laser induced fluorescence; LODs, limits of detection; MLR, mul-
tiple linear regression; NELIBS, nanoparticle-enhanced LIBS; NIR, near infrared spectroscopy; PCR, principal component regression; PLEAF, plume laser-excited atomic fluorescence;
PLS, partial least squares; RELIBS, resonance-enhanced LIBS; RM, reference material; RMSEP, root mean square error of prediction; RSD, relative standard deviation; SVM,
support vector machine; XRF, X-ray fluorescence; UV, ultra-violet.
* Corresponding author. Tel.: +86 571 88982825; Fax: +86 571 88982143.
E-mail addresses: fliu@zju.edu.cn (F. Liu); yhe@zju.edu.cn (Y. He).

http://dx.doi.org/10.1016/j.trac.2016.08.015
0165-9936/© 2016 Elsevier B.V. All rights reserved.
 J. Peng et al. / Trends in Analytical Chemistry 85 (2016) 260–272 261

6. Summary and future prospect ..................................................................................................................................................................................................................... 269

Acknowledgements .......................................................................................................................................................................................................................................... 269
References ............................................................................................................................................................................................................................................................ 269

1. Introduction performance. Therefore, more reliable and rugged instruments with

more stable quantitative methods are required.
Toxic metals contamination and nutrients management are two The objectives of this paper are to present the applications and
main issues in agriculture. Toxic metals can bind to sulfer-, nitrogen- relevant developments of LIBS in agriculture, and to provide the sub-
and oxygen-containing functional groups in biological molecules, stantial prior knowledge of instruments, quantitative methods and
such as structural proteins, enzymes, and nucleic acids, etc., inter- relevant techniques with regard to agricultural application. The paper
fering with their normal function [1]. Chronic exposure to toxic mainly focuses on research over the years 2008–2015. After the in-
metals can cause severe health problems to humans, plants and troduction of LIBS instruments, the relevant methods for LIBS signal
animals if critical levels are exceeded. Of main concern are the met- enhancement were presented. Then, we focused on the method-
alloids arsenic (As), selenium (Se), cadmium (Cd), lead (Pb), ological approaches for quantitative analysis, which are the basic
chromium (Cr) and mercury (Hg). In contrast to toxic metals, nu- for multi-element analysis in agriculture. With aforementioned tech-
trients including macronutrients [nitrogen (N), phosphorus (P), nology, the applications of LIBS were introduced concerning toxic
potassium (K), etc.] and micronutrients [iron (Fe), boron (B), copper and nutrient elements detection in soil, plants, agricultural prod-
(Cu), etc.] are essential for plants growth. These nutrients play dif- ucts and food. Finally, we summarized the recent advances of LIBS
ferent roles in plant metabolism, and the concentration of which in agriculture and listed the potential applications and problems to
may remain changing in different life stages. What’s more, because be solved.
of management practices and weather conditions, spatial varia-
tion of nutrients in soil and plants exist in a single agricultural field. 2. Instruments
As an important part of precision agriculture, a sensor for fast ac-
quisition of toxic metals and nutrients information in agriculture This section attempts to introduce the features of different LIBS
is highly required [2]. systems, including laboratory and fieldable LIBS, and to discuss
Traditionally, analytical techniques such as inductively coupled strengths and weaknesses of each system. A typical LIBS system con-
plasma with mass spectrometry (ICP-MS), inductively coupled sists of laser, optics for guiding the laser pulse onto the sample and
plasma optical emission spectroscopy (ICP-OES), atomic absorp- transferring the emitted light into a light disperse system, spec-
tion spectrometry (AAS) have been used to detect toxic metals and trograph for producing the spectra and detecting system for recording
nutrients. However, these methods are limited by complex sample the spectra and converting it to electronic signal. To compare the
preparation steps and may not meet the demand of real-time mea- differences among systems, commonly used LIBS systems in pub-
surement in agriculture. lished literature are listed in Table 1. Since researchers tend to
Laser-induced breakdown spectroscopy (LIBS) is a form of laser- assemble LIBS systems by themselves for their specialized use, we
based atomic emission technique. By analyzing spectral signal tried to cover the most common LIBS systems used in agriculture.
constituted by the light emission from laser plasma, multi-element Every row in Table 1 represents a LIBS setup mentioned in accord-
analysis is achieved. Since all that is required to create the plasma ing references.
is the focused laser pulse, LIBS has lots of well-known advantages
[3], which include (1) no or little sample preparation; (2) in-situ 2.1. Laboratory and fieldable LIBS system
and stand-off detection capabilities; (3) multi-element analysis avail-
ability; (4) micro analysis capability when connected to microscope; Benefiting from highly controlled conditions and specific re-
(5) ability to analyze gases, liquids, and solids; (6) simplicity. Thanks search demands, the laboratory LIBS systems are usually more
to abovementioned features, in the past decades, LIBS has been precise, stable and expensive, and cover various aspects of LIBS re-
applied in geochemical, environmental, biological, archaeological search. As shown in Table 1, lots of investigations have been reported
analysis, and achieved great progress in detection performance and on fundamental and feasibilities. The main concern in instru-
understanding of the mechanisms involved. Several reviews have ments is the effect of laser types. Different laser types including
been published to cover the applications and progress of LIBS tech- Nd:YAG, Ti:Sapphire, ArF excimer and CO2 lasers have been applied
nique. Specific attention was focused on explosives residues [4], in practice. These lasers have different pulse characteristics (e.g., pulse
geochemical and environmental materials [5], industrial materi- duration, wavelength, pulse width), which provide critical effects
als [6,7], and biomedical application [8,9]. on the formation of plasma. Pulse lasers are preferred in most cases
However, the application of LIBS in the field of agriculture is more because it is stable, focused, have high energy output and easy to
challenging than in other areas. These challenges are mainly due use. In addition, the performance of femtosecond lasers was also
to complex interaction between samples and sensors, as well as investigated in laboratory LIBS systems. Benefiting from its ultra-
adverse working conditions. The physical and chemical character- short pulse duration, no thermodynamic change, lower continuum
istics of samples (e.g., crops) often vary considerably over time and emission and little matrix effect can be found in fs-LIBS [63]. Thus,
space. As for other detected specimens, such as soil and agricul- fs-LIBS system can be used for biological elemental imaging because
tural products, the variation among samples may also differ greatly. of its good space and depth resolved capability [48]. In addition,
These may cause severe ‘matrix effect’, and the experimental pa- Khumaeni and the co-workers use CO2 laser pulse to directly analyze
rameters which perform well in other areas may not be suitable in minerals and toxic metals contained in food powder [55,56]. Due
agriculture. Furthermore, the regular standard for toxic metals, as to the long wavelength and duration of CO2 laser, the plasma can
well as the recommended nutrients, is usually around the level of be created more easily, and the food powder can be analyzed di-
ppm, even ppb. The detection demand is higher than that in in- rectly without pressing. The limits of detection (LODs) of Cr and Cd
dustry. On the other hand, the working conditions in agriculture in the powdered food were as low as 9 and 50 mg/kg, respectively
(usually outside the laboratory) have detrimental effects on detection [56].
262 J. Peng et al. / Trends in Analytical Chemistry 85 (2016) 260–272

Stand-off LIBS system and portable LIBS system are both fieldable
LIBS instruments, which are usually applied for industrial applica-
tion, environmental diagnosis and hazardous work. A critical review
has been given by Fortes et al., and the recent developments of
fieldable LIBS were well introduced [64]. Different from laborato-
ry LIBS system, telescopes are usually involved in stand-off LIBS
system to focus the laser pulse and collect the signal. Chamcam’s
LIBS instrument onboard the Curiosity rover is a successful appli-
cable example for stand-off LIBS. A semi-quantitative or qualitative
analysis for soil in Mars has been successfully achieved [57,58].
However, when it comes to field application, the light transmitted
in the atmosphere is affected by various factors (e.g., the presence
of particles, wind, humidity, and the travel distance). As for porta-
ble LIBS system, a more compact LIBS system is needed. As the
development of laser (featured by more powerful and compact con-
figuration and efficient cooling system), analysis of soil with portable
LIBS becomes achievable [60,61]. LIBSCAN 25 + from Applied Pho-
tonics Ltd. and MobiLIBS III from IVEA are two kinds of commercial
LIBS portable systems (for more potable LIBS devices, please refer
to Ref [65].). In addition, since the laser used in LIBS system is usually
Class III or IV, eye safety should be considered [66].
Furthermore, there are some issues concerning both laborato-
ry and fieldable LIBS systems. As shown in Table 1, different
wavelengths of nanosecond lasers were applied to analyze the
samples in agriculture. In general, shorter wavelengths have higher
mass ablation rates and lower penetration depths, which is attrib-
uted to higher photon energy for bond breaking and ionization
[67]. It was also reported that ultra-violet (UV) pulse can help to
reduce the elemental fluctuation with lower relative standard de-
viation (RSD) compared with near infrared (NIR) pulse [67,68].
Besides, the use of NIR wavelength is limited in some cases when
the specimens have low absorbance in NIR region (e.g., glasses) or
when the specimens contain lots of fluid medium (e.g., fresh plant)
[69]. In this case, UV laser is more suitable for the analysis in ag-
riculture, especially for fresh plants or when mapping is required.
However, NIR laser is usually economic and powerful (the energy
reduces greatly when it changes to UV wavelength), and many mea-
surements (e.g., soil, dried plant samples) were still carried by NIR
pulse.
Choosing a suitable spectrograph-detector combination is im-
portant in self-assembled LIBS systems design. As shown in Table 1,
there are three dominating spectrograph-detector combinations:
(1) Czerny-Turner spectrograph and ICCD detector, (2) Echelle spec-
trograph and ICCD detector, (3) multi-channel Czerny-Turner
spectrograph and CCD detector. Czerny-Turner spectrograph usually
offers high resolution with a limited spectral coverage, while the
limitation can be overcome with Echelle spectrograph, which has
the advantages of broad spectral range, compactness and high res-
olution. However, Echelle spectrograph also has some drawbacks,
such as restricted working condition (e.g., temperature), low ac-
quisition rate and high cost. Thus, Echelle and Czerny-Turner
spectrographs combined ICCD detectors are often applied for fun-
damental research in laboratory. In addition, some multi-channel
compact spectrographs with relatively high resolution (usually
around 0.1 nm) and broad spectral range (usually range from 200 nm
to 1000 nm) have been marketed by a few manufacturers (e.g., Ocean
optics Inc., Avantes). As for detectors, ICCD detector is composed
of a microchannel plate and a CCD detector, and provides time-
gated detection, and of course is more expensive than CCD detector.
However, some arguments concerning the performance of these two
detectors should be further investigated in aspects of agricultural
applications [69]. In conclusion, multi-channel spectrograph mounted
with CCD is more suitable for fieldable LIBS systems (e.g., portable
LIBS system), which offers compact configuration and acceptable
resolution with broad spectral range. For fundamental research in
laboratory, Echelle spectrograph combined with ICCD is preferred.
Since the specimens in agriculture are usually inhomogeneous, si-
multaneous measurement in broad spectral range is required to avoid
shot-to-shot fluctuation. Besides, time-resolved analysis of spectra
is a critical point in fundamental research.
2.2. Commercial LIBS system
Many companies which used to concentrate on spectrograph now
start to produce commercial LIBS systems. In general, commercial
LIBS systems tend to be more stable, have a good user interface, and
even provide basic data preprocessing software. As stated in Table 2,
almost every type of LIBS system including laboratory, remote,
potable, micro and stand-off LIBS is covered in the category of these
companies.
In other words, the advantages of LIBS gave rise to the inter-
ests of companies, which accelerated the developments of LIBS
devices. In agriculture, some specific attention should be paid to

Table 1
Commercial LIBS systems and self-assembled LIBS systems mentioned in published literature

Type Laser Spectrograph Detector Sample Ref.

Laboratory Ti:Sapphire, 800 nm; C-T ICCD Plant [10]

Nd:YAG, 1064, 532, 266 nm
Nd:YAG, 266, 355 nm Echelle ICCD Vegetables, Milk [11–13]
Nd:YAG, 266, 532 nm C-T ICCD Plant [14–20]
Nd:YAG, 532 nm Multi-channel, C-T CCD Plant, Food, Soil [21–34]
Nd:YAG, 532 nm C-T ICCD Vegetable oils [35]
Nd:YAG, 532 nm Echelle ICCD Plant [36]
Nd:YAG, 1064 nm Echelle ICCD Plant, Soil [37–43]
Nd:YAG, 1064 nm Multi-channel, C-T CCD Orange [44–46]
Nd:YAG, 1064 nm C-T PMT Algae [47]
Nd:YAG, 355 nm; C-T ICCD Sunflower seedling [48]
Ti:Sapphire, 790 nm
Ti:Sapphire, 795 nm Echelle ICCD Plant [49,50]
Ti:Sapphire, 800 nm C-T ICCD Poplar tree leaves [51]
Nd:YAG, 532 nm; Echelle; C-T ICCD Wheat Grains, Potatoes [52–54]
ArF Excimer, 193 nm
CO2, 10.6 μm C-T ICCD Food powder [55,56]
Stand-off ChemCam (Nd:KGW, 1067 nm; Multi-channel; CCD) Soil [57,58]
Nd:YAG, 1064 nm C-T ICCD Soil [59]
Portable IVEA, MobiLIBS III (Nd:YAG, 266 nm; Echelle; ICCD) Soil [60,61]
Nd:YAG, 1064 nm C-T ICCD Soil, Leaf mustard [62]

Abbreviations: ICCD, intensified charge-coupled device; CCD, charge-coupled device; PMT, photomultiplier tube; C-T, Czerny-Turner.
 J. Peng et al. / Trends in Analytical Chemistry 85 (2016) 260–272
Table 2
the main commercial LIBS systems
Company Products Type
Oxford Instruments mPulse Potable
Ocean Optics Inc. LIBS2500plus Laboratory
Applied Spectra Inc. J200 Laboratory
Bertin Technologies LIBSorter 300 Laboratory
LIBSlab Laboratory
Avantes AvaSpec-ULS2048-LIBS Laboratory
IVEA MobiLIBS Laboratory
RemoteLIBS Remote
EasyLIBS Potable
MEEP Micro
Applied Photonics Ltd. ST-LIBS Stand-off
LIBSCAN 25 + Potable
Note: Manufacturers usually provide laboratory system with customize adaption.
developing commercial LIBS devices for agricultural use, such as soil
type sorting, agricultural products adulteration discrimination and
toxic metals detection.
3. Relevant techniques for signal enhancement
In order to further improve analytical performance comparing
to conventional methods (e.g., ICP-MS, XRF, AAS), signal enhance-
ment methods were introduced in this section. For most cases, the
LODs vary from 1 ppm to 100 ppm with conventional LIBS setup.
The sensitivity of LIBS may not meet the demand in agriculture es-
pecially for trace elements detection. Therefore, a great effort has
been devoted to increasing the sensitivity, mainly including dual-
pulse LIBS (DPLIBS), spatial-confinement LIBS, resonance-enhanced
LIBS (RELIBS), nanoparticle-enhanced LIBS (NELIBS) and so on. No
attempt was done to list all signal enhancement methods. We mainly
emphasize on the potential possibility of using signal enhance-
ment methods for agricultural application, and introduce the recent
development of these techniques.
3.1. Dual-pulse LIBS
The dual-pulse LIBS (DPLIBS) was first introduced in 1969 by
Piepmeier and Malmstadt when analyzing the plume of an alumi-
num alloy with single and multiple pulses [70], and then drew great
attention among the researchers since 2000. By impinging on the
samples with two or more pulses in several microseconds delay, the
intensity of emission lines can be enhanced up to 100 folds. Al-
though the mechanism of DPLIBS has not been fully understood,
many researchers tried to explain the actual working factors, and
a great progress has been made [71–73]. Three reviews concern-
ing the mechanism of DPLIBS have been published [74–76].
According to the irradiation mode and the DPLIBS configurations,
the DPLIBS can be classified into three modes (e.g., collinear, or-
thogonal pre-spark and orthogonal re-heating). The mechanisms of
these three DPLIBS configuration are quite different, and have been
well elaborated in Ref. [74].
Limited by the article, we mainly focused on the potential ap-
plication with these three DP-configurations in agriculture. Collinear
DPLIBS is more acceptable for practical application, since it’s easier
to align compared with orthogonal configuration. Therefore, it may
be more suitable for in-situ, stand-off detection of soil and plant
in real time. As for orthogonal configuration, it allows researchers
to obtain quite strong spectral signal with low energy, resulting in
high spatial resolution and little damage. This is particularly im-
portant for mapping the elemental distribution of the plant.
Krajcarova et al. investigated the copper transport and accumula-
tion in spruce stems and mapped the distribution of copper and
263
Main features
Total weight of 1.8 kg; Design for metal alloys sorting
Analysis speed of 25 piece/s; Design for scrap metals sorting
Total weight of 30 kg; A transportable system
Working distance of 3–10 meters with telescope optic and 10–20 meters with fiber optic
Total weight of 7 kg with laser energy less than 25 mJ; Option dual-pulse
Spatial resolution better than 8 μm; Energy range from 0.2 mJ to 1 mJ
Working distance more than 100 meters
Total weight of 14 kg; Laser energy up to 50 mJ
calcium on slices of stems with orthogonal re-heating DPLIBS [14].
With the combination of the information from LIBS and ICP-MS,
the quantitative result of elemental spatial distribution was suc-
cessfully obtained. However, further effort is needed to improve
the quantitative analytical ability of LIBS. Furthermore, the
spatial resolution in this article is 150 μm, and higher resolution
can be achieved by the use of picosecond or femtosecond lasers
[77,78].
3.2. Spatial-confinement LIBS
Attracted by the effect of cavity induced by laser [79,80], many
researchers tried to enhance the signal intensity of plasma emis-
sion using spatial confinement methods. By compressing the plasma
expansion with a small obstacle (e.g., plate, cylindrical wall) across
the front propagation, the enhancement factor is range from a few
to tens folds. Thanks to its advantages of simplicity, cost perfor-
mance and powerful enhancement capability, a great effort has been
devoted to improving the performance of spatial-confinement LIBS.
Different shape and materials of the cavity have been studied such
as hemispherical cavity [81], cylindrical chamber with polished brass
walls [82], metal disks with 2 mm hole [83], etc. In addition, the
effects of size and depth of cavity were also investigated [84].
However, these optimal factors are heavily dependent on the ma-
terials of sample and experimental parameters, and general rules
of optimal parameter remain unstudied.
Some pioneering work has been carried out on soil. Popov et al.
[82] studied the performance of spatial confinement for trace el-
ements determination in soil and found out that the LODs of As,
Hg, Pb, Mn, V and Ba decreased with the range of 2–5 times (see
Fig. 1). The authors also pointed out that the relative standard de-
viation (RSD) of emission lines was increased in 1.5 times with spatial
confinement, which was also mentioned in Ref. [85]. This phenom-
enon may be caused by the ignition of surrounding atmosphere
which was formed by previous pulse. However, this detrimental effect
can be eliminated by the optimization of experimental param-
eters (e.g., laser energy, lens to samples distance, delay time). As
proved by Hou and the co-workers, the RSD of C I 193.09 nm from
the plasma spectrum of coal was even reduced with optimized laser
energy and delay time [86]. In this case, study should be focused
on carefully selecting experimental parameters, as well as under-
standing the mechanism of spatial-confinement enhancement. A
main problem for this technique with regard to practical applica-
tion is the impurities of micro particles depositing on the surfaces
of chamber. Some attempts have been made by Popov et al., who
cleaned internal surfaces with ablation of pure aluminium before
every analytical measurement [82]. However, more efficient and
simple procedure should be involved in further study.
264 J. Peng et al. / Trends in Analytical Chemistry 85 (2016) 260–272

Fig. 1. Normalized emission spectra obtained in two spectral regions of 234–239 nm (a) and 430–439 nm (b) for soil No.2710 samples ablation. Profiles are obtained by
using chamber (1) and without it (2). Details of spectra obtained in spectral range for Hg I line observation in the soil sample are given in the inset of figure b.{based on
[82]}.

3.3. Resonance-enhanced LIBS

Resonance-enhanced LIBS (RELIBS), firstly proposed by Cheung

and co-workers in 2000 [87], has been proved as an efficient signal
enhancement approach with enhancement factors from a few to
hundreds folds. The configuration of RELIBS is similar to LIBS-LIF
(combination of LIBS and laser induced fluorescence), while the
wavelength of second pulse is tuned to the wavelength of reso-
nant excitation of the plasma. However, in LIBS-LIF, the second pulse
is applied to resonantly excite the interested analyte [88]. Unlike
LIBS-LIF, RELIBS is not restricted to the one-wavelength-one-
transition specificity, and can be applied for multi-element analysis.
Furthermore, RELIBS is particular suitable for trace elements de-
tection with minimal destruction, of which the ablation laser fluence
is often close to ablation threshold (usually several mJ). Because of
these unique advantages, RELIBS can be a potential tool for the de-
tection of trace elements in fresh plant.
Recently, a new signal enhancement approach named PLEAF
(plume laser-excited atomic fluorescence) has been proposed
[89–91]. As a variant of both LIBS-LIF and RELIBS, PLEAF can elim-
Fig. 2. Emission spectrum of Rhododendron obtusum with silver colloidal par-
inate the background emissions completely compared with RELIBS, ticles applied to the leaf. {based on [96]}.
and the LOD is as low as ppb. The excellent detecting capability of
PLEAF has been proved for analyzing lead in aqueous lead colloids
[89], aluminium alloys [92], ceramic and polymeric samples [93] the effect of NELIBS on different types of samples, and to under-
and laser printed ink [90]. The LODs can be as low as μg/g. However, stand the mechanism of laser-nanoparticle interaction.
the capability of PLEAF should be further investigated in agriculture. The use of metallic colloidal particle in LIBS has been reported
before in other literature. Ohta et al. and the co-workers investi-
3.4. Nanoparticle-enhanced LIBS gated the emission enhancement effect of metallic particles (which
they called as localized surface plasmon resonance) on LIBS when
In this section, we introduced a newly proposed signal intensi- analyzing plant nutrients [96]. As shown in Fig. 2, a great enhance-
ty enhancing method, which is called nanoparticle-enhanced laser- ment was observed in plasma spectrum with the help of silver
induced breakdown spectroscopy (NELIBS). NELIBS was firstly particle. Furthermore, both of the size, distribution and material of
proposed by De Giacomo et al. [94] in 2013 with the signal en- the metallic particles can affect the enhancement factor. It is nec-
hanced up to 1–2 orders of magnitude. The basic principle of NELIBS essary to clarify the dependence of emission enhancement on these
[95] is to increase the ablation efficiency by decreasing the mate- factors. Although the mechanism and influence factors of NELIBS
rial ablation threshold, which is mainly attributed to the presence haven’t been fully understood, this technique is still very promis-
of multiple ignition points and the instantaneous escape of elec- ing because of the preliminary results, simplicity and efficiency.
trons. With a drop of colloidal solution, the signal can be enhanced
up to several orders of magnitude. However, the enhancement factor 4. Methodological approaches for quantitative analysis
differs in various substrate types. Signal intensity increased to 1–2
orders of magnitude for metals, whereas no enhancement was ob- As referred to by Hahn and Omenetto [97], the quantitative anal-
served for insulators (including basalt mineral, soil sample, and Teflon ysis of LIBS is considered as its Achilles’ heel because of its complex
pellet) [94]. It may be attributed to high ablation threshold of these procedure of laser-sample and plasma-particle interactions. In other
samples. However, further investigation should be taken to verify words, quantification can be the main issue of LIBS which the
 J. Peng et al. / Trends in Analytical Chemistry 85 (2016) 260–272
researchers should continuously focus on. Some methodological ap-
proaches including univariate analysis, multivariate analysis and
calibration-free (CF) analysis have been proposed to improve the
reproducibility and accuracy and to eliminate the matrix effect.
4.1. Univariate analysis
Univariate analysis (also called calibration curve method) is a tra-
ditional calibration method, which establishes calibration curves by
relating the detection signal with the concentration of element to
be detected. To develop calibration curve and eliminate matrix effects,
matrix-matched certified reference material (CRM) and reference
material (RM) are often preferred. However, it’s challenging for ag-
ricultural application because of the lack of reference material and
severe matrix effects. Therefore, synthetic standards based on the
main sample matrix component or spiked sample material can be
another choice, and these matrix-matched calibration samples have
been widely used in laser ablation inductively coupled plasma mass
spectrometry (LA-ICP-MS) [98]. Silva Gomes and the co-workers [99]
introduced a novel approach to prepare synthetic standards for the
analysis of plant specimens. They prepared the blank sample with
vortex-assisted acid extraction of plant materials, and then mixed
it with original materials in a certain proportion. Good perfor-
mance in calibration curves was achieved for Mg (correlation
coefficient = 0.9998) and Si (correlation coefficient = 0.9999).
Besides, the main job of univariate analysis is to maximize the
signal-to-noise ratio and to eliminate the interference with irrel-
evant spectral lines through optimizing the experimental parameters
(fluence, lens-to-sample distance, delay and integration time, etc.).
These optimizations can be achieved by multivariate experimen-
tal designs (including orthogonal test design [100], response surface
methodology [101], chemometrics [36], etc.) and univariate exper-
imental designs. Univariate experimental design usually requires a
lot of experiments, and cannot clarify the relation between differ-
ent variables, which can be overcome in multivariate experimental
designs. Furthermore, internal calibration method is usually used
in univariate analysis. By calibrating spectral lines to known ele-
mental concentration, the shot-to-shot variations (caused by sample
heterogeneity, system error, etc.) can be corrected. However, this
method is hard to realize in practical application, especially in ag-
riculture, since it is difficult to find a constant element or to know
the concentration of element in advance.
4.2. Multivariate analysis
Unlike univariate analysis, multivariate analysis involves more
signal information, which can help to deal with matrix effect and
shot-to-shot fluctuation, and to predict even in the case of over-
lapped spectral lines. After gaining a great achievement in near
infrared spectroscopy analysis, the use of chemometrics in LIBS has
drawn a great attention in recent years. Common multivariate
methods for LIBS analysis were principal component regression (PCR),
partial least squares regression (PLSR), multivariate linear regres-
sion (MLR), support vector machine (SVM), artificial neural network
(ANN), etc. For more comprehensive understanding of multivari-
ate analysis in LIBS, readers are referred to read Chapter 7 by
Gottfried et al. in Cremers and Radziemski’s book [102]. As for prac-
tical application, calibration and classification are two main targets
of chemometrics. In most cases, LIBS combined with chemometrics
has been proved to be an efficient tool for classification, mainly due
to the ‘fingerprint’ feature of LIBS and ‘data mining’ capability of
chemometrics. Practical applications in agriculture comprise clas-
sification of soil types [103], contaminated food [104,105], plant
growing condition [106] and adulterated food [32], etc. On the other
hand, multivariate analysis has been applied as a calibration strat-
egy to predict elemental concentration. Detailed applications include
265
determination of toxic metals in soil, plant and agricultural prod-
ucts, which will be introduced in section 5.
Although the benefits of chemometric methods have been em-
phasized, there are some issues remaining unsolved. We listed some
advice below:
1 In order to develop a robust model, large and diverse training
samples or random effects are preferred [107]. This may greatly
extend practical application, and help to develop commercial LIBS
systems in agriculture.
2 Fully understand of the capabilities and limits of chemometrics,
as well as relating it to the mechanism of laser-sample and
plasma-particle interactions.
3 More attention should be paid to deal with the overfitting. Since
the spectra of LIBS contain thousands of wavelengths, overfitting
can be a big issue when simply tens or hundreds of samples are
involved. To find a suitable method of chemometrics which can
reduce redundant information (e.g., noise, irrelevant signal) while
retaining the most important variables is recommended.
4.3. Calibration-free analysis
Calibration-free method for LIBS analysis, which was first pro-
posed by Italian scientists Ciucci et al. to deal with matrix effect,
has now provided a novel way for quantitative analysis. The main
advantage of this approach is to free the use of matrix matched stan-
dard and it is suitable for ‘unknown’ samples detection. These
characteristics make CF method very promising in agriculture
because of the lack of matrix matched standard and the severe
matrix effect in agricultural samples. However, depending on its
modeling approach and assumptions (stoichiometric ablation, the
existence of local thermodynamic equilibrium and optically thin
plasma), studies should be concentrated on avoiding or compen-
sating for self-absorbed lines and accurate calculation of plasma
temperature. More detailed information including the premise of
application, limits and accuracy has been mentioned in a critical
review [108].
In agriculture, since its beginning, CF method has been applied
to determine elements in soil [109–111], sludge [112], fresh pota-
toes [113], food supplements [33], etc. Different from other
specimens (e.g., metallic alloy), the samples in agriculture often
consist of carbon (C), hydrogen (H), oxygen (O), nitrogen (N), which
are also the main elements in ambient air. Therefore, the analysis
of these elements in ambient air with CF method may cause large
error, and this can be avoided by analyzing in neutral environ-
ment. In general, CF method is more suitable for the major elements
detection, and the results of CF analysis for minor elements detec-
tion especially for trace elements may not meet the demand of
practical application. Herrera et al. [111] used CF method to analyze
Al, Ca, Fe, Mg, Si, Ti in soil. The best result was achieved for Si (ac-
curacy < 2%), which was the most abundant element in measured
soil. As for the remainder of the elements, the relative errors were
distributed in the range of 20–120%. In order to improve the de-
tection capability of CF method, some variants of conventional CF
method have been proposed. Representative studies include an op-
timized calibration procedure for elemental ratios determination
[114], and a one-point calibration approach for improving the true-
ness of traditional CF-LIBS [115].
5. Applications in agriculture
Thanks to the development of LIBS instruments, relevant ana-
lyzing techniques, methodological approaches, and the better
comprehensive understanding of mechanism, the application of LIBS
for complex matrix samples in agriculture become available. In this
section, we mainly focus on the recent progress of toxic and growing
266 J. Peng et al. / Trends in Analytical Chemistry 85 (2016) 260–272
Fig. 3. The application of LIBS in agriculture.
elements detection in soil, plants, agricultural products and food.
A schematic diagram is shown in Fig. 3. Although the applications
of LIBS in agriculture are not limited to aforementioned aspects, we
simply summarize the main research areas.
5.1. Soil
Soil is the basic element of traditional agriculture, which pro-
vides the nutrients (micronutrients and macronutrients) for the
growth of plants. However, caused by the atmospheric deposition
and contaminated irrigation waters, the toxic metals in soil would
be absorbed by plant and affect human health indirectly. Several
reviews regarding the application of LIBS for soil are available [5,116].
Table 3 summarizes the recent applications of LIBS for soil.
The analysis of toxic and heavy metal in soil gains continuous
attention for LIBS, with a great number of papers devoting to im-
proving the detection performance and investigating the potential
of in-situ measurement. Most researchers have drawn similar con-
clusion that LIBS is suitable for most heavy metals (Pb, Cu, Cd, Ni,
Ag, Mo, Zn, Hg, Cr) detection in soil, and the results are in accor-
dance with reference methods [e.g., atomic absorption spectroscopy
(AAS)] with the LODs around 1 ppm [120,123,124,127,129]. Several
methods have been proposed to improve the sensitivity of LIBS and
reduce the matrix effect. Choosing a suitable data analysis method
can help to solve this problem. Kim et al. proposed that Kriging in-
terpolation method instead of calibration for Zn detection in soil
could reduce matrix effect and improve the results with determi-
nation coefficient increasing from 0.94 to 0.99 [123]. Furthermore,
multivariate methods (e.g., PLSR, ANN) have been proved helpful
comparing with univariate analysis [61,130]. Although the ben-
efits of multivariate methods are well known, the application should
be cautious before fully understanding the capabilities and limita-
tions of these methods as was recommended by Hahn et al [131].
LIBS has also been used to detect nutrients in soil, including Ca,
Mg, Zn, Ba, N, P, K, C and other trace elements. Some trace ele-
ments (such as Zn, Ca, Ni) are considered as toxic elements if the
concentration exceeds the demand of plant, and the analytical result
has been aforementioned. Therefore, we mainly focus on the anal-
ysis of total carbon and nitrogen in soil. A great effort has been
devoted to detecting the concentration of total carbon in soil. Emis-
sion lines of 247.86 nm and 193.03 nm are the feature lines of C,
which are commonly used in the quantitative determination of
carbon content. Nguyen et al. compared the performance of these
two lines for detecting carbon content in soil, both lines can provide
a good linear calibration curve [122]. However, the emission line
at 247.86 nm had an interference with Fe lines at 247.86 nm and
247.95 nm. The detection of N content in soil is challenging due to
the high N content in atmosphere. Dong et al. investigated the re-
lationship between laser energy and time evolution spectral
characteristics, and good linear relationship was found between N
content and signal intensity at wavelength of 744.23 nm and
746.83 nm in argon atmosphere [128].
As the improvement of its performance, portable LIBS system
attracts more and more attention with regard to the application in
agriculture. Cunat et al. used a portable LIBS analyzer to analysis
lead in road sediments in real time, and the LOD was 190 μg/g [118].
Rakovský et al. presented a test report concerning home-made por-
table LIBS on geological samples [132]. The total weight of this system
 J. Peng et al. / Trends in Analytical Chemistry 85 (2016) 260–272 267

Table 3
A summary of the application of LIBS for soil

Samples Analytes LOD (ppm) Remarks Ref.

Soil Cd 1.3 Univariate [43]

Soil Hg 8 Stand-off, Univariate [59]
Soil Pb Portable, ANN [60,61]
Slurry Al, Ca, Fe, Ni, Si Univariate, MLR, PLS [117]
Road sediments Pb 190 Portable, Univariate, [118]
Soil Cu, Zn, Ca 4.785, 6, 4.35 Univariate [119]
Soil Pb, Cu, Fe, Ni 3.96, 0.33, 178.2, 2.11 Univariate [120]
Soil Ca, K, P, Mg, Fe, S, Ni, Ba 12, 9, 7, 9, 7, 10, 8, 12 Univariate [121]
Soil C Univariate [122]
Soil Pb 48 Univariate, CF [109]
Soil Zn Univariate, Kriging interpolation method [123]
Soil, ore Ag, Mo, Cu, P 0.3, 0.3, 0.6, 8 Univariate [124]
Soil Cr, Cu, Pb, V, Zn 17, 61, 20, 29, 55 Univariate [125]
Soil Cu Univariate, Microwave-assisted [126]
Soil Hg 483 Univariate [127]
Soil N Univariate [128]

Abbreviations: CF, calibration free; ANN, artificial neural network; MLR, multiple linear regression; PLS, partial least squares.

was as light as 5 kg, with resolution of 0.4 nm and energy up to 40 enhancement methods can help to improve the LODs. Further-
mJ. The depth profile in geological samples was qualitatively de- more, the growing elements detection is also influenced by the
termined, and the performance is comparable to a portable X-ray matrix effect, which is rather severe in plant materials. Arantes de
Fluorescence (XRF). Haddad et al. dedicated to in-situ analysis of Carvalho et al. [10,136] proved that multivariate analysis as well as
lead in soil sample with portable LIBS – MobiLIBS III from IVEA SAS fs-LIBS was an effective way to reduce the matrix effect and to
[60]. A serial artificial neural networks were applied to establish improve the performance. Better accuracy and less uncertainty for
quantitative models according to the matrix feature of samples, re- nutrients in plants were found when using fs-LIBS, which was cred-
sulting the relative error of prediction close to 20%. ited to its special pulse feature (ultrashort laser pulse). As for ns-
LIBS, multivariate analysis can significantly improve the accuracy,
5.2. Plants with root mean square error of prediction (RMSEP) two times lower
than univariate analysis. In addition, instrumental parameters (e.g.,
LIBS can also be used as a powerful analytical tool for the anal- laser focusing, fluence, wavelength) and sample preparation are also
ysis of growing elements and toxic metals in plant and tracing the important to the growing elements detection [39]. Smaller parti-
transport of the elements in plant. Kaiser’s group and Krug’s group cle size can help to enhance the emission signal intensity and to
are two main groups in this field, which come from Czech Repub- improve the measurement precision. It’s recommended by Arantes
lic and Brazil, respectively. Kaiser mainly focuses on the analysis of de Carvalho et al. [37] that samples particle size smaller than 100 μm
fresh plant samples with no preparation, while Krug is devoted to is decisive for plant pellets analysis. However, these kinds of re-
improving the performance of LIBS for laboratory use with the press searches may be applicable under special conditions, while the
of dried samples. Two interesting reviews [133,134] concerning the mechanism is in need of further study, and a universal rule remains
application of LIBS for plant and biological samples have recently unstudied.
published. Table 4 lists the main issues in recently published papers. Toxic metals detection in plant is also very important, which is
Growing elements detection is the main purpose of the appli- concerning the growing status of the plant and early protection. The
cation of LIBS in plant, and the growing elements can be divided analysis of toxic metals including Cr (VI) [21,23], Cu [14,17,19,47],
into micro-nutrients (B, Cu, Fe, Zn, etc.) and macro-nutrients (N, P, Pb [16,17,20,62], Ag [18,19] has been investigated. There are two
K, Mg, Si, etc.). Since the micro-nutrients in plant are usually in the main purposes of the application of LIBS for plants. One purpose
range of several ppm to tens of ppm, it is a little beyond the tra- is to monitor the metals accumulation in plant, and try to indicate
ditional LIBS detection limitation. As mentioned in section 4, LIBS the pollution of environment or alleviate the metal toxicity with
physical or chemistry methods. A portable LIBS device was suc-
cessfully used for the analysis of Pb in contaminated soils and in
Table 4 leaf mustard [62]. Leaf mustard played a role in restoring the pol-
An overview of main issues discussed with the application of LIBS in plant luted soil called as phytoremediation. Good correlation was found
Samples Main issues of the application of LIBS Ref. between LIBS and atomic absorption spectroscopy, with determi-
Spruce Monitor the transport of copper in [14] nation coefficient better than 0.7 for soil and determination
stems coefficient of 0.9738 for plant samples. LIBS has also been used to
Sunflower Map the distribution of elements [16–20,48] investigate toxic metals in algae [47,139], which can be applied as
Wheat seedling Monitor the transport of Cr in root, [23] an indicator of environmental pollution. Thanks to its space-
stem and leaves
resolved ability and minimal destructive feature, another purpose
Sugar cane Nutrient elements detection [38,41]
Bean Micronutrients detection [42] of LIBS is to trace the transport of elements in plant. Kumar et al.
Poplar tree Nutrient elements detection [51] used LIBS to monitor the Cr uptaking in different parts (shoot, stem,
Leaf mustard Toxic elements detection [62] leaf) of wheat seedling with chromium stress [23]. The Cr content
Crops Nutrient elements detection [10,135,136]
in different parts of wheat seedling was compared based on signal
Folium lycii Micronutrients detection [137]
Cotton Toxic and nutrient elements [138]
intensities at 357.8 nm, 359.3 nm and 360.5 nm. For further study,
detection the quantitative results compared with reference methods should
Algal Toxic element detection [47,139] be conducted for different parts of plants, as well as tracing the trans-
Capsicum annuum L. Map the distribution of lead and [140] port of metals in plant with several time periods. In addition, LIBS
nutrient elements
was also used to study the metal accumulation in plant leaf [16–20]
268 J. Peng et al. / Trends in Analytical Chemistry 85 (2016) 260–272

Fig. 4. The 3D map of the accumulation of Cu in Spruce Stems after cultivation in 50 mM CuCl2 for 4 hours. The X position of the top pane represents the distance from the
bottom stem. {based on [14]}.

and cross sections of plant stem [14], which was usually revealed
by mapping of metal accumulation in these plant tissues. Krajcarova
et al. [14] revealed that a quantitative and spatial distribution of
Cu in stem was successfully obtained by combining with ICP-MS,
LIBS and fluorescence (Fig. 4). Mapping of Mg, Pb, Cu accumula-
tion in sunflower’s leaf [17] was successfully achieved by Kaiser et al.
with LIBS and LA-ICP-MS. Although the accuracy of the spatial dis-
tribution of metal in plant leaf is difficult to validate, good correlation
for overall concentration was found among AAS, LIBS and LA-ICP-MS.
5.3. Agricultural products and food
In addition, LIBS has also served as a powerful analytical tool for
agricultural products and food. Most investigations are concen-
trated on the nutrients diagnosis and safety control.
Some efforts have been devoted to detecting the nutrient ele-
ments in agricultural products and food, including milk powder
[12,13,141], rice [104] and food supplements [33]. Matrix effect
is a big issue that affects the analytical performance. Through
 J. Peng et al. / Trends in Analytical Chemistry 85 (2016) 260–272
calculating the plasma parameters, matrix effect was obviously ob-
served in milk powder [12]. However, acceptable results for Mg, K,
Ca were achieved with CF-LIBS analysis. The performance of CF-
LIBS was also proved by Agrawal et al. for determining the nutrient
elements in food supplements [33].
LIBS has also been successfully used for the detection of glyce-
mic elements in Indian medicinal plants. High concentration of
glycemic elements (e.g. Mg, Ca, Fe) was found to be associated with
antidiabetic potential in medicinal plants. A review concerning the
application for glycemic elements detection has been recently pub-
lished [142].
Another application of LIBS is in food safety control, including
the detection for pesticide residue [104,105,143], biological con-
tamination [144], toxic metals [45,145], and other elements which
are important for food quality control (e.g., Ca, Na) [146,147]. The
application of LIBS for pesticide residue detection was firstly pro-
posed by Kim et al. in 2012, and now gains more and more attention
for its promising potential application. Previous studies mainly
focused on qualitative analysis and classification according the
amount of pesticide, and multivariate methods were applied to dis-
criminate the contaminated food. In addition, the detection of Na
and Ca in food has been studied by Bilge et al. and Ferreira et al.,
respectively [146,147]. The signal intensity at 589 nm was used to
determine the concentration of Na, and the LOD was of 69 ppm. As
for Ca detection, the LOD was of 9.5 ppm with emission line of
393.3 nm.
6. Summary and future prospect
In this study, we present an overview concerning the recent pro-
gress of LIBS, including the advances in instruments, signal
enhancement techniques, data processing methods and the appli-
cations in agriculture. As a versatile analytical tool, LIBS has shown
promising potential in fast detection of toxic and nutrient ele-
ments in soil, plants, agricultural products and food. The
developments of portable and stand-off LIBS systems provide a bridge
to bring LIBS into practical application. However, the performance
of these fieldable systems needs to be improved to become more
compact and powerful. The low sensitivity and severe matrix effects
are considered as critical problems for LIBS compared with other
conventional analytical techniques, especially in the field of agri-
culture. In this study, we summarized several commonly used signal
enhancement methods (DPLIBS, spatial-confinement LIBS, RELIBS
and NELIBS) which can significantly improve the signal while with
simple operation. Univariate analysis with matrix matching stan-
dard, multivariable analysis and CF-LIBS are introduced to mitigate
the severe matrix effect. With aforementioned technologies and
methods, the applications of LIBS can cover the whole procedure
of modern agricultural industry, and provide a fast, in-situ and real-
time approach to monitor toxic and nutrient elements in soil, plants
and agricultural products.
In regard to the further improvements and practical applica-
tions of LIBS in agriculture, some advice was proposed as follows:
(1) To improve the performance of calibration and classification, we
urge to use chemometric methods to make full use of LIBS signal
information. Since the capability of chemometrics has been proved
in spectroscopy analysis such as near infrared spectroscopy, we
believe that it will also play an important role in LIBS. (2) The data
fusion technology by integrating LIBS with other analytical tech-
niques and tools. Since the situation in agriculture is complex, the
detecting results from a single detector may not meet the demand.
The detection and analytical performance can be more precise with
the aid of raman spectroscopy, near infrared spectroscopy and other
sensing technology. (3) The development of fieldable LIBS sensors
or instruments. Although several commercial fieldable LIBS systems
have been proposed, they were designed to be suitable for universal
269
application. Therefore, LIBS systems specifically designed for the very
target in agriculture with more compact configuration and better
performance are preferred. (4) The mechanism of laser-sample in-
teraction for agricultural samples should be further studied for a
better analysis and practical application. Although improved per-
formance has been achieved with the methods of signal
enhancement and data processing, the mechanisms beyond these
methods remain unclear. Only if the mechanisms are revealed will
it be the true maturity of LIBS analytical technique. In all, with the
development of instruments and analytical approaches, LIBS will
play a more and more important role in future agriculture.
Acknowledgements
This study was supported by 863 National High-Tech Research
and Development Plan (2013AA102405), Natural Science Founda-
tion of China (31671579), Zhejiang Provincial Natural Science
Foundation (LY15C130003) and Zhejiang Provincial Public Welfare
Technology Research Projects (2014C32103).
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