Computers and Electronics in Agriculture 177 (2020) 105628

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Computers and Electronics in Agriculture

journal homepage: www.elsevier.com/locate/compag

Terahertz spectroscopy and imaging: A review on agricultural applications T

Leili Afsah-Hejri, Elnaz Akbari, Arash Toudeshki, Taymaz Homayouni, Azar Alizadeh,
Reza Ehsani
⁎

Mechanical Engineering Department, School of Engineering, University of California Merced, 5200 N. Lake Rd., Merced, CA 95343, United States

ARTICLE INFO ABSTRACT

Keywords: Terahertz (THz) waves are non-ionizing radiations with unique properties of both microwave and infrared. THz
Terahertz imaging and spectroscopy have been widely used for non-destructive testing, security screening, medical ima­
Spectroscopy ging, and quality control both in the agricultural and food industries. This review briefly describes the principles
Imaging of how THz is generated, discusses its current agricultural applications and highlights the research gaps. THz
Drought stress monitoring
spectroscopy has primarily been used for measuring the water content of plant leaves. Later, it was used to detect
Pesticides detection
Soil inspection
dead and live insects and pests in agricultural products. A combination of THz spectroscopy with chemometric
Transgenic seed discrimination methods, machine learning, and search algorithms helped scientists to construct classification models for dis­
crimination of transgenic seeds, pesticides, harmful compounds, and poisonous plants. THz spectroscopy has also
been used for soil inspection and detection of heavy metals and buried objects. In recent years, there have been
significant technological improvements in developing THz sources and detectors, which enabled researchers to
perform ultra-fast scanning and obtain high-resolution images. Using these new THz technologies, researchers
can differentiate between fresh and old leaves, monitor the water status of plants, and estimate the crop yield.
Although THz has proved to be a useful tool for non-destructive quality control of agricultural products and soil
inspection, the technique has some limitations such as a low limit of detection (LOD) for pesticides, low spatial
resolution, and limited penetration. It can also be influenced by the physical properties of samples such as
particle size, and surface roughness. On the sensor side, more research is needed to improve the performance of
THz systems, reduce THz sensor costs and ruggedness of the system for applications in agriculture. Also, more
research is required to explore new potential applications of this technology in agriculture.

1. Introduction
Terahertz region, a part of the electromagnetic spectrum with a
frequency range between 0.1 and 10 terahertz (THz), refers to a very
small gap between the infrared (IR) and microwave (MW) regions of the
electromagnetic spectrum (Fig. 1). THz waves share some unique
properties with both MW and IR (Yin et al., 2016) and THz spectro­
scopy reflects the interface of MW and IR techniques (McIntosh et al.,
2012). THz spectroscopy is a useful tool to study the vibrational ac­
tivities of molecules, such as torsional and rotational modes (Ueno &
Ajito, 2008). Many molecules demonstrate a unique absorption or
scattering spectrum in the THz range, and this means that THz radiation
can be used as an excellent non-ionizing alternative to the use of X-rays
in generating high-resolution images from inner parts of an object.
(Blanchard et al., 2007). Materials can be a) transparent to THz waves,
such as nonpolar, nonmetallic, and dry materials, b) THz absorbents,
such as polar molecules (Mathanker et al., 2013) like water which is a
strong THz absorber (Jin et al., 2017) or c) THz reflectors such as
metals (Naftaly & Dudley, 2011). Laser, optical, or electronic sources
can be used for the generation of THz waves. Measurements made from
THz spectroscopy can be performed in either time-domain measure­
ments (time-domain spectroscopy (TDS)) or frequency-domain mea­
surements that use continuous-wave (CW) THz sources and detectors.
Time-domain measurements provide phase information of the signal in
a very short time, usually < 100 fs (Hangyo et al., 2005). THz detection
techniques are based on thermal absorption or free-space electro-optic
sampling. Recent improvements in the THz sources and detectors en­
abled researchers to acquire high-resolution images in a very short time
(Ueno & Ajito, 2008). THz spectroscopy and imaging techniques have
been used for non-destructive testing (Rutz et al., 2006), communica­
tion (Akyildiz et al., 2014), security screening (Liu et al., 2007), med­
ical imaging (Dougherty et al., 2007), biomedical (Sharma et al., 2016),
pharmaceutical industries (Sibik & Zeitler, 2016), agricultural products
(Ogawa et al., 2006) and food inspection (Afsah-Hejri et al., 2019). This

⁎
Corresponding author at: Mechanical Engineering Department, School of Engineering, UC Merced, 5200 N Lake Rd., Merced, CA 95343, United States.
E-mail address: rehsani@ucmerced.edu (R. Ehsani).

https://doi.org/10.1016/j.compag.2020.105628
Received 14 September 2019; Received in revised form 5 July 2020; Accepted 6 July 2020
Available online 28 August 2020
0168-1699/ © 2020 Elsevier B.V. All rights reserved.
L. Afsah-Hejri, et al. Computers and Electronics in Agriculture 177 (2020) 105628

2005). Frequency-domain spectroscopy can be performed using fre­

Fig. 1. Location of THz region in the Electromagnetic spectrum.
review focuses on the applications of THz TDS and imaging to the field
of agriculture and the current technological limitations in these appli­
cations.
THz generation sources: THz radiation can be generated by a)
optical sources (Zhong et al., 2017a,b), b) quantum cascade laser
(Consolino et al., 2017; Lepeshov et al., 2017), or c) solid-state elec­
tronic devices (Vilkoe et al., 2018; Hesler et al., 2019). THz generation
methods, average power, range, type of output and detectors are clas­
sified in Table 1.
THz measurement techniques: Measurements in THz spectro­
scopy or imaging is performed in either frequency-domain measure­
ments or time-domain measurements.
Frequency-domain measurements: CW THz sources and detectors are
used for frequency-domain measurements. The experimental setup is
very simple for frequency-domain measurements. A sample is placed
between the source and detector and transmission of the THz wave
through the sample is directly sensed by the detector (Karpowicz et al.,
quency-tunable CW THz sources and detectors (Preu et al., 2011).
Time-domain measurements: THz time-domain spectroscopy (THz-
TDS) systems measure THz radiation in a time domain and get the
frequency domain information by performing a Fourier transform
spectroscopy (Nishizawa et al., 2005). Compared to other THz techni­
ques that directly measure frequency domain data, THz-TDS can also
acquire the phase information of the signal. A typical THz-TDS system
consists of a THz source, a detector, an optical delay line, and other
necessary optics (Hangyo et al., 2005). The most common method of
generating a pulsed THz wave is through the application of an ultrafast
laser beam to a photoconductive semiconductor with a biased voltage.
THz detection methods: One of the primary methods for THz de­
tection and characterization is based on the free-space electro-optic
sampling technique (Wu & Zhang, 1995). This falls under time-domain
THz detection techniques and offers an ultra-wideband spectrum. Sev­
eral materials have been used for electro-optic samplings, such as ZnTe
and BBO crystals (Cook & Hochstrasser, 2000; Wu et al., 1996).
Another type of THz detection method is based on thermal ab­
sorption. Helium cooled silicon, germanium, and InSb bolometers are
the most common systems based on thermal absorption. Although they
provide high sensitivity for THz detection, compared to the THz-TDS
detection method, bolometers lack the ability of frequency spectrum
detection (Salmon et al., 2018). An interferometer is often used to ex­
tract the spectral information for bolometer detection. Some polymer
and semiconductor materials such as Teflon and silicon have high THz
transmission. Therefore, THz optical components (e.g., lenses and
windows) are usually made from these transmissive THz materials.
Metal wire grids are commonly used as THz polarizers (Cho, 2018).
Thin metallic meshes are used as THz bandpass filters. Recently, me­
tamaterials (Rao et al., 2018) attracted a lot of attention because of
their unusual electromagnetic properties, which enable researchers to
manipulate electromagnetic waves in different ways (Al-Naib, 2018).
Recent advances in THz spectroscopy confirm that metamaterials have
an important role in the future THz optical components development. A

Table 1
THz generation methods. (See below-mentioned references for further information.)
Source Generation Average Usable Output Type Detection Reference
Power Range
Quantum cascade mW 2 10 THz CW or Pulsed (Williams,
laser 2007)
QCLs by self-mixing
Laser P-type germanium Few tens of a 1 4 THz CW (Hübers et al.,
laser mW up to 10 2005)
W
Silicon-based laser µW 0.5- 5 THz Pulsed (Hübers et al.,
2005),(Sharma
et al.,
2016),(Hu et
al., 2018)
Free electron laser Tens of watts 1.25 2.5 THz Pulsed (Billardon et
to 200 W al., 1983)

Photoconductive W 100 GHz and (Brown, 2008)

Optical switch mW 1.0 THz Photoconductive
Pulsed switch

Optical rectification µW 0.8 Thz Electro-optic (Meyer et al.,

sampling 2018)

Backward-wave mW 0.9- to 1.1- CW/Pulsed (Mineo &

oscillator THz Schottkey diode Paoloni, 2010)
Backward diode
Electronic Gunn diode 0.1-1 mW 1 THz CW HEMT transistor (Gallerano &
Bolometer(~4K) Biedron, 2004)
Golay cell
Pyroelectric
Resonant tunneling 60 µW 2.3 THz CW/Pulsed detector (Asada et al.,
diode 2008)
Direct multiplied 200-500 mW 0.1-0.3 THz Pulsed, CW (Siles et al.,
sources >0.5 mW 1.5 THz 2018)

2
L. Afsah-Hejri, et al.
Fig. 2. Schematic diagram of a typical experimental THz spectroscopy setup. (Absorbance and reflectance spectrum from Zhong et al., 2017b).
schematic diagram of a typical experimental THz spectroscopy setup is
presented in Fig. 2.
Data Processing: THz spectroscopy provides a large amount of
spectral data. The information about the structural, physical, and che­
mical properties of the sample should be extracted from these THz
spectra. A combination of THz spectroscopy with chemometric
methods, machine learning, and search algorithms helps scientists to
construct classification models for discrimination of transgenic seeds,
pesticides, harmful compounds, and poisonous plants. Chemometric
methods are mathematical and statistical methods used for processing
THz spectral data and implementation of these methods will reduce a
large number of variables and facilitate the data analyzing process
(Zhang et al., 2018; Nie et al., 2017; Liu et al., 2017). Over the past
decade, a combination of THz spectroscopy with chemometric methods
had been used as an analytical technique (Wang et al., 2017). These
analytical methods are used for identification purposes. Table 2 shows
some of the most popular models used in food and agricultural studies.
Spectral pre-processing methods are used to remove irrelevant in­
formation from the optical parameters and increase the signal-to-noise
ratio.
2. Agricultural applications of THz technology
Due to the strong absorbance of THz radiation by water molecules,
THz imaging was initially used to monitor the water content of plant
leaves and observe the drought stress response in plants. THz has also
been used for soil inspection, detection of pesticides and harmful
compounds in crops, quality control of seeds, detection of transgenics,
and crop yield estimation.
1. Water content measurements and drought stress monitoring
The water content of plant leaves is an indicator of drought stress
and can potentially be used for irrigation management and planning.
Mittleman et al. (1996, 1999) were the first to capture a THz image
from a houseplant leaf and used it for measuring the water content of
the plant. They monitored the water uptake in a dehydrated plant and
showed that the THz relative transmission decreased as a result of water
intake into the plant leaf. Hadjiloucas et al. (1999) described the non-
invasive water content measurement method for plant leaves. Later, the
group used a combination of THz-TDS with principal component ana­
lysis (PCA) to predict the water content of plant leaves. They presented
quantitative models of leaf water content that can be used for the
3
Computers and Electronics in Agriculture 177 (2020) 105628
classification of wet and dry leaves (Table 3). Hadjiloucas et al. (2002)
used a range of linear transforms to analyze THz spectroscopic data and
showed that Karhunen–Loève transform was suitable for the classifi­
cation of plant leaves.
Ogawa et al. (2004) used THz spectroscopy where the frequency of
Gunn oscillator was set on 35 GHz at the output power of 10 mW to
monitor water/ice state and understood the relationship between the
crops and their cultivation method. They observed that the THz ab­
sorption spectrum of plant leave was directly proportional to its water
content. The absorption coefficient of water showed temperature-de­
pendency, and they observed a drastic change at 0 °C, due to the phase
transition from water to ice. They suggested using THz spectroscopy as
a non-destructive technique for monitoring the growth of plants. They
also performed a series of time intervals and illumination studies on
plant leaves and observed differing THz spectrum depending on the
illumination time. The group suggested that their technique can be used
in the watering plan of agricultural plants.
Zhang et al. (2008) introduced an algorithm for calculation of water
in the spinach leaves using their THz images. They made an assumption
that the Beer-Lambert attenuation law was applied and calibrated their
THz absorbance images. They also studied the distribution of water in
the spinach leaves and observed a good agreement between the cal­
culated and measured values (Table 3). THz images contained absor­
bance information from both plant leaf and the water in the leaf. THz
absorption by the spinach leaf must be removed from calculations. They
assumed that the water content of spinach leaf was zero after four days
of the natural drying process. They measured the pure water content
based on the differences between THz images of the 3rd day and other
days.
The water content of coffee leaf was measured based on the per­
mittivity under different watering conditions (Jördens et al., 2009).
Plant leaves are considered mixtures of particles with irregular shapes.
The permittivity of such complex mixtures can be described using ef­
fective medium theory. They used Landau, Lifshitz, Looyenga (LLL)
model to characterizes coffee plant leaves. They modified the model
and presented a 3rd order extension of the LLL model as the original
LLL model was only suitable for two-component mixtures. Leaf thick­
ness was found to be a function of the water content. The water content
of spinach leaf was calculated based on the measured permittivity at 0.9
THz. They reported a significant increase in THz transmission of
drought-stressed plants. The group designed a compact handhold THz
spectrometer for contact-free measurement of leaf thickness.
One of the main problems in drought-stress studies is the relocation
L. Afsah-Hejri, et al. Computers and Electronics in Agriculture 177 (2020) 105628

Table 2
THz Models used in food and agricultural studies.
Model Equation Reference

Exponential decay k cd Herrmann et al., 2002

A c
=e
A0
Li et al., 2010
I = I0 e ( a×2 d )
Correlation of time decay with speed, reflectance and dimension t=
d (n 1) Jördens and Koch, 2008
c

Square of transmission ratio Es ( )

2 Hiromoto et al., 2013
T( ) =
ER ( )

Power as a function of × direction which is perpendicular to the z direction Ok et al., 2013

Pr (x ) =
P0
2
1 + erf ( 2 (x x 0 )
r )
Fast Fourier Transform for spectral distribution E( ) A ( )e i ( ) = dtE (t ) e i t Qin et al., 2014; Nie et al., 2017

(w ) =
(w ) c
+1 Qin et al., 2018
wd

Linear regression for change of reflective index and excitation coefficient as a function y= ax + b Qin et al., 2017a
of TCH concentration

Frequency dependent model for each type of fluoroquinolones with combination of y=b+ aXi Long et al., 2018; Hu et al., 2017
wavelengths i

Linear regression for average signal or absorption coefficient as a function of y = ax + b Chen and Lijuan, 2014; Baek et al., 2014
concentration

Linear regression based on Lambert–Beer law parameters for absorption coefficient of ( )=[ 1( ) 2( )] b1 + 2( ) Cui et al., 2009
the mixture

Partial least squares regression based on two-dimensional correlation for synchronous 1

m Zhang et al., 2017b
(f1 , f2 ) = yj (f1 ). yj (f2 )
2D correlation m 1
j =1

Partial least squares regression based on two-dimensional correlation for asynchronous 1

m m Zhang et al., 2017b
(f1 , f2 ) = yj (f1 ). Njk yj (f2 )
2D correlation m 1
j =1 k= 1

Absorption as a function of frequency ( )~ 2 Sk Globus et al., 2012

2
k 2 2 2 2
k

The THz optical refractive index of the bacteria is calculated using standard algorithm Yang et al., 2016
s (f ) ref (f ) c
n (f ) = +1
2 fd

Triple term Debye relaxation model 3

n
Fawole et al., 2018; Federici, 2012
(f ) = +
1 + i2 f n
n= 1

Principal component analysis (PCA) X = TPT + E Liu and Kan, 2018; Zhang et al., 2017a

Principal component analysis clustering algorithm by fast searching and finding of N dij2 Qin et al., 2017b
density peaks (PCA-CFSFDP) i = exp
j = 1, j i d c2

i = minj : > i (dij )

Partial Least Squares (PLS) f Nie et al., 2017; Wang and Guo, 2017
X = TPT + EX = tk pkT + EX
k =1
f Cortes and Vapnik, 1995; Zhang et al.,
Y = UQT + EY = uk qkT + EY 2017a
k=1

Support vector machine (SVM) 1

N Qin et al., 2017a; Liu and Kan, 2018
min w 2 +C Xi
2
i=1

Two-dimensional correlation spectroscopy partial least-squares regression (2DCOS- N 1 Zhang et al., 2017b
PLSR) X (k ) = x (n ) W nk
n=0

Variable importance projection - stacked partial least squares (VIP-SPLS) h h Zhang et al., 2018a
VIPj = p bk2 tkT tk (wjk k )2 bk2 tkT tk
k= 1 k=1

Ray-tracing method Ei = E0 e jk1 z Afsharinejad et al., 2017a

4
 Table 3
THz spectroscopy and imaging for monitoring the drought stress and water content of plant leaves.
Application and product
Water content of plant leaf
Prediction of leaf water
content
Monitoring water/ice state
5
Quantification of water
content
Permittivity model for plant
leaves
Measuring the permanent
wilting point
THz range Mode/THz Experiment details
Type
94 GHz − 0.5 THz CW Null-balance quasi-optical transmissometer; Single-pass dispersive
Fourier transform spectrometer (DFTS); Femtosecond Ti: sapphire
laser; Flann Microwave point-contact crystal detector; Samples: Fatsia
japonica and Phormium tenax leaves
100–500 GHz THz-TDS Samples: wet leaves (~60% water content) and oven-dried leaves;
Optimal linear transform was compared with the Karhunen–Loève
transform to differentiate between wet and dry leaves; PCA1 model:
was used for prediction of the water content from a group of
transmission measurements at different wavelengths; PCA2 model: was
used for qualitative classification (such as very dry, dry and wet);
Univariate calibration was used for comparison purposes
0–3 THz THz-TDS 35 GHz Gunn oscillator coupled to a horn antenna; Leaf samples were
placed in a 2 mm layer of water in a plastic cell for the freezing and
defrosting processes; Measurement area of the leaf: 4.5 × 5.5 cmLight
source: white fluorescent lamp
0.1–4 THz THz-TDS Used a Tunnel injection TransitTime THz wave generator;
Measurements at 0.189 THz; Samples: spinach leaf (fresh, natural dried
after 1, 2, 3 days) and filter paper (thickness = 0.15 mm); Scanning
area: 42x30 mm for spinach leaf, 24x24 mm for filter paper; Applied
the attenuation law of Beer-Lambert to their THz data
0.3–1.8 THz THz-TDS Samples: a) coffee plant drought-stressed for 21 days, b) regularly
watered coffee plant; Measurement of air content: by pressing the disk
under a load of 10 tons for 1 min; The thickness of dried leaf disks:
60–90 μm; The thickness of pressed leaf disks: 31 ± 1 μm; Disk
diameter = 13 mm; Disk weight = 5 mg; Simultaneous thickness
measurement by a micrometer screw
1.5–3 THz THz-TDS Erbium fiber laser; Two sets of horn antennas; Designed a specific
holding device for samples; Samples: 1-week old Silver fir (Abies alba)
seedlings; Irrigation: 25 ml of tap water every 2 days; Drought
condition: no irrigation at all; Gravimetric water content measurement:
drying the seedlings in the oven (110 °C)
Findings References
L. Afsah-Hejri, et al.
*Non-invasive measurements of leaf water content (Hadjiloucas et al.,
*The thickness of the leaf is a critical factor and must be measured 1999)
simultaneously
*Leaf thickness had an insignificant effect on the refractive index at
frequencies < 1 THz
*Good correlation between THz transmittance with leaf thickness and
water content
*Linear transforms were used to analysis THz spectroscopic data (Hadjiloucas et al.,
*Lagrange multipliers resulted in the maximum separation between 2002)
different leaf spectrums
*Differentiated between wet and dry leaves based on their transmission
spectrum
*Built quantitative models for leaf classificationKarhunen–Loève
transform was suitable for classification purposes
*PCA1 resulted in RMSEP = 1.3x10-3
*Univariate calibration had RMSEP = 3x10-3
*The THz absorption spectrum was affected by the water content of (Ogawa et al., 2004)
plant leaves
*The absorption coefficient of water was temperature-dependent
*Water had a 3-times higher absorption coefficient than ice
*The absorption coefficient was used to monitor water/ice state
*THz spectroscopy can be used as a non-destructive technique for
monitoring the growth of plants
*THz transmittance of leaves increased by 0.3 dB when the white
fluorescent lamp turned on
*Presented an algorithm for calculation of water content from THz (Zhang et al., 2008)
imaging
*The THz spectrum of spinach leaf was time-dependent
*Filter paper with different water content was used to verify the
accuracy of the method
*Good agreement between calculated and experiment results
*Non-invasive, non-contact method for measuring the water content of
agricultural products
*Leaf thickness increased with rising water content (Jördens et al. 2009)
*Developed a leaf permittivity model to calculate leaf water content at
0.9 THz
*Dielectric material parameters were used to evaluate the water status
of coffee leaves
*The permittivity of pure water was derived by a dual Debye model
*The medium theory was used to build an electromagnetic model3rd
order extension of LLL model was effective in describing permittivity at
THz range
*Rayleigh roughness factor was used to describe the scattering
influence at high frequencies
*A good method for monitoring drought stress in plants
*Good agreement between simulation andmeasurement data for
refractive indices
*An accurate method for measurement of water deficiency and monitor (Born et al., 2014)
drought stress (especially the invisible effects)
*Good correlation between the THz transmission spectrum and
gravimetric water content
*Water content affected the thickness of the seedlings
*Permanent wilting point of the seedlings was measured
(continued on next page)
Computers and Electronics in Agriculture 177 (2020) 105628
 Table 3 (continued)

Application and product THz range Mode/THz Experiment details Findings References
Type

*Pearson product moment correlation coefficient calculated for

L. Afsah-Hejri, et al.

different relative water content

Evolution of water content in
plant leaves
Monitoring water status for
irrigation purposes
Active inspection of water
content
Differentiate between fresh
and old leaves
Long-term water status
monitoring
0.14–0.22 THz THz-TDS Transmission and reflection modes; Imaging setup: based on two vector *Plant leaf was green after 48 h of cutting, and no visible change (Iriarte et al., 2011)
network analyzer (VNA) extenders; 3D scanning; Time period = 48 h observed (Iriarte et al., 2010)
*THz image of plant leaf showed 5 dB variation due to the loss of water
*Observed significant differences between the nerves and edges of the
leaf
*THz imaging can be used for water content monitoring, leaf
inspection, irrigation planning, and reducing irrigation costs
400 GHz CW Dehydration (18 days) and rehydration (0–400 min); Sample: Coffea *THz transmission of plant leaves increased during the drought stress (Shakfa et al., 2009)
arabica leaves *The observed decrease in THz transmittance short after water uptake
*Inexpensive CW THz systems can be used for water monitoring and
irrigation planning
0.14–0.22 THz THz-TDS Transmission and reflection modes; Quasioptical setting; Horn antenna; *High-resolution 3D images (Etayo et al., 2010)
Vector network analysis *High water content resulted in higher signal level
*Plant nerves with higher water content showed higher intensity
*Gradually dying parts of the leaf (such as edges) had a lower signal
level
*Nerves and edges were clearly visible at 215 GHz
*Both water content and dept of layers were evaluated with the THz-
TDS system
340 GHz CW Time period = 12 days *Phase and magnitude information collected (Seo et al., 2010)
0–6 THz THz-TDS Automated long-term setup; The digital scale under sample holder; *THz transmission and weight measurements (Gente & Koch, 2015)
Plant samples = rye (Secale cereale), oat (Avena), barley (Hordeum *Transmission values increased while the plant was deprived of water

6
Water monitoring in live
plant leaves
Transmission behavior of
plant leaves
Water content measurement
vulgare)Time period = 30 daysNo watering after day 6, Re-watering
after day 22; Weight & THz transmission measurement: every 1 h; For
gravimetric studies: barley leaves were oven-dried and measured every
10 min
0.05–2.1 THz CW CW was used because it offers a larger S/N ratio and a dynamic range
below 0.4 THz; Leaf samples: cabbage, coffee, lettuce, mint, radish,
rhubarb, strawberry; Leaves from different height or positions on the
stem; Factors affecting the water content of leaf: position, thickness,
age, cellulose content, texture; Transmission loss: a combination of
reflection, absorption and scattering effects; Factors affecting
transmission loss: water content, leaf thickness, texture, density, and
surface roughness
0.3–2 THz THz-TDS Samples: coffee leaves (thickness = 0.1, 0.15and 0.2 mm), relative
permittivity of leaf = 2.5Data analysis: based on the thickness,
permittivity, and electric field
0.1–3.5 THz THz-TDS Ti-sapphire femtosecond laser; Nitrogen filled system to avoid
humidity effects; Samples: two variety of rapeseed plants (New oil and
Long oil varieties); Natural dehydration at room temperature and oven
drying at 100 °C for 1 h; Weight measurement every 30 min of
evaporation; Savitzky-Golay method for preprocessing the spectra
*Higher standard deviation observed for drought stress response
during daytime (due to higher use of water by the plant during
photosynthesis in the daytime)
*Immediate plant recovery after re-watering
*Gravimetric measurements of the water content gave an average
value for the whole leaf
*Pearson correlation coefficient r = 0.94
*High transmission variability in plant leaves (Std > 0.3 Mean value) (Afsharinejad et al.,
*Cabbage leaves: the largest variability of THz transmission loss 2017b)
*Coffee leaves: the least variability of THz transmission loss
*To make a realistic estimate and develop a model for each plant, a
statistically large number of samples must be studied.
*Extinction coefficient and refractive index of coffee leaves were (Afsharinejad et al.,
measured 2017a)
*Performed calculations based on the electrical properties of coffee
leaves, thickness, and permittivity
*Propagation model for coffee leaves
*The water content of rapeseed leaves was quantified in the frequency (Nie et al., 2017)
range between 0.3 and 2 THz
*KPLS model had the best prediction accuracy for the water content of
rapeseed leaves
*KPLS model results based on transmission: RMSEP = 0.1015,
Rval = 0.8508KPLS model results based on absorption
*RMSEP = 0.1009, Rval = 0.8574
Computers and Electronics in Agriculture 177 (2020) 105628
L. Afsah-Hejri, et al.
of the leaves during the measurement period. Baek et al. (2014)
avoided this problem by using silver fir seedlings (Table 3). They ob­
served a good correlation between the THz transmission spectrum and
gravimetric water content. They also reported that the thickness of the
seedling was affected by its water content and measured the permanent
wilting point of the seedling. They presented an accurate method for
measuring water deficiency and monitoring the drought stress when it
is not visually detectable.
Iriarte et al. (2011) investigated the evolution of water in plant
leaves and observed significant changes in the THz spectrum of leaves
while no visible changes were noticed. They also showed that their
active THz inspection method could potentially be used in vineyards to
reduce irrigation costs (Iriarte et al., 2010). Water monitoring for irri­
gation purposes has also been reported for Coffea arabica leaves over a
drought test period of 6 h (Scheller & Koch, 2009) and 18 days (Shakfa
et al., 2009).
Etayo et al. (2010) captured high-resolution images of leaves at
215 GHz. The edges of the leaves were clear at this frequency. Their
quasioptical measurement set-up increased the resolution of the images,
and they were able to distinguish the stalked layers of leaves. Seo et al.
(2010) simultaneously measured phase and magnitude information of
plant leaves at 340 GHz and differentiated between fresh and old
leaves. Measurement of chlorophyll content of the leaves was also re­
ported at 360 GHz (Wagner et al., 2011).
Gente and Koch (2015) designed a long-term automated setup for
monitoring the water status in plants. Both weight and THz transmis­
sion data were collected every hour over a period of 30 days (Table 3).
Dehydrated plants showed higher transmission values and an im­
mediate reaction of the plant was visible in the THz spectrum of re-
watered plants. Their results were in agreement with Born et al., 2014.
For the first time, Gente & Koch (2015) reported different standard
deviation for day and night measurements and attributed it to the
photosynthesis during the daytime. More research is needed to under­
stand and compare the behavior of different plant species under de­
hydration and drought stress. They used a commercially available
mobile THz-TDS setups to study barley leaves in a greenhouse. Al­
though THz measurement was performed on a small surface of the leaf,
the gravimetric measurements of the water content gave an average
value for the whole leaf. Gente and Koch (2015) also described THz
quasi-TDS (QTDS) for measuring the water status dynamics of the
plants. QTDS technology is an excellent candidate for building in­
expensive and compact THz devices for drought stress monitoring.
Afsharinejad et al. (2017b) investigated THz characteristics of seven
popular plant leaves (Fig. 3). They calculated the transmission loss in
cabbage, coffee, lettuce, mint, radish, rhubarb, and strawberry and
reported a huge variability of THz transmission loss at around 0.3 to 0.4
THz. They calculated the transmission loss for all plant samples at 0.4
Fig. 3. (a) Experiment setup of CW THz system, (b) THz transmission spectra of seven different plant leaves, (c), and transmission spectra of the coffee leaf at
different areas on the leaf by Afsharinejad et al. (2017b).
7
Computers and Electronics in Agriculture 177 (2020) 105628
THz and showed that they all had a standard deviation > 0.3 of their
mean values. Variability of THz transmission loss depends on some
factors such as leaf thickness, density, uniformity, and texture of the
leaf. Cabbage leaves showed the largest variability of THz transmission
loss while coffee leaves had the least. Coffee leaves are uniform in
texture and thickness. A sharp peak at 0.3 THz was reported for most of
the plants. The group was not able to identify the origin of this peak and
recommended more investigation. They also recommended the in­
vestigation of a statistically large number of samples to make a realistic
estimate and modeling for each plant. The group also studied the
transmission of the THz signal through multiple layers of coffee leaves
(Afsharinejad et al., 2017a). Calculations were based on the thickness
and permittivity data and they observed a repeat pattern at about
130 GHz. They proposed a propagation model for THz transmission
through coffee leaves. They stated that their future research will focus
on the application of their model on the coffee leaves data to study the
effect of leaf thickness and surface roughness on the ratio of the
transmission/reflection data.
Nie et al. (2017) used a combination of THz-TDS spectroscopy with
chemometric methods for quantification of water in rapeseed leaves.
They observed different transmission and absorption spectrums for ra­
peseed leaves at different moisture levels. Lower absorption and higher
transmittance coefficients were observed for leaves with low water
content. The group used the Savitzky-Golay method to process their
spectral data and conducted partial least squares (PLS), Boosting-PLS
and kernel PLS (KPLS) to establish an efficient model for prediction of
water content in leaves. KPLS model showed the best prediction accu­
racy. The root means square error (RMSEP) and prediction coefficient
correlation (Rval) values for the KPLS model are presented in Table 3.
Nie et al. (2017) suggested that the combination of THz spectroscopy
with mathematical modeling methods can be used for quantification of
leaf water content in the field. Challenges for measuring the water
content of leaf in the filed include 1) leaves show different absorption
and transmission spectrums at different moisture levels, 2) a few che­
mometric methods need to be tested to find the most efficient model for
that particular leave, and 3) good mathematical and modeling knowl­
edge is required. Although the combination of THz-TDS spectroscopy
with chemometric methods has good accuracy, more research is needed
to turn it into a practical approach for the prediction of water content at
the filed level.
2. Detection of pesticides, fungicides, insecticides, and harmful
compounds
Pesticides, including insecticides, herbicides, and fungicides, are
used to control pests, weeds, molds, bacteria, rodents, and insects in
agricultural fields. There is a maximum residue limit (MLRs) for
 Table 4
THz spectroscopy and imaging for detection of pesticides, fungicides, insecticides & harmful compounds.
Application and product
Cyfluthrin in solutions
Imidacloprid, carbendazim,
tricylazole, and buprofezin in
powders
Six pesticides in vegetables
Fludioxonil and cis-Permethrin in
spinach
Carbendazim in orange skin
8
Carbendazim, chlorothalonil and
isoprothiolane in polished rice
Nitrofen
Thiabendazole
Pesticides in wheat flour
Imidacloprid in rice powder
THz range Experiment details
0.5–1.5 THz Femtosecond Ti-sapphire laser; A photo-conductive antenna and two parabolic
mirrors and a ZnTe crystal detector; Nitrogen filled system to avoid humidity
effects; Cyfluthrin concentration = 0.5–10 μg
0.5–1.6 THz Femtosecond laser; ZnTe detector; Samples: sticky rice, sweet potato, and
lotus root
0.7–14 THz (20 to Pesticides (at 3% concentration): Fludioxonil, cis-Permethrin, Metalaxyl,
400 cm-1) Chlorfenapyr, Mepanipyrim, and Acetamiprid; Samples: freeze dried spinach,
tomato, strawberry and cabbage; 14 samples of cis-Permethrin were used for
PLS model
0–14 THz(0 to Sample: freeze-dried spinach (Spinacia oleracea L.); Pesticides: Fludioxonil
400 cm-1) (3%), cis-Permethrin (3%)
0.2–1.3THz Ti: sapphire femtosecond laser; Samples: orange skin dried at 373 K for 1 h,
grounded and mixed with fungicide at 0, 50, and 100%, pressed into pellets
with a thickness of1.031, 0.906 and 0.856 mm)
0.2–3.5 THz Femtosecond mode-locked; Ti: sapphire laser; The system was purged with
N2Humidity < 4%
0.3–1.6 THz Femtosecond Ti:sapphire laser; Coplanar strip line antenna; Samples: nitrofen,
thiacloprid and acetamipyrid purities of 98, 99 and 99.5%; Pellet thickness:
1.178–1.6 mmN2 purged system (0–51.84% (w/w)), Humidity < 0.1%
0.3–2 THz Mode-locked Ti: sapphire laser; N2 purged system, Humidity < 0.1%;
Samples: thiabendazole (98%), benomy (99%) and thiophanate-methyl
(99.7%), vacuum dried at 423 K for 2 h; Thiabendazole pellet
thickness = 1.321 mm; Thiophanate-methyl pellet thickness = 1.252 mm;
Benomyl pellet thickness = 1.441 mm
0.1–3 THz Femtosecond laser; ZnTe detectorSamples: wheat flour; Pesticides:
imidacloprid, chlorpyrifos, daminozide, diethyldithiocarbamate,
chlorpyrifosmethyl, dimethyldithiocarbamate, and dicofol,
0.3–1.7 THz Ti: sapphire femtosecond laser; ZnTe photoconductive antenna; N2 purged
system, Humidity < 10%; Manually rotated the pellets to reduce the effect
Findings References
*Cyfluthrin had an absorbance spectrum between 0.5 and 1.5 THz; (Hua et al., 2010)
L. Afsah-Hejri, et al.
*PLS was an effective method for quantification of Cyfluthrin
(RMSECV = 0.565 μg/mL)
*Imidacloprid, carbendazim, tricylazole, and buprofezin were studied in (Hua & Zhang,
food powders 2010)
*Imidacloprid showed sharp peaks at 0.89, 1.13 1.24, 1.46, and 1.57THz.
*Imidacloprid in sticky rice powder had only three sharp peaks at 0.89, 1.13
1.24THz.
*PLS predicted the weight ratio of imidacloprid with relative error < 5%
*Carbendazim had two peaks at 1.15 and 1.32 THz
*Tricylazole showed four peaks at 0.83, 0.92, 1.03, and 1.48 THz
*Absorption peaks of buprofezin appeared at 0.90 and 1.29 THz
*All four pesticides were differentiated in a mixture based on their
absorbance spectrum at 1.54 THz
*All pesticides were identified in freeze-dried vegetables (Suzuki et al.,
*A high correlation was observed between the concentration of each 2010)
pesticide and the 2nd derivative value (R > 0.96)
*PLS showed a good performance for cis-Permethrin (R2 = 0.95 and
RPD = 3.95)
*Fludioxonil and cis-Permethrin were detected in freeze-dried spinach (Suzuki et al.,
*Fludioxonil and cis-Permethrin had similar absorption spectrum before and 2011)
after freeze-drying
*Carbendazim had a sharp peak at 1.16 THz (Ma et l., 2011)
*The average refractive index of orange = 1.72
*The average refractive index of Carbendazim = 1.85
*The absorbance trend in the orange + Carbendazim mixture changed due
to the strong absorbance ability of orange
*Chlorothalonil showed a specific fingerprint between 2.7 and 3 THz (Kim et al.,
*Carbendazim had waveforms similar to methanol 2012a)
*Isoprothiolane had spectrum similar to acetonitrile
*THz spectroscopy is a good method for detection of fungicide residues
*Nitrofen, thiacloprid and acetamipyrid showed specific absorption (Wang & Ma,
spectrums 2013)
*Nitrofen: absorption peaks at 0.48, 0.98 and 1.33 THz, average
absorption = 6.6 cm−1
*Thiacloprid absorption peaks at 0.65 and 1.25 THz, average
absorption = 12.38 cm−1
*Acetamipyrid peaks at 1.08 and 1.48 THz, average
absorption = 12.44 cm−1
*biPLS had highest performance (R = 0.9995 and RMSEP = 0.4064,
LOD = 2.52%)
*Thiabendazole had two obvious absorption peaks at 0.96 and 1.25 THz (Ma et al., 2013)
*Thiabendazole was detected at a concentration of 1.1% in the water
solution.
*mwPLS (based on interval 43–51 (1.06–1.22 THz) was the most accurate
model for prediction of Thiabendazole (R = 0.9995, E = 3.75%,
RMSECV = 0.2392 and RMSEP = 0.3629), LOD 1.1%
*All pesticides exhibited frequency-dependent refractive indices (Maeng et al.,
*Imidacloprid: unique absorption peaks in wheat flour 2014)
*Linear correlation between the weight ratio and absorption coefficient of
imidacloprid
*Maxwell-Garnett was the effective medium model for imidacloprid
*Imidacloprid was quantified in rice powder with LOD = 0.99%; (Chen
*PLS had a high performance in quantitative prediction of imidacloprid et al.,2015)
(continued on next page)
Computers and Electronics in Agriculture 177 (2020) 105628
 Table 4 (continued)
Application and product
Methomyl in wheat and rice flours
Methomyl in apple peel
Carbaryl in rice powder
Carbendazim in tomato powder
Carbendazim in solutions
9
Aflatoxin B1 (AFB1) in corn
Aflatoxins in acetonitrile and corn
Auramine O (AO) in medicinal herbs
THz range Experiment details Findings References
caused by pellet heterogeneous; Asymmetric least square (AsLS) was used to (RMSEP = 0.3%)
correct the slope baselines and improve S/N ratio of imidacloprid *PLS had a smaller root mean square error value of prediction (0.5%) than
L. Afsah-Hejri, et al.
SVR (0.7%)
0.1–3 THz Methomyl thioacetimidate (99.9%) *Methomyl: absorption peaks at 1,1.64, 1.89 THz (Baek et al.,
*Sharp peak at 1 THz: the fingerprint of methomyl 2016)
*Methomyl absorption was dose-dependent.
*Recovery range: 78 to 96.5%R2 > 0.957, RSD = 2.83–4.98%,
LOD = 3.74%
0.5–2.5 THz Ti: sapphire femtosecond laser; Photo-conductive-antenna and a ZnTe *Methomyl was detected based on its sharp absorption peaks at 1 THz (Lee et al., 2016)
nonlinear crystal, high-resistivity silicon beam splitter and three metal *Methomyl absorption was concentration-dependent
mirrors; The system was purged with ultra-dry and purified compressed air, *Improved LOD = 8 mg/kg
relative humidity = 0% *Possible quick, precise and non-destructive detection of pesticide in a real-
time inspection
0.5–6.5 THz THz-TDS combined with chemometric methods and Fourier transform far-IR *Carbaryl had absorption peaks at 3.2 and 5.2 THz (Sun et al., 2016)
spectroscopy; Sample: rice powder; Pellets diameter = 13 mm and thickness *PLSR model was effective in quantification of Carbaryl in rice powder
about 1 mm (R2 = 0.98, RMSECV = 0.0025 and RMSEP = 0.0044)
*FT-Far-IR model had Rv = 0.99, RMSEP = 0.0086, and
RMSECV = 0.0077
0.1–2 THz Femtosecond laser; Cubic beam splitter; ZnTe detector; Quater-wave-plate and *Carbendazim had peaks at 1.15 and 1.32 THz at the weight ratio > 15% (Qin et al. 2017b)
a Wollaston prism; System was purged with dry air, relative humidity < 4%, w/w
and temperature 295 K *Combination of PCA with CFSFDP detected Carbendazim in tomato
powder
*Results compared with K-means clustering method
*PCA-CFSFDP had a higher performance comparing to the solely used
clustering method
0.4–1.4 THz Ultra-fast femtosecond laser; Cubic beam splitter; ZnTe detector; *Trace amounts of carbendazim were detected (Qin et al., 2018)
Photoconductive antenna; Quater-wave-plate and a Wollaston prism; *Resonance peak of metamaterial was affected by the concentration of
Transmission mode system was purged with dry air, relative humidity < 1% carbendazim
and temperature 295 K; Metamaterial composed of metal ohm ring arrays; *Higher concentrations of carbendazim resulted in lower frequency
Metamaterial placed in a sample cell and carbendazim solution was dropped resonance of metamaterial
on the surface of the metamaterialThe thickness of metamaterial = 350 μm *LOD = 5 mg/L
*Metamaterial combined with THz spectroscopy can detect pesticides at
trace level with very high sensitivity
*This method had 104 times sensitivity enhancement compared to squash
method
0.2–1.2 THz Mode-locked Ti: sapphire laser;Microstripline antenna on a GaAs *AFB1 was detected in all samplesIn 94% of the samples, the correct (Zhao et al.,,
crystalSystem was purged with N2, relative humidity < 2%, concentration of AFB1 was determined 2015)
temperature = 293 KSpecific sample holder (called removable liquid cell) to *Combination of information-fusion technology with THz spectroscopy
avoid THz absorption by the cellSample: Corn (aflatoxin extraction with successfully identified and quantified AFB1 in corn
immunoaffinity columns, kept at 2 °C in a mixture of chloroform/acetonitrile),
powdered and pressed into pellets
0.4–1.6 THz Mode-locked Ti: sapphire laser *Linear regression models, such as PCR and PLS, were more precise for (Ge et al., 2016b)
aflatoxin B1 range of 1–50 µg/ml
*Nonlinear-regression-based models (PCA-SVM and SVM) showed more
accuracy in the range of 1–50 µg/l AFB1
*For PLS and PCR, the correlation coefficient was 0.985 and 0.986,
respectively
*RMSE was 0.753 and 0.587 in the aflatoxin B1 range of 1–50 µg/ml.
*PCR resulted in 87.5% prediction accuracy in the 1–50 µg/ml range
*SVM and PCA-SVM had prediction accuracy 85% and 93.75% in the
1–50 µg/l range, respectively.
*AFB1 in maize was quantified within 5 s
0.2–1.6 THz Two-dimensional correlation spectroscopy (2DCOS); The system was purged *2DCOS: highlighted the spectral differences at specific concentrations, (Zhang et al.,
with dry air, relative humidity < 2%Sample: Pollen Typhae (a kind of reduced the effects of noise, and improved the PLSR model and accuracy of 2017b)
the results
Computers and Electronics in Agriculture 177 (2020) 105628
(continued on next page)
L. Afsah-Hejri, et al. Computers and Electronics in Agriculture 177 (2020) 105628

pesticide residues in food and agricultural products. Some costly and

time-consuming spectrometry and chromatography techniques are used

(Zhang et al.,
(Zhang et al.
(Zhang & Li,
for the detection and quantification of pesticides in food. THz spec­
References

troscopy can be used as a rapid and non-destructive technique for the

2017a)

2018a)
2018)
detection of pesticides in agricultural products (Qin et al., 2013). Cy­
fluthrin is a pesticide commonly used for cotton, corn, cereals, peanuts,
fruits, vegetables, and potatoes. Hua et al. (2010) used a combination of

*Compared receiver operating characteristic (ROC) curve and also the area
RMSEC = 0.5544%, RMSEP = 0.7527%, Rp = 0.9962, and RPD = 15.38.

under the ROC curve (AUC) for each model to evaluate the performances of
*VIP-SPLS showed the best performance (Rc = 0.9958 and Rp = 0.9464,
*Rapid, accurate and reagent-free detection method for AO in medicinal

chemometric methods with THz-TDS for the detection of Cyfluthrin in

*2DCOS-PLSR: accurate quantitative analysis of AO with Rc = 0.9978,

accuracy 97.78–100% for discrimination of poisonous from non– toxic

solutions. Cyfluthrin had an absorbance spectrum in the range of

*Combination of THz spectroscopy with PCA resulted in prediction

RMSEC = 0.0921 and RMSEP = 0.3237) in quantification of AO

0.5–1.5 THz. PLS method showed to be an effective method for quan­

tification of Cyfluthrin in solutions. THz-TDS was also used for the
*VIP-SPLS showed better performance than PLS and SPLS

detection of imidacloprid, carbendazim, tricylazole, and buprofezin in

sticky rice, sweet potato, and lotus root powder samples. All four pes­
*PCA-RF method had a prediction accuracy of 99%

*Classification accuracy of CS-KELM = 98.8889%

ticides had specific absorption spectrums between 0.5 and 1.6 THz

*Classification accuracy of GA-KELM = 96.6667

(Table 4). Specific absorption at 1.54 THz was used to differentiate the
*PCA-RF had the best ROC curve and AUC

pesticides in a mixture. Hua & Zhang (2010) used PLS to predict the
weight ratio of imidacloprid in a mixture with a relative error of < 5%.
They recommended further research to develop non-destructive multi-
component detection and trace-amount detection methods for pesti­
the classification algorithms

cides.
Fludioxonil, cis-Permethrin, Metalaxyl, Mepanipyrim Acetamiprid,
and Chlorfenapyr were detected in vegetables (Suzuki et al., 2010). All
six pesticides showed unique absorption spectrums between 0.7 and 14
THz. Suzuki et al. observed a high correlation (R2 > 0.96) between the
concentration of pesticide and the second derivative value of each
Findings

spectrum. Such a high correlation showed that pesticides could be

herbs

herbs

quantified based on their THz spectrums. Their method had some

shortcomings as well, such as low sensitivity and lengthy sample pre-
Femtosecond laser, ZnTe crystal detector; The system was purged with dry air,

Femtosecond laser, System was purged with dry air, relative humidity < 3%;
medicinal herb), powdered and vacuum dried at 50 °C for 2 h and pressed into

relative humidity < 2%Sample: Pollen Typhae (a kind of medicinal herb),

treatment procedures. The low sensitivity of the technique was due to

Mollissimae, Herba Solani Nigri, and Herba Solani Lyrati), powdered and

humidity < 3%; Sample: poisonous herb (Gelsemium elegans) and non-

the sample ingredients/interfering compounds that resulted in the

powdered and vacuum dried at 50 °C for 2 h and pressed into pellets

broad absorption spectrum. They suggested the inclusion of a purifying

Sample: similar traditional herbal medicines (Herba Aristolochiae

Femtosecond laser; The system was purged with dry air, relative

step together with THz spectroscopy to eliminate the interfering com­

poisonous herbs (Lonicera japonica Thunb, and Ficus Hirta Vahl)

pounds. In another study, they investigated the effect of freeze-drying

on the detection of cis-Permethrin and Fludioxonil in spinach samples.
Results showed that freeze-drying did not affect the absorption spec­
vacuum dried at 50 °C for 2 h, pressed into pellets

trum of cis-Permethrin, and a similar THz spectrum was observed after

freeze-drying (Suzuki et al., 2011). They showed that freeze-drying was
an effective method for removing the effect of water interference from
samples.
Carbendazim, a benzimidazole fungicide used for controlling worms
in fruits and cereals, has harmful effects such as infertility. Ma et al.
(2011) detected carbendazim in orange skin using THz-TDS. Carben­
dazim showed a clear absorbance spectrum at 1.16 THz and an average
refractive index of 1.85. Although orange skin didn’t show any obvious
Experiment details

peak, it affected the absorbance trend in the carbendazim-orange

mixture due to its strong absorbance ability. Kim et al. (2012a) also
detected pure carbendazim and two other fungicide residues (chlor­
pellets

othalonil and isoprothiolane) in polished rice. Pure carbendazim

showed a similar THz fingerprint to methanol, whereas pure iso­
prothiolane had a similar spectrum to acetonitrile. Specific fingerprints
were only observed for chlorothalonil between 2.7 and 3 THz.
THz-TDS spectroscopy was used for quantification of, selective
0.2–1.6 THz

0.2–1.2 THz

0.2–1.4 THz
THz range

herbicides widely used for weed control in vegetable gardens (Wang &
Ma, 2013). The THz spectrum of nitrofen was compared with two
commonly used soil pesticides, thiacloprid, and acetamipyrid (Table 4).
They used four linear techniques (PLS, interval PLS (iPLS), backward
interval PLS (biPLS), and moving window PLS (mwPLS)) to build their
calibration models. Nitrofen showed unique absorption peaks at 0.48,
0.98 and 1.33 THz. They successfully quantified nitrofen using a com­
Application and product

bination of THz spectroscopy with biPLS model (R = 0.9995 and

AO in medicinal herbs
Table 4 (continued)

RMSEP = 0.4064) and limit of detection (LOD) of 2.52%. In another

Poisonous herbs

study, the group studied the THz spectrum of Thiabendazole, a widely

Medicinal herbs

used bactericide used for fruits, vegetables, and cereals (Ma et al.,
2013). Thiabendazole had two distinct absorption peaks at 0.96 and
1.25 THz. Their method detected thiabendazole at the concentration of
1.1% in the water solution, and they achieved satisfactory results with

10
L. Afsah-Hejri, et al.
the mwPLS model (based on interval 43–51 (1.06–1.22 THz) (Table 4).
Their method quantified thiabendazole with high accuracy, and they
concluded that interval selection was the critical step for producing
optimal results in multi-variable analysis.
The technique reported by Hua & Zhang (2010) was used by Maeng
et al. (2014) for the detection of pesticides in wheat flour. Maeng et al.
(2014) broadened the THz range (0.1–3 THz) and expanded the number
of target pesticides (dicofol, chlorpyrifos, chlorpyrifosmethyl, damino­
zide, imidacloprid, diethyldithiocarbamate, and dimethyldithiocarba­
mate) in their study. They reported that all pesticides had frequency-
dependent refractive indices. Imidacloprid had unique absorption peaks
in wheat flour, and a linear correlation was found between the weight
ratio of the imidacloprid and its absorption coefficient. They claimed
that Maxwell-Garnett was an effective medium model for imidacloprid.
Chen et al. (2015), quantified imidacloprid in rice powder. They ob­
served some background noise due to the THz absorbance of rice
components such as protein, cellulose, and starch. The sensitivity of the
method for imidacloprid in rice powder was less than imidacloprid in
the polyethylene matrix. They used asymmetric least square method to
correct the slope baselines and improve the signal to noise (S/N) ratio
of imidacloprid THz spectra. As a result, four sharp peaks at 0.89, 1.13,
1.25, and 1.50 THz were observed for imidacloprid in rice powder.
They used PLS, biPLS, iPLS, support vector regression (SVR) to build
quantitative models and showed that PLS had a high-performance in
the quantitative prediction of imidacloprid (RMSEP = 0.3% and LOD of
0.99%) than SVR.
Methomyl is a highly toxic carbamate insecticide used for crop
protection. Methomyl exhibits three absorption peaks at 1, 1.64, and
1.89 THz and Baek et al. (2016) used the sharp peak at 1 THz as a
fingerprint of methomyl in wheat and rice flour samples. Similar to
other pesticides, THz absorbance of methomyl was dose-dependent.
Density functional theory (DFT) and cluster calculations were used to
analyze the spectrums. Their method had a recovery range between 78
and 96.5% with higher recovery for methomyl in wheat flour samples.
Although methomyl was detected in a rapid and non-invasive way, the
sensitivity of their technique was low (LOD = 3.74%) and couldn’t
reach the regulatory limits set for the detection of methomyl in cereals.
In another study, Lee et al. (2016) developed a highly sensitive and
selective detection method for methomyl in apple peels using nanoscale
metamaterials-based THz-TDS. Nanoscale slot-antenna-based metama­
terials have a strong THz resonance at a specific frequency, matching
with the target molecule’s intra- or inter-molecular collective vibration.
Using a specific nano-slot-antenna array-based SC for specific resonance
at 1THz, they achieved a great THz field localization in transmission
and THz field enhancement. They performed tests on both reflection
and transmission mode and achieved excellent performance and sen­
sitivity results in both modes. Under the transmission mode, their
method resulted in LOD = 8 mg/kg for methomyl as well as real-time
monitoring of the contaminated samples. Their reflection images
showed an obvious color difference around the methomyl-con­
taminated area, suggesting that THz imaging can be used as a sensitive
and non-destructive detection method for pesticides in agricultural
products.
Carbaryl is another highly toxic, wide-spectrum carbamate in­
secticide widely used for grain protection. Sun et al. (2016) compared
Fourier transform far-IR spectroscopy with a combination of THz
spectroscopy and chemometric methods for quantification of carbaryl
in rice powder. Both methods successfully quantified carbaryl in rice
powder (Table 4). Carbendazim, a benzimidazole broad-spectrum fun­
gicide, was detected in tomato powder based on its unique fingerprint
between 0.1 and 2 THz (Qin et al., 2017b). Carbendazim showed to
11
Computers and Electronics in Agriculture 177 (2020) 105628
have a dose-dependent absorbance and had two absorption peaks (at
1.15 and 1.32 THz) at the weight ratio > 15% w/w. The authors sug­
gested that integrating statistical procedures with clustering methods
can successfully detect pesticide in food samples. Combining PCA with
clustering by fast search and find of density peaks (CFSFDP), they pri­
marily reduced dimensions of THz spectrum data and then detected
Carbendazim in tomato powder. They also compared their results with
the K-means clustering method and claimed that their method, PCA-
CFSFDP, had a higher performance compared to the solely used clus­
tering method. Recently, Qin et al. (2018) developed a highly sensitive
method for the detection of carbendazim using THz-TDS combined with
a metal ohm ring arrays metamaterial. The resonance peak of meta­
material was affected by the concentration of carbendazim. Higher le­
vels of carbendazim resulted in lower frequency resonance of meta­
material. For example, 0.5 mg/ L carbendazim showed a resonance at
1.15 THz, while 300 mg/L carbendazim had a transmission spectrum at
1.11 THz. The LOD was significantly improved to 5 mg/L.
Aflatoxins (AFs) are carcinogenic fungal metabolites causing severe
health problems in animals and humans (Afsah-Hejri et al., 2020, 2011;
2013a). Analytical methods for the detection of AFs in food and feed are
destructive, expensive, time-consuming, and labor-intensive (Afsah-
Hejri et al., 2013b). Zhao et al. (2015) used a combination of THz
spectroscopy with a data fusion method for quantification of aflatoxin
B1 (AFB1) in corn. As there was no distinct absorption peak in the THz
region, the group used the information-fusion method for the identifi­
cation of AFB1 in the samples. They improved the Dempster–Shafer (D-
S) method, and after eliminating the interfering factors, the THz ab­
sorption coefficients of different AFB1 concentrations were measured.
Their technique successfully quantified AFB1 in all samples (with 94%
accuracy). To quantify AFB1 in acetonitrile, Ge et al. (2016b) analyzed
THz absorption data using chemometric methods and observed that
linear regression models were more precise for higher AFB1 con­
centrations (1000–50,000 µg/L) while nonlinear-regression-based
models showed more accuracy for lower AFB1 concentrations (1–50 µg/
L). Their THz-chemometric method successfully quantified AFB1 in corn
samples in < 5 s (Table 4). Although their method was faster than
chromatographic methods, the results are not satisfying enough to re­
place chromatographic methods with THz-based quantification. For
example, the limit of detection (LOD) of a liquid chromatography and
electrospray ionization coupled with mass spectrometry was 0.19 μg/kg
for both aflatoxins B1 and G1 and the overall recoveries for all four
aflatoxins ranged between 57.1% and 108.7% (Tan & Wong, 2013).
A combination of THz spectroscopy with an improved PLSR model
was used for the detection and quantification of a carcinogenic dye,
Auramine O (AO), in medicinal herbs (Zhang et al., 2017b). They used
two-dimensional correlation spectroscopy (2DCOS) to highlight the
spectral differences at specific concentrations, reduce the effects of
noise, improve the PLSR model, and increase the accuracy of the results
(Table 4). The new 2DCOS-PLSR resulted in a fast, accurate, and re­
agent-free quantitative analysis of AO. They also compared the PLS
model with the stacked partial least squares (SPLS) for the quantifica­
tion of AO (Zhang & Li, 2018). To calculate the specific contribution
value, they applied variable contribution sorting (VIP) scores to their
models. VIP-SPLS showed the best performance results for AO quanti­
fication (Table 4).
Three similar traditional herbal medicines were identified (with
high prediction accuracy of 99%) using a combination of chemometric
methods with THz spectroscopy (Zhang et al., 2017a). Later the group
used this technique to discriminate between poisonous and non-poiso­
nous herbs (Zhang et al., 2018a). They used extreme learning machine
(ELM) and Cuckoo Search (CS) algorithm to construct their
 L. Afsah-Hejri, et al.

Table 5
Soil inspection using THz imaging and spectroscopy techniques.
Application and product THz range Experiment details Findings References

Zinc sulfate and Copper 0.2–1.6 THz Mode-locked Ti: sapphire laser; THz emitter: coplanar stripline antenna on an SI-GaAs
sulfate in soil wafer; An aplanatic hyper-hemispherical silicon lens (to increasethe coupling efficiency)
and highly resistive silicon lenses (for focusing the beam); ZnTe detector; The system was
purged with N2, temperature 295 KCuSO4 and ZnSO4
Heavy metals in soil 0.1–1.1 THz The group designed and built the system; Mode-locked Ti: sapphire laserZnTe detector;
Designed two specific sample holders; Cu2+, Zn2+, Pb2+ and Cr3+ (at 50, 300 and
700 µg/ml); Soil sample: heated at 85 °C for 24 h, grinded for 5 min (particle
*Copper sulfate-polluted soil had three peaks at 1.568, 1.364, and 1.022 THz (Li et al.,2009)
*Zinc sulfate-polluted soil had absorption peaks at 1.568, 1.364, and 0.954 THz
*Absorption intensity increased with frequency increase
*Zinc sulfate-polluted soil had an average refractive index between 1.468 and
1.595
*THz-TDS is a useful method for characterization of heavy metals in the far-IR
region
*Soils contaminated with Cu2+, Zn2+, Pb2+ and Cr3+ showed different (Li et al,, 2011)
absorption fingerprints
*Heavy metal’s absorption was dose-dependent

12
size < 0.1 mm), soil layer thickness: 1.5 mm and 3 mm; System was purged with N2,
relative humidity < 5.2% for Cu2+ & Zn2+ and 0.5% for Pb2+ and Cr3+
Dieldrin, aldrin, and 0.2–1.8 THz Mode-locked Ti: sapphire laserZnTe crystal detector; Parabolic mirrors; System was
endrin in soil purged with N2, relative humidity < 1%, temperature = 298 K; Used Becke-
3–Lee–Yang–Parr (B3LYP) for calculations
Soil sensor 0.3–5 THz Yttrium Iron Garnet (YIG)-oscillator; Gaussian beam horn antenna; Made a specific
wedge sample holder; Soil sample: heated at 105 °C for 24 h, grinded (particle size = 25,
63, 355 and 500 μm); Soil layer thickness: 1 mm – 2 cm; Hidden objects: carrot, garden
bean, and asparagus; Transmission measurements at 1.6–2.5 THz
*Heavy metals can be quantified based on their absorption spectrum
characteristics
*Soil particles had high scattering effect that affected the
measurementsLOD = 50 µg/ml
*Time delays for pure soil = 2.4 ps, soil/aldrin mixture = 2.73 ps, soil/dieldrin (Song & Li, 2012)
mixture = 2.2 ps and soil/endrin mixture = 1.73 ps.
*Absorption coefficient of soil/aldrin mixture at 1.41 THz = 19.64 cm−1, at 1.57
THz = 20.91 cm−1, at 1.78 THz = 13.69 cm−1
*Absorption coefficient of soil/dieldrin mixture at 1.29 THz = 16.73 cm−1, at
1.4 THz = 18.85 cm−1, at 1.56 THz = 24.5 cm−1
*Absorption coefficient of the soil/endrin mixture is at 1.58 THz = 6.24 cm−1, at
1.67 THz = 12.58 cm−1
*THz spectroscopy can be used in quality evaluation of soil
*Compared regular dish sample holder with wedge holder (Dworak et al.
*Regular dish sample holder showed low reproducibility due to difficulties in 2011)
alignment and filling
*The wedge sample holder was very effective, and no calibration or position
adjustments were needed
*The absorption coefficient was independent of sample thickness
*Penetration depth at 340–360 GHz: > 2 cm
*Penetration depth at 1.5 THz: < 1 mm
Computers and Electronics in Agriculture 177 (2020) 105628
L. Afsah-Hejri, et al.
classification models. Later they verified the performance of the method
by comparing the fitness curve of the CS-KELM model with the genetic
algorithms (GA). CS-KELM showed the highest accuracy (Table 4). CS-
KELM had 100% accuracy in the classification of poisonous herb (Gel­
semium elegans) and an average accuracy of up to 99.33% in classifi­
cation of poisonous and non-poisonous herbs. They also showed that
using metamaterial resonator in THz spectroscopy can significantly
improve the sensitivity of the technique for the detection and identifi­
cation of herbs (Zhang et al., 2018b).
3. Soil Inspection
Soil pollution with heavy metals is a serious issue affecting the
quality of agricultural products, food and human health (Hajeb et al.,
2014a,b). Heavy metals are metal compounds with a relative den­
sity > 5, such as Pb, Hg, As, Cd, Cu, Ni, Cr, Zn, and F. Agricultural
products from heavy metal-polluted farmland usually contain heavy
metals. There is a strong need to detect heavy metals in the soil before
they enter the food chain through polluted crops. The first report on the
use of THz spectroscopy for the detection of zinc and copper in polluted
soil was published by Li et al. in 2009. Zinc sulfate-polluted soil showed
a different THz fingerprint from copper sulfate-polluted soil (Table 5).
Later, the group studied the feasibility of using THz spectroscopy for the
detection of two other heavy metal ions in agricultural soil. They re­
ported that each heavy metal showed a unique and dose-dependent THz
fingerprint. All four heavy metal ions (Cu2+, Zn2+, Pb2+, and Cr3+)
were detected at their lowest concentration of 50 µg/ml. Although THz
spectroscopy was reported as a useful tool for the detection of heavy
metals in agricultural soil, further research is needed to reduce the cost,
improve the sensitivity and increase the S/N ratio of the system (Li
et al., 2011). In another study, the group detected Pb2+ in soil using a
combination of THz spectroscopy with the GA-PLS model (r = 0.81 and
RMSEP = 58.75) (Li & Guo, 2013).
Other pollutants such as endrin, dieldrin, and aldrin, known as
persistent organic pollutants (POPs), may exist in the soil. Song and Li
(2012) used a combination of chemometric methods with THz spec­
troscopy to quantify three long half-life environmental pollutants. Un­
ique THz fingerprints were observed for endrin, dieldrin, and aldrin
(Table 5). They discussed phonon or inter-molecular vibrations and
intra-molecular collective motions based on DFT calculation. They
found more absorption peaks than what they have predicted and related
this difference to the following factors: a) the normal modes of single-
molecule did not apply for these pollutants and b) the temperature
difference between the experiment (at 298 K) and simulation (at 0 K)
measurements.
The majority of THz radiation is scattered by soil particles or in­
gredients, whereas the absorption spectrum of a diluted soil sample can
be used for the identification of soil fertilizers and contaminants (Lewis,
2017). Dworak et al. (2011) initiated a series of studies to analyze the
THz absorption coefficient of different soils for building a non-de­
structive soil sensor. To avoid problems associated with alignments and
filling, they designed a specific wedge sample holder and compared it
with the dish holder. The wedge sample holder was very effective, and
they reached a penetration depth of > 2 cm at frequencies between 340
and 360 GHz. Previous studies only detected buried objects under 2 mm
of sand (Dodson et al., 2005). Dworak et al. (2011) also distinguished
organic objects, such as fresh vegetables, from the mineral soil matrix.
THz images had good and clear contrast for different soil types. Their
sensor can be used for either imaging of buried objects in the soil or soil
analysis. Detection accuracy can be increased by using more powerful
sources and more sensitive detectors (e.g., heterodyne amplifier). More
13
Computers and Electronics in Agriculture 177 (2020) 105628
research is needed to solve difficulties related to soil penetration, spa­
tial resolution limitation, and influence of particle size and soil in­
gredients.
4. Seed inspection and insect damage measurement
THz spectroscopy has been used for non-destructive quality control
of seeds. Chua et al. (2004) reported one of the first applications of THz
spectroscopy in quality control of wheat (Table 6). Chua et al. (2004;
2005) investigated the relationship between moisture content and THz
absorption of whole-grain and crushed wheat. Their preliminary results
showed that THz sensors can be used for in-line moisture measurement
and quality inspection of grains. Healthy wheat with normal size em­
bryo can also be differentiated from wrinkled wheat (slightly budded
embryo) or necrosis wheat with the degraded embryo (pre-harvest
germinated) (Gua et al., 2013). Jiang & Zhang (2014) used THz spec­
troscopy to identify moldy, insect-infested, sprouted, and normal wheat
grains (Table 6). They applied Fast Fourier Transforms to the THz time
pulses and calculated the absorption spectra of 120 wheat samples
(Jiang & Zhang, 2014; Ge et al. 2014). Results of PLS, back-propagation
neural networks (BPNN), PCA-support vector machine (SVM) methods
were compared and the PCA-SVM model showed the best performance.
The performance of the PCA-SVM model with linear and polynomial
kernels was > 95%, and the prediction accuracy of this model for both
sprouting and normal wheat grains was 100%. They showed that
combination of THz spectroscopy with computational methods suc­
cessfully identified different wheat grains and this combination can be
used as a useful tool for non-destructive quality control of wheat, spe­
cifically mixed grains from different geographical origins. Typically,
wheat grains are stored at a moisture content between 8 and 10% to
prevent germination. Humidity increase results in wheat germination
and THz spectrum of wheat will change.
Jiang et al. (2016) studied the THz spectrum of wheat grains at
different stages of germination. They reported two thresholds, the first
at 6 h due to the release of α-amylase and the second between 24 and
36 h when α-amylase reached a steady state. They compared some
chemometric methods, such as PCA, PLSR, SVM, BPNN, least squares
support vector machines (LS-SVM) and showed that the LS-SVM model
had the highest prediction accuracy for classification of germinated
wheat grains at the early stage (at 6 h). To achieve an accurate classi­
fication, damaged grains (such as worm-infested and fungal-infected
kernels) and wheat grains from different geographical origins must be
tested. The group studied THz spectra of fungal-infected wheat grains at
different stages of mold growth (Jiang et al., 2015). Based on PCA re­
sults, six optimal frequencies (0.32, 0.59, 0.87, 1.0, 1.29, and 1.58 THz)
were selected for spectrum analysis. They constructed BPNN, PLSR and
SVM models based on the full spectra and used them together with the
information from optimal frequencies to discriminate between different
stages of mold infection. PCA-SVM model showed the highest overall
prediction accuracy (95%) for discrimination of moldy wheat grains.
Ge et al. (2015) used a combination of PLS and THz spectroscopy
and successfully differentiated between eight wheat varieties. They
compared two PLS models (absorption spectrum-based PLS model and
refractive index-based PLS model) and reported that the absorption
spectrum-based PLS model was more accurate for prediction of wheat
varieties between 0.2 and 1.5 THz (Table 6). The prediction accuracy of
the model was absorption-dependent. In general, all THz spectroscopy
methods are sensitive to the experimental environment. Factors such as
sample preparation process, experimental setup and background noise
affect the performance and accuracy of the prediction model. To avoid
the influence of these factors, Ge et al. (2015) performed three
 Table 6
Seed inspection and insect damage measurement using THz imaging and spectroscopy techniques.
Application and THz range Chemometrics Experiment details Findings References
product
L. Afsah-Hejri, et al.

Wheat grains 0.1–4 THz NA Ti: sapphire femtosecond laser; Parabolic mirrors and high-resistivity SI lens; ZnTe *THz absorption of whole-grain depended on the shape, size, and (Chua et al., 2004)
crystal detectorSample holder: PTFE + aluminum; Samples: whole wheat grain, orientation of grain (scattering effect)
crushed wheat grain (8, 12 and 18% moisture Content) *The THz absorption spectrum of whole wheat grain was observed
between 0 and 1 THz
*Crushed wheat samples showed an absorption spectrum in a wider
THz frequency range (0–2.5 THz)
*THz absorption increased at a higher moisture content
Crushed wheat grains 0.1–2 THz NA Sample holder materials: PTFE, clear Perspex and PTFE, clear OHP acetate, glass- *PTFE + aluminum sample holder was used for the moisture study (Chua et al., 2005)
clearpolypropylene, and quartz; Samples: crushed wheat grain (12, 14 and 18% *THz sensors can be used for in-line moisture measurement and
moisture Content), particles size < 45 mm diameter quality inspection of grains
Wheat quality 0.2–1.6 THz PCA Mode-locked femtosecond Ti-sapphire laser; The system was purged with N2, *Four types of wheat grains (normal whole grain,worm-eaten, (Ge et al., 2014)
PLS temperature = 292 K; Samples: normal whole grain,worm-eaten, sprouting wheat sprouting wheat grains, and moldy grains) were identified (Jiang & Zhang,
SVM grains, and moldy (Aspergillus niger contaminated) grains, samples moisture *PCA-SVM method showed the highest performance 2014)
BPNN content = 12.5%; Grinded samples were pressed to round slices: diameter = 13 mm, *Method accuracy = 95%Performance stability of the system was
PCA-SVM thickness = 1–1.5 mm demonstrated by the similarity of the waveforms in different tests
*PCA-SVM model with linear and polynomial kernels had
performance > 95%
*Prediction accuracy of PCA-SVM model was 100% for sprouting and
normal wheat grains
*Prediction accuracy of PCA-SVM model = 95% for all 4 types of
wheat grains
Wheat germination 0.2–2.5 THz PCA Both transmission or reflection modes; Femtosecond Ti: sapphire laser; *THz images showed that maltose and starch content of wheat grain (Jiang et al., 2016)
PLSR Photoconductive dipole antenna on an LT-GaAs wafer; ZnTe crystal detector; Two changed during germination
SVM metal parabolic mirrors; Samples: wheat grains, germination time: 0, 6, 12, 18, 24, 36, *Two thresholds were observed: 1) at 6 h due to the release of α-

14
BPNN and 48 h, removed after some time and dried to 10% moisture level amylase and 2) between 24 and 36 h when α-amylase reached a
LS-SVM steady-state
*Prediction accuracy of the PLSR model = 92.85%
*Prediction accuracy of the LS-SVM model = 93.57%
*Prediction accuracy of the BPNN model = 90.71
*Classification errors in the prediction set at the single-grain level:
7.15% for PLSR,6.43% for LA-SVM & 9.29% for the BPNN model
Moldy wheat grains 0.2–1.6 THz PCA Femtosecond Ti: sapphire laser; Photoconductive dipole antenna on an LT-GaAs *THz spectra of moldy what grains were acquired (Jiang et al., 2015)
PLS wafer; ZnTe crystal detector; Wheat samples: normal, slightly moldy, moderately *Optimal frequencies based on PCA results: 0.32, 0.59, 0.87, 1,
RSVM moldy, and seriously moldy 1.29,and 1.58 THz
BPNN *PCA-SVM showed the highest overall prediction accuracy (95%)
PCA-SVM *Prediction accuracy of PCA-PLSR = 93% and for PCA-BPNN = 87%
PCA-PLSR
PCA-BPNN
Wheat varieties 0.2–2.5 THz PLS Transmission mode; Mode-locked Ti-sapphire femtosecond laser; GaAs *Wheat samples showed featureless THz absorption spectra, but (Ge et al., 2015)
iPLS photoconductive antenna; silicon hyperhemisphericallens, Parabolic mirrors, ZnTe different varieties had different spectra
crystal detector; Sample: 8 wheat varieties (Aobiao, Jiamai, Zhouyuan 9369, DNS, *Chemometric methods were used to differentiate between these
Zhengmai 9023, Yunong 416, Zhoumai 27, and Jinan17 wheat) all harvested at the featureless spectra
same year; Pre-analysis treatment time = < 5 min; The system was purged with N2, *Absorption spectrum-based PLS model was more accurate for
relative humidity < 3%, and temperature 294 K prediction of wheat varieties between 0.2 and 1.5 THz (R2 = 0.987,
RMSEC = 0.759)
*For iPLS model, model performance was affected by the subinterval
range
*iPLS model with 8 interval variables had the best prediction results
for wheat varieties (R2 = 0.992, RMSECV = 0.967)
Maize 0.1–2 THz CPA Mai-Tai laser; Parabolic mirrors and ZnTe crystal detector; S/N ratio up to 600, *DNA samples showed different THz absorption patterns (Lu et al., 2005)
spectral resolution = 50 GHz; The system was purged with air, relative *Maize seeds were identified using a component pattern analysis
humidity < 30%, temperature = 22 °C; Samples: DNA samples from embryo and 3 method
different DNA (fish DNA, 958 DNA and 108DNA)
(continued on next page)
Computers and Electronics in Agriculture 177 (2020) 105628
L. Afsah-Hejri, et al. Computers and Electronics in Agriculture 177 (2020) 105628

NA: not applicable, N2: Nitrogen gas, PCA: principal component analysis, CPA: component pattern analysis, PLS: partial least squares, iPLS: interval PLS, PLSR: partial least squares regression, CA: cluster analysis, SVM:
replications under the same conditions. They employed iPLS analysis

(Wang & Guo, 2017)

(Li et al., 2014); (Li

for comparison between varieties and observed that the selection of the

(Tan et al., 2014)

subinterval range directly affected the performance of the iPLS model.

et al., 2010)
The best prediction results for wheat varieties achieved by the iPLS
References

model with 8 interval variables (R2 = 0.992, RMSECV = 0.967). They

recommended more research on the mixture of wheat varieties har­
vested in different years.
Lu et al. (2005) reported the first application of THz spectroscopy

*The living insect had higher absorption than dry weevil and nutmeat
*For refractive indices’ R2 = 0.9967 and RMSE = 1.0596 and for the
*Caoyuan series alfalfa had greater amplitudes (0.0565 and 0.05959)

*Different stages of insect life stage (larval, pupal and adult) could be
*Data from refractive indices between 0.1 and 2.2 THz were more for purity check and quality control of maize seeds. DNA of maize

*Infested wheat kernels had different THz pseudo-color images

*Location and size of the infestation reveled through the high-

*The system must be purged with N2 to avoid moisture effect

samples showed different THz absorption patterns. They applied spec­

*Nutmeat, inner separator and shell had different absorption
*Two alfalfa series showed different time delays (> 0.08 ps)

absorption coefficient’s R2 = 0.9906 and RMSE = 1.7789

trum information to THz images using the component pattern analysis

method to identify maize type. Their method had some shortcomings,
such as long imaging process, relative changes in laser pulses, and water
coefficients at frequencies higher than 1.2 THz

absorption by the samples.

*THz-TDS can be used for maize identification

Wang and Guo (2017) used both amplitude and time delay differ­

support vector machine, BPNN: back propagation neural network, RMSECV: root mean square errors of cross-validation, RMSEP: root mean square errors of prediction.
depending on the life stage of the insect
*THz cannot penetrate the whole pecan

ences for the differentiation of alfalfa varieties. As differences in time

accurate for the classification of alfalfa

differentiated with THz spectroscopy

and amplitude are related to refractive indices and THz absorption

coefficients, they used this information to differentiate between two
series of alfalfa. They used PLS and cluster analysis to verify their
classification and achieved R2 = 0.9967 and RMSE = 1.0596 for re­
fractive indices’ and R2 = 0.9906 and RMSE = 1.7789 for the ab­
contrast THz images
than gannong series

sorption coefficient. They showed that data from refractive indices

between 0.1 and 2.2 THz are more accurate for the classification of
alfalfa varieties with little characteristic differences.
Findings

Insect-infestation of seeds affects the quality of grains. Li et al.

(2010) investigated the feasibility of using THz-TDS spectroscopy for
the detection of insect damage and quality control of pecans. Live and
CO2 laser-pumped THz laser; Sample: wheat kernels (un-infested and infested kernels
Mode-locked Ti: sapphire femtosecond laser; Parabolic mirrors and high-resistivity SI
lens; Designed a specific sample holder; Pecan samples: nutmeat, inner separator and

3 mm, length = 2 cm X width = 1 cm; Insects: dry pecan weevil and alive Manduca

incubated at 30 °C, at RH = 70%), Time period = 15 daysInsect: Sitophilus zeamais

dry insects showed different THz spectrum and were distinguished in

detector; Sample: Six kinds of alfalfa (gannong series and caoyuan series), grinded

shell; Whole pecan: length = 4.1 cm × width = 2.2 cm; Slice thickness: 1, 2 and

layers of nutmeat (Li et al., 2014). Insect contamination in the whole

photoconductive antenna, Parabolic mirrors, ZnTe crystal and Wollaston prism

pecan couldn’t be detected due to the THz penetration limitation. Tan

et al. (2014) used CW THz spectroscopy for the detection of insect-
into powder, sieved (100-eyes mesh), dried at 60 °C for 5–6 h), pellets
Transmission mode; Mode-locked Ti-sapphire femtosecond laser; GaAs

infested wheat. Infested wheat kernels had different THz pseudo-color

images depending on the life stage of the insect. They successfully
distinguished the location, size and life stage (e.g., larval, pupal and
adult) of insect-infested wheat kernels. More research is needed to­
wards using more powerful sources and increasing the sensitivity of the
THz systems for insect detection.

5. Detection of transgenics and genetically modified crops

(Motschulsky) (Coleoptera: Curculionidae)
thickness = 1.19–1.21 mm, r = 30 mm

There are some concerns associated with the consumption of ge­

netically modified (GM) products. Methods for identification of GMs are
DNA-based, destructive, expensive, and time-consuming. Currently,
there is no easy, accurate and reliable method for the identification of
GM seeds. Liu et al. (2015a) used a combination of THz spectroscopy
sexta (2-weeks old)
Experiment details

with chemometric methods for the identification of GM cotton. GM

cotton had very similar THz spectrums, and they used pattern re­
cognition methods to differentiate between them. Active learning affi­
nity propagation clustering algorithm (ALAP) was used to optimize the
training set, and SVM was employed to build the classification model.
ALAP-SVM was then compared with three SVM algorithms (random
Chemometrics

SVM, entropy SVM, and uncertainty SVM) and showed higher classifi­
cation accuracy. The recognition rate of the ALAP-SVM model was
97.79% for GM cotton. In another study, the group differentiated be­
PLS

NA

NA
CA

tween parent and transgenic cotton seeds (Liu et al., 2015c). They used
SVM based on the structural risk minimization principle and Vapnik–­
0.1–1.6 THz
THz range

0.2–2 THz

0–2.5 THz

Chervonenkis theory to minimize the generalization errors. A combi­

nation of GA with SVM showed the highest recognition rate of 96.67%
between parent and transgenic cotton seeds. They also combined THz
spectroscopy with weighted discriminate analysis (Liu et al., 2017) and
Insect damaged wheat
Insect damaged Pecan
Table 6 (continued)

weighted linear discriminant analysis (WLDA) (Liu et al., 2015d) for the
identification of transgenic cotton seeds (Table 7). WLDA, an improved
Application and

Alfalfa varieties

linear discriminate analysis method, increased the identification rate of

their method to 98.3%. They showed that the identification rate of their
product

WLDA method was higher than their previous ALAP-SVM method for
the same transgenic cotton. A multi-population genetic algorithm

15
 Table 7
Detection of transgenics and genetically modified crops using THz imaging and spectroscopy techniques.
Application and product THz range Chemometrics Experiment details Findings References

Genetically modified 0.2–1.2 THz PCA Ti-sapphire femtosecond laser; Parabolic mirrors, and ZnTe crystal detector; The *Genetically modified cotton was identified using a combination of (Liu et al., 2015a)
L. Afsah-Hejri, et al.

cottons ALAP-SVM system was purged with N2, relative humidity < 2%, and temperature 292 K; THz spectroscopy with ALAP-SVM model
Sample: 8 different GM cotton (Lumianyan 28, 29, and 36, Xinqiu k638, 107, New *Classification accuracy of ALAP-SVM was more than SVM
Luzhong 6, Zhongmian 28, and Yinmian 8) algorithms (Random SVM, Entropy SVM, and Uncertainty SVM)
*Recognition rate of ALAP-SVM model = 97.794%
Transgenic cotton seeds 0–1.5 THz PCA Ti-sapphire femtosecond laser; Parabolic mirrors and ZnTe crystal detector; The *Different transgenic cotton seeds showed unique THz spectrums (Liu et al., 2015c)
GM-SVM system was purged with N2, relative humidity < 2%, and temperature = 292 K; *The first 3 principal components (PC1, PC2, and PC3) accounted
Sample: 8 different GM cotton: (Ken GK12 is its parent and transgenic cotton Guan for > 97.467% variance in the data set
4, Hang 5518 and LuKen 33) *PC1, PC2, and PC3 explained the most spectral variations related
to the origin
*GA-SVM pattern recognition method had a recognition rate of
96.67% for discrimination of parent from transgenic seeds
Transgenic cotton 0.1–1.2 THz PCA-WDA Ti-sapphire femtosecond laser; Relative humidity < 0.2%, temperature = 292 K; *WDA model had identification rate = 92.5% for Coker 312 (Liu et al., 2017)
Sample: transgenic cottons (Coker 312, HD-73, and HD-1) transgenic cottons
*WDA model had identification rate = 89.4% for HD-1transgenic
cottons
*WDA model had identification rate = 89.7% for HD-73transgenic
cottons
Transgenic cottons 0.2–1.2 THz PCA-WLDA Ti-sapphire femtosecond laser; Parabolic mirrors and ZnTe crystal detector; The *WLDA is an improved linear discriminate analysis method (Liu et al., 2015d)
system was purged with N2, relative humidity < 2%, and temperature = 292 K; *WLDA increased the identification rate to 98.3%
Sample: 8 different GM cotton (Lumianyan 28, Xinqiu 107, New Luzhong 6,
Zhongmian 28, and Yinmian 8)
Transgenic cotton seeds 0.2 and 1.2 THz PCA Transmission mode; Femtosecond laser; The system was purged with dry air, *PCA reduced the dimensions of THz absorption spectrum (Qin et al., 2017a)
MPGA-SVM relative humidity < 4%, and temperature = 295 K; Sample: GM cotton *MPGA-SVM (with dimensionality of 12) had recall > 97.9%,
DA (Lumianyan 36, Lumianyan 18, Yinmian 8, Xinqiu k638); MPGA-SVM was precision = 96%, F-score = 0.9796, and accuracy = 99%

16
KNN compared with discriminant analysis (DA), k-nearest neighbor (KNN) and decision *Accuracy of KNN = 95.3%
DT trees (DT) *Accuracy of DT = 94.8%
*Accuracy of DA = 86.5%
*Performance of MPGA-SVM was better than the performance of
traditional classifiers
Transgenic cotton seeds 0–1.2 THz PSO-SVM Ti-sapphire femtosecond laserThe system was purged with N2, relative *Algorithm-based methods were used to reduce the amount of (Li et al., 2016)
APSO-SVM humidity < 2%, and temperature = 292 KSample: 165 samples from GM cotton calculation on THz spectrum data
(Lumianyan 36, Xinqiu k638, New Luzhong 6) *Identification rate of PSO-SVM = 89.3%
*Identification rate of APSO-SVM = 97.3%
Transgenic cotton seeds 0–1.2 THz SVM Mode-locked Ti, sapphire femtosecond laser; InAs emitter, two pairs of gold- *All three transgenic cotton seeds showed unique THz absorption (Liu & Fan, 2016)
PSO-SVM coated parabolic mirrors, ZnTe crystal detector, with a Wollaston prism (PBS), a spectra
ADPSO-SVM quarter-wave plate (QWP), and a pair of photodiodes; The system was purged with *Lumianyan 36 had absorption at 0.57, 0.8 and 0.98 THz
N2, relative humidity < 2%, and temperature = 21 °C; Sample: transgenic cotton *Xinqiu k638 had peaks at 0.57, 0.75 and 0.94 THz
seeds (New luzhong 6, Xinqiu k638 and Lumianyan 36) *New luzhong 6 had a peak at 0.55 THz
*Combination of THz spectroscopy with ADPSO-SVM accurately
detected transgenic cotton seeds
*Recognition rate of ADPSO-SVM = 96.97%
*The recognition rate of PSO-SVM = 90.90%
Transgenic cottons 0.2–2 THz Random-SVM Femtosecond laser; The system was purged with dry air, relative humidity < 2%, *SVM based on affinity propagation clustering algorithm on the (Liu & Kan, 2018)
BVSB-SVM and temperature = 292 K; Sample: 5 varieties of Gossypium hirsutism L (2 Non-GM THz spectrum of transgenic cotton
GA-SVM varieties, 3 GM varieties) *Human errors were reduced and identification accuracy was
improved
*The random-svm method has 17 misjudgments and total
recognition rate = 80%
*BVSB-SVM had 11 misjudgments and recognition rate of 87.78%
*GA-SVM had 8 misjudgments and recognition rate = 91.11%
*SVM based on affinity propagation clustering algorithm resulted
in 4 misjudgments and total recognition rate = 95.56%
(continued on next page)
Computers and Electronics in Agriculture 177 (2020) 105628
 Table 7 (continued)

Application and product THz range Chemometrics Experiment details Findings References

Transgenic sugar beets 0.2–1.5 THz PCA Femtosecond laser; The system was purged with N2, relative humidity < 2%, and *The cumulative contribution rate of PC1, PC2, and PC3 (Liu et al., 2015)(Liu
HSN temperature = 292 K; Sample: parent and transgenic sugar-beets, baked at 50 °C was > 97.28% et al., 2015b)
L. Afsah-Hejri, et al.

for 48 h, sliced (thickness = 1.5 mm and diameter = 1.2 cm) *HSN model identified, classified and differentiated between
parent and transgenic sugar-beets
*The average correct recognition rate was > 95%
*The method had a very little false recognition, average correct
rejection rate = 95.75%
Transgenic sugar beets 0–1.5THz PCA Sample: parent and transgenic sugar-beets (purity > 99%) 20 GM samples and *PCA-WLDA: rapid, non-destructive identification of transgenic (Liu, 2017)
WLDA 30 non-GM organisms
PCA-WLDA *The recognition rate of PCA-WLDA for transgenic sugar
beet = 100% (both in original and cross-validation groups)
*The recognition rate of LDA model = 88.9% in the original
group, and 86.7% in cross-validation
Transgenic sugar beets 0.2–1.2 THz. PCA Femtosecond laser; The system was purged with dry air, relative humidity < 2%; *DPLS method produced the finest classification results (100% (Chen et al., 2016)
DA Sample: parent and transgenic sugar-beets (purity > 95%) 36 GM samples and successful classification for both GM and non-GM sugar beets)
DPLS 48 non-GM *DPLS had R2 = 100, RMSECV = 100 for classification
Genetically modified 0–1.5 THz SVM-DA Femtosecond laser; Sample: parent and transgenic sugarcanes (purity > 99%) 30 *The highest identification rate of 98% was achieved with PLS-DA (Liu et al., 2018)
sugarcane LDA GM samples and 30 non-GM model
PLS-DA
Transgenic cotton seeds 0–1.5 THz NA SRR (gold layer on a 0.5 mm thick p-Si substrate); Thin liquid layers *The redshifts in the THz response peak depended on the type of (Liu et al., 2015e)
and sugar beets (thickness = 50 nm); Femtosecond laser,; Parabolic mirrors, and ZnTe crystal liquid films
detector; System was purged with N2, relative humidity < 2%, and *Transgenic sugar beets and transgenic cotton seeds showed
temperature = 292 K; Sample: parent and transgenic sugar-beets and cotton seeds different degrees of redshift from their parents
*Transgenic products were identified based on their SRR THz
response peaks
Transgenic rice 0.1–2.6THz PCA Femtosecond laser; GaAs photoconductive antenna; ZnTe electro-optical crystal *Transgenic samples had a higher average transmittance between (Xu et al., 2015)

17
DA detector; System was purged with N2; rRelative humidity < 1%, and 0.2 and 0.4 THz
PLS temperature = 23 °C; Sample: parent (Ming Hui 63) and transgenic rice *GM rice samples showed a huge difference from parent seeds at
containing Cry1Ab protein (Hua Hui 1)Tests were done in triplicate 0.4 THz
*DA model successfully discriminated transgenic from non-
transgenic rice with 89.4% accuracy for their calibration and
85.0% for the validation set
Transgenic rice 0–5 THz PCA Reflection mode; Femtosecond laser; Sample: parent (Wanjing97 rice seeds) and *Combination of the 1st derivative pre-treatment with RF model (Liu et al., 2016b)
PCA-BPNN transgenic (Bt) rice seeds (Bt Wanjing97) resulted in prediction accuracy = 96.67%
LS-SVM
RF
SNV
Transgenic rice 0.1–4 THz SR Reflection mode; Femtosecond laser; Sample: parent (Wanjing97 rice seeds) and *Transgenic samples had lower reflection amplitude between 0.1 (Hu et al., 2017)
RF transgenic (Bt) rice seeds (Bt Wanjing97); System was purged with dry air, relative and 1.2 THz
LS-SVM humidity < 3%, and temperature = 22 °C *SR-RF model works well for discrimination purposes (100%
SR-RF accuracy in calibration set and 95% accuracy in prediction set)
Transgenic soybean 0–4 THz PCA Both reflection and transmission modes; Fiber-Coupled THz system; Sample: *Pre-treatment of THz spectra with SNV in combination with LS- (Liu et al., 2016a)
LS-SVM conventional soybean seeds (Wandou 28), Glyphosate-resistant GM seeds SVM resulted in 88.33% accuracy in the validation set
SNV (DP4546RR), and their hybrid descendants (DP4546RRxWandou 28)
PCA-BPNN

NA: not applicable, N2: Nitrogen gas, PCA: principal component analysis, PLS: partial least squares, SVM: support vector machine, BPNN: back propagation neural network, DA: discriminant analysis, BVSB: best verses
second best, WDA: weighted discriminate analysis, WLDA: weighted linear discriminant analysis, LDA: linear discriminant analysis, KNN: k-nearest-neighbors, APSO: adaptive particle swarm optimize, ADPSO: adaptive
dynamic particle swarm optimization, GA: genetic algorithm, MPGA: multi-population genetic algorithm, CM: confusion matrix, DT: decision trees, HSN: hyper Sausage Neuron, DPLS: discriminant partial least squares,
RF: random forest pattern recognition method, SR: sparse representation, SNV: standard normal variate transformation, RMSEC: root mean square errors of calibration, RMSECV: root mean square errors of cross-
validation
Computers and Electronics in Agriculture 177 (2020) 105628
L. Afsah-Hejri, et al.
(MPGA) was also used for tuning the parameters of SVM. Qin et al.
(2017a) considered more evaluation criteria, such as average accuracy
and confusion matrix, on a large number of transgenic cotton seeds
(1112 transgenic cotton seeds samples). MPGA-SVM had a recall
of > 97.9%, with 96% precision, and 99% accuracy in discrimination of
transgenic cotton seeds. The 95th percentile of accuracy for MPGA-SVM
was > 95%. MPGA-SVM showed a better performance than the tradi­
tional classifiers (Table 7).
Most of the chemometric methods are based on complex calcula­
tions on the THz spectrum data. Furthermore, it is not easy to set up the
parameters for the SVM model. Li et al. (2016) combined SVM with an
adaptive particle swarm optimization (APSO) method and built a THz-
based classification method for transgenic cotton seeds. A combination
of SVM with particle swarm optimize (PSO) was compared with APSO-
SVM model, and APSO-SVM showed the highest identification rate of
97.3%. Despite the reduced amount of calculations in APSO-SVM
model, its identification rate was less than the identification rate of
ALAP-SVM model (97.79%) in their previous study.
Experiment conditions are continually changing in a dynamic en­
vironment. Li et al. (2016) proposed a novel THz spectroscopy re­
cognition method that is less affected by experiment conditions and
transgenic cotton seeds showed unique THz absorption spectra under
the new conditions (Table 7). Ninety transgenic cotton samples were
divided into two groups, one group as the training set for model cor­
rection and the other as the test set for prediction purposes. Using THz
spectrum data, they performed adaptive dynamic particle swarm opti­
mization (ADPSO)-SVM in which the algorithm precepted the changes
of the external environment and updated the particle swarm to acquire
a globally optimal solution. The recognition rate of ADPSO-SVM model
was 96.97% (about 6% higher than the PSO-SVM model).
Manual labeling of the training samples is one of the problems in
establishing an identification model. Human error during the labeling
process will reduce the identification accuracy of the model. To solve
this problem, Liu & Kan (2018) used the affinity propagation clustering
algorithm to facilitate both the cluster analysis and labeling process.
With this technique, SVM training data will be constantly updated with
the iterative process of the clustering algorithm. They showed that the
following parameters affect the performance of the classifier in a
modeling process: data distribution on the classifier, class re­
presentative points of the model, and the clustering center. They
compared their method with three different discrimination models
(such as random support vector machine, best vs. second-best, and
genetic algorithm support vector machine) and showed that SVM based
on affinity propagation clustering algorithm resulted in only four mis­
judgments and had a high recognition rate of 95.56% for transgenic
cotton (Table 7). Their method improved identification accuracy and
reduced human errors.
There have been some reports on the detection of defects in sugar
beet seeds using THz spectroscopy (Gente et al., 2016). Liu et al. (2015,
2015a) investigated the feasibility of using THz spectroscopy for the
identification of GM sugar beet seeds. Since parent and transgenic sugar
beets show very similar THz transmittance spectra, Liu et al. (2015,
2015b) used a pattern recognition method for identification purposes.
First, they used PCA to create a 2D spatial distribution graph of the
samples and then used hyper sausage neuron (HSN), a specific two-
weights neuron, to identify transgenic beets (Table 7). They successfully
identified, classified, and differentiated between parents and transgenic
sugar beets, with an average correct recognition rate of > 95%. HSN
model had a small false recognition rate for transgenic sugar beets. The
group showed that a combination of the THz spectroscopy with the
WLDA resulted in a 100% recognition rate for transgenic sugar beets
(Liu, 2017). It was also shown that a combination of THz spectroscopy
with discriminant partial least squares (DPLS) model produced the best
classification results for both GM and non-GM sugar beets (Table 7)
(Chen et al., 2016). For sugarcane, a combination of the THz spectro­
scopy with PLS-DA resulted in the highest identification rate of 98% for
18
Computers and Electronics in Agriculture 177 (2020) 105628
genetically modified sugarcanes (Liu et al., 2018).
A split-ring resonator (SRR), a type of metamaterials used in some
THz systems, has unique properties and potential to be used for the
identification of transgenics. THz response peak can be affected by the
dielectric constant around SRR, and any change in the dielectric con­
stant around SRR will result in THz peak redshift. GM products can be
identified based on the degree of redshift, and Liu et al. (2015e) used
this phenomenon for the identification of transgenic cotton seeds and
transgenic sugar beets. They measured the changes in the dielectric
constant around SRR when a very thin liquid membrane of the sample
was used. They differentiated parents from GMs based on their SRR THz
response peaks.
Cry1Ab protein protects rice seeds against pests. Transgenic rice
seeds containing Cry1Ab protein has been subjected to THz spectro­
scopy for identification and differentiation purposes (Xu et al., 2015).
Higher average transmittance differences were observed between 0.2
and 0.4 THz. Transgenic rice seeds showed a considerable difference
from parent seeds at 0.4THz. The transmittance spectrum of samples
was analyzed using linear discriminant analysis (DA). DA model suc­
cessfully discriminated transgenic from non-transgenic rice (Table 7). In
another study, transgenic rice seeds containing Bt gene, a gene that
encodes toxin proteins against lepidoptera pests, were identified using
random forest (RF) model (Liu et al., 2016b). First, THz images were
pre-treated with methods such as 1st and 2nd derivative and standard
normal variate transformation (SNV), and then subjected to back­
propagation neural network (BPNN), PCA, LS-SVM, and RF models.
Results showed that the combination of the first derivative pre-treat­
ment of THz frequency-domain spectra with RF model resulted in a
prediction accuracy of 96.67% for transgenic rice seeds and prediction
accuracy of 100% for non-transgenic rice seeds.
Hu et al. (2017) used sparse representation (SR) to reduce the fea­
ture dimension and extract THz spectral features of transgenic rice
seeds. Later, they applied an RF method to their THz data and com­
pared it with the LS-SVM method. They showed that SR-RF had a higher
accuracy, 95% in prediction set and 100% in the calibration set for
discrimination of transgenic rice seeds. Pre-treatment of THz spectra
with SNV in combination with LS-SVM successfully discriminated
transgenic soybeans with 88.33% accuracy in the validation set (Liu
et al., 2016a). All of the above-mentioned studies showed that the
combination of THz spectroscopy with chemometric methods could be
used as a rapid, non-destructive and accurate technique for the iden­
tification of transgenic seeds without any sample preparation.
6. Quality control and adulteration detection
THz spectroscopy has been used for the quality evaluation of agri­
cultural products. An in-house-built THz system was used for the non-
destructive detection of living insects in pecan (Li et al., 2010). Live and
dead insects were detected based on their absorption coefficients at
frequencies higher than 1.2 THz. Living insects showed higher THz
absorption than dry insects and nutmeat. Defects in ginseng were also
detected using THz spectroscopy (Kim et al., 2012b).
Xi-Ai et al. (2011) evaluated the quality grade of four types of green
tea based on their absorption spectrum and refractive indices. Because
of the high dimensionality of the inputs, the first naive Bayes classifier
technique was applied to the spectral data, and then backpropagation
artificial neural network was used for classification purposes. They
compared five classification algorithms and showed that LS-SVM had
the best classification results for green tea with a recognition rate of
98.75%.
The moisture content of grains is a critical factor affecting the sto­
rage of seeds. Chua et al. (2005) showed that THz spectroscopy could be
used as a non-destructive and effective tool for the measurement of
moisture in crushed grains. Some preservatives in grains have also been
detected with this technique (Table 8).
L. Afsah-Hejri, et al. Computers and Electronics in Agriculture 177 (2020) 105628

7. Crop yield estimation

(Kim et al., 2012b)

(Chua et al., 2005)

(Xi-Ai et al., 2011)

(Ge et al., 2016a)

(Li et al., 2010) THz spectroscopy has the potential to be used for active inspection
References

of water content in plants and crop yield estimation (Etayo et al., 2010).
Federici et al. (2009) performed THz imaging over some curved sur­
faces and used THz-TDS imaging to differentiate between grape berries,
flower, stem, and leaves. THz images from curved and flat surfaces were

*Absorption peaks of potassium sorbate and sorbic acid were observed

*Live and dead insects were detected in different parts of pecan (shell,

*Absorption coefficients of inner separator, shell and nutmeat showed

*Sodium diacetate showed absorption peaks at 1.08,1.29 and 1.58 THz

*Higher transmitted power (up to 6 times) than of the system with a

*THz images were more clearly recognizable for samples containing

obtained in reflection mode via THz Gouy phase shift (Fig. 4). Curved

*THz absorption peaks at low frequencies were assigned to inter-

*Samples at 18% moisture level had the highest THz absorption

surfaces such as fruits displaced the image focal plane from the detector
*80 samples of Chinese green tea were classified based on their
*Living insects had higher THz absorption than dry insects and

molecular, intra-molecular collective motion or phonon modes

*LS-SVM showed better classification results: recognition plane. They measured this Gouy phase shift and showed that berries,
stems, and leaves had different reflectance spectra between 0 and 1 THz
significant difference at frequencies higher than 1.2 THz

(Table 9). They tested their method in a vineyard and distinguished

fruit from stems and leaves. Their technique detected grape berries as
early as their appearance in June. They also detected a grape berry
inhomogeneous tissues such as red ginseng
hidden behind leaves. Workable standoff distance (1 m in their study)
refractive index and absorption spectrum

at 0.97 THz and1.49 THz, respectively

was one of the limitations of their method. Although they didn’t ela­
*High spatial resolution up to 500 μm

borate on the reasons for the limitation of standoff distance, it is pos­

sible that this limitation caused by the limitation of the frequencies in
nutmeat and inner separator)

this range and specification and type of equipment that they used in
their experiments. More research is needed to measure the standoff
distance for high-water-content crops.
pinhole aperture

According to Federici et al. (2009), THz spectroscopy can be used

rate = 98.75%

for fruit differentiation purposes. Fruits with high-water-content, thin-

skinned crops such as blueberries, cherries, and plums can easily be
Findings

nutmeat

detected with this method, but the main question is to what extent can
this method be applied in crop yield estimation? Canopy size was an­
other limitation of their technique. THz spectroscopy is only effective
In-house designed and built a THz system with a special sample holder; Mode-locked Ti: sapphire
femtosecond laser; Frequency resolution = 1 GHz; Signal-to-noise (S/N) ratio = 10000:1; Living

Mode-locked femtosecond laser; GaAs crystal emitter and ZnTe crystal detector; Sample pellets:

for thin-canopy crops, and measurements will be complicated for thick

Mode-locked; Ti: sapphire laser; ZnTe electro-optic crystal; Time-domain S/N ratio = 5000:1;

Ti– Sapphire laser, parabolic mirrors and ZnTe detector; System was purged with N2; Special

canopy crops due to the ‘shadowing’ effect. Further research is needed

insects (Manduca sexta, two weeks old)Pecan insects (Weevil); Sample thickness: 1–3 mm,

sample holder; Sample: crushed wheat grains with moisture level: dry, 12, 14, and 18%

to increase the sensitivity of the method and also the possibility of real-
Preservatives: benzoi acid, sorbic acid, sodium benzoate, potassium sorbate, sodium

time THz imaging.

3. Current pitfalls of THz technology and its future outlook

THz spectroscopy is a non-invasive, non-destructive, safe and con­

venient method with great flexibility, however, THz technology has
some limitations and drawbacks such as high cost of THz source &
detector, strong absorption of THz radiation by water, scattering effect,
limited penetration, thickness limitation, low LOD for chemicals, lim­
Gunn oscillator; Horn antenna; GaAs Schottky diode

ited sensitivity, and application specificity (Afsah-Hejri et al., 2019).

The agricultural-specific limitations include:
thickness = 1.08 mm and diameter = 13 mm

Strong absorption of THz radiation by water: The water content

of a plant leaf is an indicator of drought stress and can potentially be
THz spectroscopy and imaging for quality control and adulteration detection.

dehydroacetate, and sodium diacetate

used for irrigation management; however, the thickness of the leaf is a

function of its water content (Jördens et al., 2009). THz images of plant
width = 1 cm, length = 2 cm

leaves contain absorbance information from both plant leaf and the
water in the leaf. Factors such as leaf position, thickness, age, cellulose
content, and texture affect the water content of the leaf. Performing CW
Experiment details

THz spectroscopy can lessen the effect of these factors as it offers a

larger S/N ratio and a dynamic range below 0.4 THz (Afsharinejad
et al., 2017b). Some studies showed that a combination of THz imaging
with some algorithms and chemometric methods could be used as a
useful tool for the classification of wet and dry leaves, drought stress
monitoring and water content measurements (Zhang et al., 2008;
0.2–1.5 THz

Hadjiloucas et al., 2002). Although the combination of the THz spec­

THz range

0.2–2 THz
0–2 THz

0.2 THz

troscopy with mathematical modeling methods showed good accuracy

0-5THz

for quantification of leaf water content in the field (Nie et al., 2017),
more research is needed to turn it into a practical method for prediction
Quality evaluation of pecan

of water content at the field level. Also, more research is needed to find
Moisture of crushed wheat
Quality grade of green tea
Application and product

the workable standoff distance for different high-water-content crops

Preservatives in grains

and to understand and compare the behavior of different plant species

Defects in ginseng

under dehydration and drought stress. In addition, a statistically large

number of plant samples must be studied to make a realistic estimate
and modeling for each plant.
Table 8

Using a quasioptical measurement set-up in moisture control studies

can increase the resolution of the images and reveal the stalked layers

19
L. Afsah-Hejri, et al.
of leaves (Etayo et al., 2010). A THz quasi-TDS system, measuring the
water status dynamics of the plants, seems an excellent candidate for
building an inexpensive and compact THz device for drought stress
monitoring (Gente & Koch, 2015). Higher THz frequency range de­
clining the size of the dipole at both transmitter and receiver antennas.
Therefore, the frequency range above 0.3–0.4 THz can reduce the size
of THz passive electromagnetic elements from millimeter to micrometer
scale. The RF MEMS technology can offer enhanced performance to
build antennas in the micrometer scale (Lucyszyn and Pranonsatit,
2013; Oberhammer, 2016; Basak et al., 2017; Shah et al., 2017) that
leads to a more compact solution.
Low sensitivity and limited LOD for pesticides: The high corre­
lation between the concentration of pesticides and the 2nd derivative
value of their THz spectrum showed that pesticides could be quantified
based on their THz spectrums (Suzuki et al., 2010, 2011; Ma et al.,
2013; Chen et al., 2015); however, these techniques have some short­
comings, such as low sensitivity and lengthy sample pre-treatment
procedures. Some background noise was also reported due to the effect
of food components such as protein, cellulose, and starch. The recovery
range of the THz-based method for methomyl was between 78% and
96.5%, and the sensitivity of the technique was low and couldn’t reach
the regulatory limits set for the detection of methomyl in cereals (Baek
et al., 2016). The best LOD for methomyl (LOD = 8 mg/kg) was re­
ported by Lee et al., (2016) for a nanoscale metamaterials-based THz-
TDS technique. The LOD of THz-based pesticide detection methods is
lower than the conventional pesticide detection techniques. For ex­
ample, a luminescent metal–organic framework method showed a very
low LOD (0.12 µg/L) for parathion methyl (Xu et al., 2018).
Limited LOD for harmful chemicals and toxins: Several studies
showed that combination of THz spectroscopy with chemometric
methods rapidly detected and quantified harmful chemicals and toxins
in food and agricultural samples. Although the quantification time of
the THz-chemometric method is less than that of immunoassay or
chromatographic methods, the results are not yet satisfying enough to
replace the traditional analytical methods with THz-based quantifica­
tion (Ge et al., 2016b; Chen & Lijuan, 2014). Using the combination of
chemometric methods with THz spectroscopy, the best reported LOD
for the detection of AFB1 was 1 μg/kg (Liu et al., 2019b). Although
immunoassay methods and chromatographic techniques have a long
sample preparation time, they have reliable LOD for chemicals. A
20
Computers and Electronics in Agriculture 177 (2020) 105628
Fig. 4. (1.A) visible image of three grapes, (1.B)
corresponding THz image, (1.C) THz image of a
grape, and (1.D) a grape behind a leaf. (2.A) THz
time-domain waveforms of berry leaf (first trace on
top), berry flower (second), reference, (third), and
stem (bottom trace), (2.B) predicted THz reflection
from berry (top trace), reflected THz waveforms of
a berry (middle), and reference waveform (bottom
trace) by Federici et al. (2009).
fluorescent probe-based method had LOD = 3.1 pg/mL for AFB1 (Wang
et al., 2019) and the LOD of a real-time immune-PCR method was
0.03 ng/mL for total aflatoxins (Ren et al., 2019).
Suggested methods to increase the accuracy of the THz-based
quantification methods include: 1) using two-dimensional correlation
spectroscopy to reduce the effects of noise and improve the mathema­
tical models (Zhang et al., 2017b), 2) using metamaterial resonator to
improve the sensitivity of the method for the detection and identifica­
tion of harmful compounds (Zhang et al., 2018b), 3) performing pre-
treatments on high-dimensional data sets to omit the unnecessary in­
formation from THz signals (Liu et al., 2019a), and 4) improvement of
the signal processing methods, specifically for large data processing.
Besides, the detection of various toxins and harmful compounds re­
quires the implementation of different chemometric methods that need
to be improved accordingly. Toxins and harmful compounds require
rapid and inline detection, and new THz spectroscopy systems should
meet this requirement.
Scattering Effect due to soil particles and ingredients: The
physical variation of a soil sample, such as inhomogeneity, influences
the refractive index and adversely affects the quality monitoring pro­
cess (Yi et al., 2018). The majority of THz radiation is scattered by soil
particles or ingredients. Usually, the absorption spectrum of a diluted
soil sample is used for the identification of fertilizers and contaminants
(Lewis, 2017). Using a soil sensor with a wedge sample holder can help
to overcome the low reproducibility of the technique due to the
alignment of sample holders in soil studies (Dworak et al., 2011).
Penetration limitation is a significant problem in soil studies, and
usually buried objects can only be detected 2 mm below the surface of
the sand layer (Dodson et al., 2005). Studies showed that the wedge
sample holder was very effective and reached a penetration depth
of > 2 cm at frequencies between 340 and 360 GHz. Detection accuracy
of THz-based techniques can be increased by using a more powerful
source and a more sensitive detector (e.g., heterodyne amplifier). Siles
et al. (2018) presented a new terahertz system with an a high output
power in the 160 GHz to 1.6 THz range. Overall, the power consump­
tion of the existing commercial systems is low enough for applications
that require portable or mobile systems. More research is needed to
solve difficulties related to soil penetration, spatial resolution limita­
tion, and influence of particle size and soil ingredients.
Application specificity: THz technique is application-specific and
L. Afsah-Hejri, et al. Computers and Electronics in Agriculture 177 (2020) 105628

must be specifically optimized for a particular product or purpose. The

(Etayo et al., 2010)

optimization process is usually long and labor-intensive. Studies

(Federici et al.,
showed that THz sensors can be used for in-line moisture measurement
References

and quality inspection of grains (Chua et al., 2004; 2005), differ­

entiating healthy grains from wrinkled wheat (Gua et al., 2013), and

2009)
identification of moldy, insect-infested, and sprouted wheat grains
(Jiang & Zhang, 2014). Each method requires a specific sample pre­
*Grape berries were distinguished as early as their appearance in June
*Leaf defects were differentiated based on the absorption, transmission

content, thin-skinned crops (such as blueberries, cherries, and plums)

paration method, sample holder, image processing method, and clas­
sification models. Different varieties of grains have unique THz spec­
*THz imaging can be used for fruit differentiation of high-water-
*Berries, stems and leaves showed different reflectance spectra

trums, and further research is needed to build a library for the

*Stacked layers of leaves were detected at 0.2 THz-System

classification of grains.
Insect contamination is a significant problem in nuts. Insect con­
tamination in the whole in-shell nuts can’t be detected due to the THz
*Grape berry hidden behind a leaf was detected

penetration limitation. (Li et al., 2014). CW THz spectroscopy can help

with this problem and insect-infested samples show different THz
pseudo-color images depending on the life stage (larval, pupal and
adult) of the insect (Tan et al., 2014). The location and size of the in­
festation can be revealed through the high-contrast THz images. More
*Active THz imaging system for

research is needed towards using more powerful sources and increasing

the sensitivity of the THz systems for insect detection.
Complex classification process: Studies showed that combination
resolution = 2 mm

of THz spectroscopy with chemometric methods successfully (identifi­

cation rate > 97%) detected and classified transgenic seeds (Li et al.,
and reflection

2016; Liu & Kan, 2018; Gente et al., 2016; Liu et al., 2015, 2015a, b).
Findings

However, there have been some problems associated with these

methods. Most of the chemometric methods are based on complex
calculations on the THz spectrum data and it is not easy to set up the
berries,stems, and leaves); Field measurements: May (formation of flowers) through

parameters for some of the models. Manual labeling of the training

Reflection and transmission modes; Quasi-optical system and a network analyzer;

samples is another problem in establishing an identification model, and

human error during the labeling process will reduce the identification
accuracy of the model. Using the affinity propagation clustering algo­
Reflection mode; THz Gouy phase shift; Sample: Niagra grape (flowers,

rithm can facilitate both the cluster analysis and labeling process and
Frequencies between 140 and 215 GHz were used to obtain images

solve this problem (Liu & Kan, 2018). Above mentioned studies showed
that several chemometric and statistical methods can be used for THz
data processing. To find a proper model, different chemometric and
statistical methods should be tested through a long and time-consuming
process. Statistical as well as chemometrics methods should be in­
tegrated into future THz instruments to automatically analyze the re­
sults (Smith & Arnold, 2011).
Possible future outlook: Although progress has been made in THz
imaging techniques and hardware, THz imaging still has a long way to
go from a research tool to a practical control device. Possible areas for
future improvements include decreasing the cost of THz technology,
improving temperature-dependent sensing, improving the LOD and
September (harvest)

accuracy, building a THz database, improving the instruments, im­

Experiment details

proving the signal to noise ratio and the performance of THz systems,
and improving the software.

4. Conclusion
THz spectroscopy and imaging for Crop yield estimation.

THz is a relatively new sensing technology with proven applications

0.14–0.22 THz

in many different industries, including agriculture. Researchers suc­

THz range

cessfully revealed defects in agricultural products with THz imaging

0–1 THz

and also distinguished between live and dead insects. A combination of

THz spectroscopy with chemometric methods helped the scientists to
construct classification models for discrimination of transgenic seeds,
Stacked objects, holes, and unwanted

pesticides, harmful compounds, and poisonous plants. Some of the

models produced 100% successful classification for both GM and non-
GM crops. THz spectroscopy has also been used for the detection of
Application and product

fragments in leaves

heavy metals and buried organic objects in the soil. Although pesticides
Crop yield estimation

and harmful compounds were identified and quantified with a combi­

nation of chemometric methods and THz spectroscopy, the sensitivity
of the technique was not very high for some toxic compounds. THz
spectroscopy was used as a useful tool for non-destructive measurement
Table 9

of drought stress, the water content of plant leaves, and crop yield. The
technique has also been tested in the field and successfully

21
L. Afsah-Hejri, et al.
distinguished between leaves, flowers, and fruits.
In general, THz spectroscopy has some restraints such as low ac­
curacy, spatial resolution limitation, penetration limitation, influence
of particle size, and effect of plant surface or fruit roughness. Also,
workable standoff distance varies for different high-water-content
crops. Further research is needed to decrease the cost of THz tech­
nology, improve the LOD and accuracy, build a THz database, improve
the instruments and S/N ratio, and improve the performance of THz
systems as well as the software. THz technology is still in its infancy. It
is expected to see more applications in agriculture with the invention of
new, more powerful THz sources and increase the sensitivity of detec­
tors.
Declaration of Competing Interest
The authors declared that there is no conflict of interest.
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