1074

Journal of Applied Sciences Research, 9(2): 1074-1082, 2013

ISSN 1819-544X
This is a refereed journal and all articles are professionally screened and reviewed

ORIGINAL ARTICLES
Laser-Induced Breakdown Spectroscopy (LIBS) An Assessment of Treated Industrial
Wastewater Using Water Hyacinth Roots
1

H.E. Hassan, 2A.A. Abdel Rahman, 3E.A. El-Sherbini, 4Z. Abd El-Fattah, 5A.R. Abdel Tawab

1,3,4

National Institute of Laser Enhanced Science (NILES), Cairo University, Egypt.

Agricultural Engineering Research Institute, Agricultural Research Center, Cairo, Egypt.
5
Central Laboratory for Environmental Quality Monitoring (CLEQM), National Water Research Center (NWRC),
Cairo, Egypt.
2

ABSTRACT
The pollution of the environment increased rapidly during the last years. There is an increasing need to
determine concentration of contamination rapidly and precisely, in particular those of toxic heavy metals. The
rising costs of treating water and wastewater and the increasing requirement for clean water is prompting
industry and authorities to examine new methods for water conservation. Conventional chemical methods used
for the analysis of water and wastewater can be accurate, but are mainly based on sample collection and
retrospective analyses. Toxic heavy metals pollution of water is a major environmental problem, and most
conventional remediation approaches do not provide acceptable solutions. Wetland plants such as the water
hyacinth "Eichhornia crassipes" have been used successfully for the Phytoremediation of heavy metals in natural
and constructed wetlands. The present paper was undertaken to determine experimentally the treatment of
industrial wastewater collected from an industrial area in Egypt, for removal of heavy metals using different
root's type of the water hyacinth, results obtained indicated that water hyacinth roots are highly effective in
treatment of wastewater to be used for irrigation. Vaporization and ionization of the material, resulting in hot
plasma, is used to analyze that material directly by Laser-induced breakdown spectroscopy (LIBS) which is a
simple spark spectro-chemical sensor technology in which a laser beam is directed at a sample to create a hightemperature micro plasma. The obtained results were as followed: (1) The Na, Mg and Ca intensities were
decreased to the maximum within the treatment process to 1143.87, 179.42, and 560.34 a.u. , respectively, after
24 hr by using Whole plant root and to the minimum to 3962.44 a.u. for sodium using dry root after one hour, for
magnesium to 450.23 a.u. subsequent to one hour using the whole plant root, and for calcium it was 2430.42 a.u.
after one hour using the dry root., (2) For sodium the absorption efficiency (71.07%) was recorded by using
whole dry root. For magnesium it gives (48.31%), and finally for calcium it was (73.88%)., (3) The Zn, Pb, and
Fe intensities were decreased to the maximum within the treatment process to 21.32, 96.84, and 169.7 a.u.,
respectively, after 24 hr by using Whole plant root and to the minimum treatment was 188.12, 522.13, and 96.59
a.u. for Zn, Pb, and Fe respectively, and (4) The roots were attracted the trace metals on its surface but with
different intensity. From the table below it is clear that Zn, Pb, and Fe were attracted by 34.01, 45.03, and 38.42
%, respectively.
Key words: Wastewater treatment, Heavy metals, Laser-induced breakdown spectroscopy (LIBS), Water
Hyacinth.
Introduction
Egypt has a fixed and rather limited surface and groundwater resources. The present per capita water
availability is in the order of 1000 cubic meter per year which indicates that Egypt is currently under "Water
Stress". It is anticipated that water availability may drop by year 2015 to 630 cubic meter per year which brings
the country to a "Scarcity Level" (Tawfic, 2001). Consequently, one of the biggest challenges facing Egypt is to
reduce the widening gap between available water resources and increasing demands by different economic
sectors.
Wastewater is considered one of the most important resources which could be a precious one if treated and
managed well to be reused. However, in practice most of this domestic and industrial wastewater is discharged
untreated or partially treated contaminated with a wide range of toxic chemicals and pathogens, causing serious
drawbacks for human health and environment (Scott et al., 2004). Conventional treated methods are not designed
to address today's concerns. To provide better water quality at a lesser cost, it is desirable to find sustainable
alternatives more natural, new, and cost effective while minimizing the needs for chemicals.

Corresponding Author: H.E. Hassan, National Institute of Laser Enhanced Science (NILES), Cairo University, Egypt.

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One of these alternatives is the use of treatment systems known as "Wetlands". Wetlands depend mainly on
Phytoremediation using different plant species. They have high potential for application in rural areas with less
capital and operational costs. Their ability to markedly reduce biological oxygen demand, nutrients, heavy metals,
and pathogens has made them very attractive option (El-Gohary, 2006).The floating aquatic plant Water Hyacinth
is a worldwide invasion plant. It is capable of rabid reproduction in shallow water and able to tolerate a wide
range of environmental conditions (Toft et al., 2003). Hyacinth has been known to assist in the purification of
wastewater because of its settlement action and absorption capacity. Its ability to reduce organic matter
(Mangkoedihardjo, 2006), fecal coliforms (Mayo and Kalibbala, 2007) and heavy metals (Malik, 2007) has been
reported.
Laboratory studies showed that water hyacinth was an excellent accumulator for Cd, Se, and Cu (Soltan and
Rashed, 2003). While more than 93 % of arsenate and 95 % of arsenate were removed from a solution containing
200ug/l arsenic within 60 minutes of exposure to the powder of non-living dried roots of water hyacinth (Ranalli
et al., 2005).
The present study was dedicated to assign water hyacinth, "Eichhornia crassipes" as Phytoremediator for
heavy metals and some cations present in industrial wastewater, using the plant's root in different forms (whole
fresh roots, whole dry roots, coarse dry roots, and fine dry roots) under controlled experimental designed
conditions.
Materials and Methods
Using water hyacinth for wastewater treatment experiment done using a glass tank with 90 cm length; 50 cm
width and 50 cm height filled with wastewater and a plastic reservoir was hanged over the top of the glass tank
with a valve for continuous filling of the tank with wastewater. The tank also has a valve to tip out the treated
water to be collected and analyzed using Laser induced breakdown (LIBS) plasma which is obtained using a
Nd:YAG laser (Quantel) delivering 7ns laser pulses at its fundamental wavelength ( = 1064nm), with adjustable
repetition rate up to 10Hz (i.e. 10 pulses per second).The laser pulse energy was adjusted by suitable combination
of beam splitters, as an external attenuator at constant operating high voltage (1.3kV) to ensure spatial beam
profile stability.
An energy meter (NOVA, Ophir Optronics Ltd., USA) was employed to monitor the shot-to-shot pulse
energy. Plasma production on the eggshell surface was attained via a quartz plano convex lens of 100mm focal
length. A 1m length fused silica optical fiber mounted on a micro xyz-translation stage is used to collect the
emission light from the plasma plume and feed it to an Echelle spectrometer (Mechell 7500, Multichannel
instruments, Sweden). Block diagram for such instrument is shown in Figure (1).

Fig. 1: Schematic diagram for LIBS instrument.

Echelle grating spectrometer, designed for operation in high orders and high angles of incidence and
diffraction, can provide high resolution in a more compact size and cover a much wider spectral range than
conventional grating spectrometers. The Mechell 7500 provides a constant spectral resolution of 7500
corresponding to 4 pixels FWHM (Full Width at Half Maximum), over a wavelength range 200-1000nm
displayable in a single spectrum. A gettable intensified CCD camera (Di CAM-Pro-PCO Computer Optics,
Germany) coupled to the spectrometer was used for the time resolved detection of the dispersed light. The
gating of the camera and the timing for spectral data accumulation were controlled via PC.
The overall linear dispersion of the spectrometer-camera system ranges from 0.006 (at 200nm) to 0.033
nm/Pixel (at 1000 nm).To avoid electronic interference and jitters, the intensifier high voltage is triggered
optically. The ICCD camera control was performed via special Multichannel Instruments software. Echelle
spectra display, processing and analysis were done using 2- and 3-D Gram/32 software programs (National
Instruments, USA).

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J. Appl. Sci. Res., 9(2): 1074-1082, 2013

In addition to the atomic database used by the mentioned software, spectral lines identification was checked
by the most up-to-date electronically published database. LIBS where applied under laboratory conditions to the
analysis of water and ice (Knopp et al. 1996; Arca et al. 1998; Caceres et al. 2001). LIBS instruments have
been developed and are beginning to be applied to environmental and industrial analysis (Wainner et al. 2001;
Moskol and Hahn 2002; Walters and Rose 2003).
Water hyacinth sampling and preparation:
Water hyacinth was collected directly from the River Nile and was chosen according to the size of its roots
which almost ranged from 13 to 15 cm in length. The roots were separated from the whole plant and were
arranged into four groups; whole fresh roots, whole dry roots, coarse grinded dry roots, and fine grinded dry
roots. Roots drying took place in the oven at 105 oC, and samples of each root type were digested and analyzed
for heavy metals just before being incorporated into the experiment for base line data (Photos 1 and 2).

Photo 1: Whole roots and dried roots of water hyacinth.

Photo 2: Fine grinded roots and coarse grinded roots of water hyacinth.
Wastewater sampling and analysis:
Wastewater sampling was done from mixed industrial water, in Egypt. Wastewater is characterized by its
excessive input loads of heavy metals due to industrial activities. Samples were analyzed at the National Institute
of Laser Enhanced Sciences, Department of Laser Application in Metrology, Photochemistry and Agriculture
(LAMPA), for heavy metals only using Laser Induced Breakdown Spectroscopy (LIBS) instrument.
Sampling procedures as well as analytical methods were carried out according to Standard Methods for
Examination of Water and Wastewater (APHA, 2005).Water samples were collected in Polyethylene containers
(20 Gallons) and were preserved by adding concentrated nitric acid to achieve pH< 2 to protect against microbial
reactions.
Laser analysis included three trace metals which are lead (Pb), Iron (Fe), and Zinc (Zn), also three cations
where analyzed and those elements are Magnesium (Mg), Calcium (Ca), and Sodium (Na)
Results and Discussion
Laser analysis for cations:

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J. Appl. Sci. Res., 9(2): 1074-1082, 2013

LIBS was obtained using a Nd:YAG laser (Quantel) delivering 7ns laser pulses at its fundamental
wavelength is (l = 1064 nm), with adjustable repetition rate up to 10Hz. The spectrum intensity rises with the
concentration increasing, and a good linear relationship is found at low concentration region Shi Huan Zhao, et
al., (2012). Three cations elements were analyzed with LIBS which are Sodium (Na) at 588.9 nm, Magnesium
(Mg) at 285.2 nm, and Calcium (Ca) at 422.6 nm and the data are illustrated in Table (1). In the same time a
digested roots were analyzed before and after treatment for the same three metals, and the treatment percentage
were calculated.
Table 1: Cations elements analysis of water samples using LIBS.
Parameters

Control (Wastewater)
1 hr
12 hr
24 hr
1 hr
12 hr
24 hr
1 hr
12 hr
24 hr
1 hr
12 hr
24 hr

Na
(588.9nm)
Whole Plant
4625.80
3300.19
2641.37
1143.87
Dry Root
3962.44
2796.38
1216.45
Coarse Grinded Dry Root
3958.29
2786.99
1325.78
Fine Grinded Dry Root
3528.39
2758.98
1283.54

Mg
(285.2 nm)

Ca
(422.6 nm)

1332.76
450.23
332.22
179.42

3258.34
2212.90
918.76
560.34

421.81
312.70
125.35

2430.42
1076.18
630.87

416.68
257.44
114.56

1952.07
918.16
650.96

400.45
210.34
109.47

1234.04
840.47
603.65

Fig. 2: LIBS in qualitative and quantitative analysis for cations amounts (Sodium, Magnesium and Calcium) in
wastewater treatment.

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J. Appl. Sci. Res., 9(2): 1074-1082, 2013

Laser induced breakdown spectroscopy is used in qualitative and quantitative analysis of cations amounts
such as Sodium, Magnesium and Calcium in water, with ND:YAG laser as the excitation light source and high
resolution, wide spectral range Echelle spectrometer and intensified charge-coupled device (ICCD) as a line
separating and detecting device Shi Huan Zhao, et al., (2012).
From the Figure (2) and Table (1) shows recognizable improvement with an overall reduction in cations
levels compared to the wastewater. Generally; the root type as well as contact time during the treatment were the
main key factors governing the process of treatment. The results indicated that Na, Mg and Ca intensities were
decreased to the maximum within the treatment process to 1143.87, 179.42, and 560.34 a.u. , respectively, after
24 hr by using whole plant root and to the minimum to 3962.44 a.u. for sodium using dry root after one hour, for
magnesium to 450.23 a.u. subsequent to one hour using the whole plant root, and for calcium it was 2430.42 a.u.
after one hour using the dry root Figure (2).
Digested roots analysis by LIBS for cations:
The whole plant root was subjected to digestion as well as analyses before and after treatment for three
elements Na, Mg, and Ca to figure out what happened during the treatment process. Table (2) and Figure (3)
explain the absorption efficiency of the roots for cations removal.
Table 2: Heavy metal analysis of root samples by LIBS.
Digested Root
Na
(at 588.9 nm)
Before
1032.28
After
1452.3
Reduction %
71.07

Mg
(at 285.2 nm)
430.83
891.70
48.31

Ca
(at 422.6 nm)
1234.04
1670.32
73.88

According to the previous mentioned results in Table (2), it's clear that, for sodium the absorption
efficiency (71.07%) was recorded by using whole dry root. For magnesium it gives (48.31%), and finally for
calcium it was (73.88%).

Fig. 3: Digested roots analysis by LIBS before and after treatment for cations elements (Na, Mg, and Ca).

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Laser analysis for trace metals:

LIBS is obtained using a Nd:YAG laser (Quantel) delivering 7ns laser pulses at its fundamental wavelength
is (l = 1064 nm), with adjustable repetition rate up to 10Hz.The spectrum intensity rises with the concentration
increasing, and a good linear relationship is found at low concentration region Shi Huan Zhao, et al., (2012).
Three trace metals were analyzed with LIBS which are Zinc (Zn) at 330.2 nm, Lead (Pb) at 405.7 nm, and Iron
(Fe) at 404.5 nm and the data are illustrated in Table (3).
In the same time a digested roots were analyzed before and after treatment for the same three metals, and
the treatment percentage were calculated.
Table 3: Heavy metal analysis of water samples by LIBS.

Control (Wastewater)
1 hr
12 hr
24 hr
1 hr
12 hr
24 hr
1 hr
12 hr
24 hr
1 hr
12 hr
24 hr

Zn
(330.2 nm)
Whole Plant Root
210.22
188.12
49.3
21.32
Dry Root
132.28
46.68
24.65
Coarse Grinded Dry Root
55.58
43.72
38.82
Fine Grinded Dry Root
53.26
32.46
21.72

Pb
(405.7 nm)

Fe
(404.5 nm)

601.3
522.13
238.48
96.84

978.8
966.59
325.37
169.7

310.4
193.92
114.67

599.8
303.25
250.08

303.4
254.98
189.3

420.25
310.32
199.5

259.45
165.64
153.49

417.59
124.69
187.54

Laser induced breakdown spectroscopy is used in qualitative and quantitative analysis of trace amounts of
heavy metals such as Zinc, Lead and Iron elements in water, with ND: YAG laser as the excitation light source
and high resolution, wide spectral range Echelle spectrometer and intensified charge-coupled device (ICCD) as
a line separating and detecting device Shi Huan Zhao, et al., (2012).
The results indicated that Zn, Pb, and Fe intensities were decreased to the maximum within the treatment
process to 21.32, 96.84, and 169.7 a.u., respectively, after 24 hr by using Whole plant root and to the minimum
treatment was 188.12, 522.13, and 96.59 a.u. for Zn, Pb, and Fe, respectively, Figure (4).
Digested roots analysis by LIBS for heavy metals:
The roots were analyzed before and after treatment for three metals Zn, Pb, and Fe. Results indicated that
roots were attracted the trace metals on its surface but with different intensity. From the table below it is clear
that Zn, Pb, and Fe were attracted by 34.01, 45.03, and 38.42 %, respectively, shown in Table (4) and Figure
(5).
Table 4: Heavy metal analysis of root samples by using LIBS.
Digested Root
Zn
(at 330.2 nm)
Before
13.4
After
39.4
Reduction %
34.01

Pb
(at 405.7 nm)
166.61
370.02
45.03

Fe
(at 404.5 nm)
307.69
800.86
38.42

Conclusion:
In the present study, we demonstrate the floating aquatic plant water hyacinth Eichhornia crassipes as an
efficient and cost effective Phytoremediator for heavy metals present in wastewater. The whole fresh roots
showed the best efficiency in metals removal within time interval ranging between 1to 24 hours which favors
shortterm Phytoremediation systems that are usually done in suburban areas where space is limited for long
term treatments. The obtained results were as followed: (1) The Na, Mg and Ca intensities were decreased to the
maximum within the treatment process to 1143.87, 179.42, and 560.34 a.u. , respectively, after 24 hr by using
Whole plant root and to the minimum to 3962.44 a.u. for sodium using dry root after one hour, for magnesium to
450.23 a.u. subsequent to one hour using the whole plant root, and for calcium it was 2430.42 a.u. after one hour

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J. Appl. Sci. Res., 9(2): 1074-1082, 2013

using the dry root., (2) For sodium the absorption efficiency (71.07%) was recorded by using whole dry root.
For magnesium it gives (48.31%), and finally for calcium it was (73.88%)., (3) The Zn, Pb, and Fe intensities
were decreased to the maximum within the treatment process to 21.32, 96.84, and 169.7 a.u., respectively, after
24 hr by using Whole plant root and to the minimum treatment was 188.12, 522.13, and 96.59 a.u. for Zn, Pb,
and Fe respectively, and (4) The roots were attracted the trace metals on its surface but with different intensity.
From the table below it is clear that Zn, Pb, and Fe were attracted by 34.01, 45.03, and 38.42 % respectively.

Fig. 4: Zinc, Lead and Iron metals before and after treatment with different root type.

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J. Appl. Sci. Res., 9(2): 1074-1082, 2013

Fig. 5: Reduction percentages for digested root analysis by LIBS for some heavy elements.
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