International Journal of Civil & Environmental Engineering IJCEE-IJENS Vol: 14 No: 01 8

A Comparison of ICP-OES and UV-Vis

Spectrophotometer for Heavy Metals
Determination in Soil Irrigated with Secondary
Treated Wastewater
Ali , M.F and Shakrani, S. A.
Faculty of Civil Engineering, Universiti Teknologi MARA (UiTM), Malaysia
mohdfozi@salam.uitm.edu.my, shahrulazwan.shakrani@gmail.com


Abstract— The concentrations of selected heavy metals such been through the treatment process. Heavy metals are
as Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn in soil irrigated with detrimental and often associated with
secondary treated wastewater were determined by means of ICP-
OES and UV-Vis Spectrophotometer after combined acid wet environmental issues and health problems to the plants,
digestion. The results revealed that heavy metals concentrations
of secondary treated wastewater were significantly higher in the
animals and humans. Generally, there are two major sources of
FSTW as compared to the BSTW suggested that seasonal heavy metals, namely natural and anthropogenic. Heavy
variations and efficiency of the treatment system affected the metals occur naturally in soils, but human activities lead to
wastewater quality. Besides, the heavy metals characteristics of greater levels of heavy metals contamination in soils and to the
soil irrigated with secondary treated wastewater were found to be environment. Kabata-Pendias [1] revealed that Ag, Au, Cd, Cr,
relatively higher in the SPS as compared to the SEPS suggesting Hg, Mn, Pb, Sb, Sn, Te, W, and Zn are among potentially most
that cross sectional area of soil affected the accumulation of
macronutrients and trace elements. Meanwhile, the comparative
hazardous trace metals to the biosphere while Be, Cd, Cr, Cu,
study between ICP-OES and UV-Vis spectrophotometer for Hg, Ni, Pb, Se, V, and Zn are considered to be of great risk to
detection of heavy metals in soil irrigated with secondary treated environmental health. Thus, proper assessment of the
wastewater demonstrated the higher trends of heavy metals levels environmental status of heavy metals is very important in
obtained in UV-Vis spectrophotometer as compared to ICP-OES order to minimize contamination, though proper sampling and
suggesting that lots of interferences with other elements during analysis as well as appropriate analytical methods [2].
analysis under UV-Vis spectrophotometer. Thus, ICP-OES is
recommended for analysis of soil irrigated with secondary treated
wastewater as the ICP-OES was found suitable for analysis of The process of determination of heavy metals in soils
elements in soils with good accuracy due to high sample requires matrix destruction which depends on the dissolution
throughput capacity, rapid multielement characteristics, varies processes and digestion technique was performed through
detection limits makes it suitable for this kind of application while decomposition of complex substance into simple salts and
HACH DR5000 UV-Vis Spectrophotometer was suggested to volatile gases under soluble acid solution [3, 4]. There are
have better functionality towards water than soil analysis.
many techniques introduced for digestion procedures such as
Index Term— ICP-OES, heavy metals, secondary treated dry, wet and microwave. Both dry and wet digestions, are slow
wastewater, soil, UV-Vis spectrophotometer. and time consuming, whereas microwave digestion is much
more rapid and low consumption of time and reagents [5]. In
recent years, combined wet digestion has been introduced to
I. INTRODUCTION enhance the dissolution process for a short period of time,
THE reuse of secondary treated wastewater for irrigation is which provides the greater recovery as compared to single wet
believed to provide the water resources optional as freshwater digestion technique [6].
has no guarantee sufficient. However, the secondary treated
wastewater is always contaminated and possible present of In combined analytical methods, the decomposition of solid
trace elements, particularly heavy metals, although after have samples is an important stage whereby the sample is measured
in an aqueous solution and by means of highly sensitive
M. F. Ali is with the Division of Water Resources and Environmental techniques such as Flame Atomic Absorption
Systems, Faculty of Civil Engineering, Universiti Teknologi MARA (UiTM), Spectrophotometer (FAAS), Graphite Furnace Atomic
40450, Shah Alam, Selangor, Malaysia. (e-mail:
mohdfozi@salam.uitm.edu.my).
Absorption Spectrophotometer (GFAAS), Inductively Coupled
S. A. Shakrani is with the Faculty of Civil Engineering, Universiti Plasma Optical Emission Spectrometry (ICP-OES) and
Teknologi MARA, 40450, Shah Alam, Selangor, Malaysia. (e-mail: Inductively Coupled Plasma Optical Mass Spectrometry (ICP-
shahrulazwan.shakrani@gmail.com).

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 International Journal of Civil & Environmental Engineering IJCEE-IJENS Vol: 14 No: 01 9

MS) [7, 4]. These combined analytical methods are favoured Pb, Mn, Ni and Zn in soil irrigated with secondary treated
for multi element analysis of samples at very short period. wastewater. Details of the instrument and operating conditions
Previously, the calorimetric method was introduced for the for ICP-OES were described in Table I.
analysis of samples along with UV-Vis spectrophotometer
TABLE I
measurement which is considered as a low tech instrument. Instrumental Details and Operating Conditions for ICP-OES Thermo Scientific
Yet, there is little comparative information available between iCAP 6000 Series
combined analytical methods, particularly between ICP-OES Subject Descriptions
and calorimetric method assisted by UV-Vis Pump tubing Orange/white tygon sample
spectrophotometer. In this study, the levels of selected heavy White/white tygon drain
metals concentrations in soil samples irrigated with secondary Pump rate 50 rpm
treated wastewater were determined by both ICP-OES and Nebulizer Standard concentric
UV-Vis spectrophotometer after combined acid wet digestion. Nebulizer argon flow rate 0.6L/min or 0.22MPa
Spray chamber Standard cyclonic
Centre tube 2.0mm
II. MATERIALS AND METHODS
Torch orientation Duo
A. Wastewater and Soil Sampling RF forward power 1150 W
The final secondary treated wastewater (FSTW) and Auxiliary flow 0.5 L/min
biological secondary treated wastewater (BSTW) used for Integration times
High wavelengths 5 seconds
irrigation was collected six times from Mawar Wastewater Low wave lengths 15 seconds
Treatment Plant located at Universiti Teknologi MARA
Replicates 3
(UiTM) Shah Alam, Malaysia. This wastewater treatment
plant consists of screening, grit removal, primary
sedimentation and conventional activated sludge treatment The digested samples of soil and plant as well as wastewater
process with a population equivalent of 11 000. The samples were simultaneously prepared with a blank sample
wastewater sampling was conducted in accordance with contains of distilled water through the complete procedure,
APHA et al. [8], BS EN ISO 5667:1 [9], BS EN ISO 5667:3 analyzed and then used for correction of the analytical signals.
[10] and BS 6068:6.10 [11]. For both types of wastewater, Working standard solutions were prepared by suitable dilution
about 1 litre of samples was taken into polypropylene (0.25, 0.5, 1, 3, and 5 ppm) of the ICP multi-element standard
sampling bottles and later transferred to the laboratory for solution supplied by Merck Millipore (Darmstadt, Germany).
analysis. The wastewater was preserved with concentrated In this stage, calibration was performed with a blank and
nitric acid (pH<2) to prevent any microbial degradation of standard solution samples and detection limits (LOD) were
heavy metals and stored in a refrigerator at about 4 oC in order determined with a standard deviation of blank solutions. The
to prevent any possible change in volume due to evaporation. ranges of the calibration curves were selected to match the
expected concentrations of all the elements of the sample
The mustard greens (Brassica campestris Sp. parachinensis) studied. The analytical characteristics of heavy metals by ICP-
were planted on the experimental plot (SEPS) located at the OES were listed in Table II with demonstrated the detection
Faculty of Plantation and Agrotechnology, UiTM as well as limits and wavelengths.
TABLE II
polybag soil (SPS) located at Mawar Wastewater Treatment The Analytical Characteristics of Heavy Metals by ICP-OES
Plant, UiTM. Both experimental plot and polybags soil were Element Detection Limit Wavelength References
watered seven days per week with FSTW and BSTW. The soil (µg/L) (nm)
Cd >0.01 and ≤0.1 214.438 [8]
sampling was conducted in accordance with BS ISO 10381:1 Cr >0.01 and ≤0.1 205.552 [8]
[12], BS ISO 10381:2 [13] and ASTM D5633 [14]. Six Co >0.1 and ≤1 230.786 [8]
samples of top soil at 15 cm depth were manually collected Cu >0.1 and ≤1 324.754 [8]
Fe >0.1 and ≤1 271.441 [8]
from centre of experimental plot and polybag soil with clean Pb >0.1 and ≤1 220.353 [8]
stainless steel trowel of 8 cm diameter. At least 500 g of soil Mn >0.01 and ≤0.1 257.610 [8]
were collected and transported into polyethylene containers. Ni >0.1 and ≤1 231.604 [8]
Samples were later transferred to the laboratory together with Zn >0.01 and ≤0.1 213.856 [8]
label and sealed. The details of the experiments were adopted
from Ali and Shakrani [15]. As a comparison, the HACH DR5000 UV-Vis
Spectrophotometer [16] (Hach, Colorado, USA) was also used
for detection of heavy metals such as Cd, Cr, Co, Cu, Fe, Pb,
B. Instrumentation Details and Calibration Mn, Ni and Zn in wastewater and soil samples. The
A Thermo Scientific iCAP 6000 Series ICP-OES (Thermo specifications of HACH DR5000 UV-Vis Spectrophotometer
Fisher Scientific, Cambridge, UK) was used in this study to instrument were described in Table III.
determine of selected heavy metals such as Cd, Cr, Co, Cu, Fe,

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 International Journal of Civil & Environmental Engineering IJCEE-IJENS Vol: 14 No: 01 10

TABLE III TABLE V

The Instrumental Specifications for HACH DR 5000 UV-Vis The Precision and Sensitivity Analysis of Heavy Metals
Spectrophotometer Characteristics by HACH DR 5000 UV-Vis Spectrophotometer
Subject Descriptions Element Precision Sensitivity
Operating Mode Transmittance (%), Absorbance and Standard 95% Confidence Limits ΔConcentration
Concentration Solution of Distribution
Source Lamp Tungsten (VIS) and Deuterium (UV) Cd 40.0 μg/L Cd 39.3–40.7 μg/L Cd 0.73 μg/L Cd
6+
Wavelength Range 190 to 1100 nm Cr 0.500 mg/L Cr 0.497–0.503 mg/L Cr6+ 0.005 mg/L Cr6+
Wavelength Accuracy ± 1 nm in wavelength range 200 to 900 nm Co 1.00 mg/L Co 0.99–1.01 mg/L Co 0.01 mg/L Co
Wavelength Resolution 0.1 nm Cu 1.00 mg/L Cu 0.97–1.03 mg/L Cu 0.04 mg/L Cu
Wavelength Calibration Automatic Fe 2.00 mg/L Fe 1.99–2.01 mg/L Fe 0.021 mg/L Fe
Wavelength Selection Automatic, based on selected program Pb 150 μg/L Pb 140–160 μg/L Pb 2.3 μg/L Pb
method Mn 0.500 mg/L Mn 0.491–0.509 mg/L Mn 0.006 mg/L Mn
Scanning Speed 900 nm/min in 1 nm steps; 1 complete Ni 0.500 mg/L Ni 0.492–0.508 mg/L Ni 0.006 mg/L Ni
scan/1 min Zn 1.00 mg/L Zn 0.97–1.03 mg/L Zn 0.013 mg/L Zn
Spectral bandwidth 2 nm Note: Portion of Curve=Entire range, ΔAbs=0.010
Photometric Measuring Range ± 3 Abs in the wavelength range 200 to 900
nm
Photometric Accuracy 5 mAbs at 0.0-0.5 Abs, 1 % at 0.50-2.0 Abs
C. Reagents and Glassware
Photometric Linearity: < 0.5 % up to 2 Abs, ≤ 1 % at > 2 Abs All reagents were prepared using water previously deionized
Stray Light KI-solution at 220 nm > 3.3 Abs or < with PURELAB Option-Q (ELGA Labwater, UK). Analytical
0.05% reagents-grade chemicals were used in the preparation of all
Sample Cell Compatibility 1-in. square; 1-in. round; 1x1, 2x1, 5x1,
10x1 cm; 13 mm round; 16 mm round; 1 solution. The sulphuric acid (65%) was purchased from
cm, 5 cm, and 1-in. Pour-Thru Cells; Mallinckordt Chemicals Inc. (St. Louis, MO, USA) while
AccuVac Ampules chloroform (65%), nitric acid (65%) and hydrogen peroxide
Operating Temperature Range 10 to 40 °C at 95% Relative Humidity (non-
condensing) (50%) were obtained from Merck Schuchardt OHG
Storage Conditions -40 °C to 60 °C ; 80% Relative Humidity (Hohenbrunn, Germany). The ICP multi elements standard
Power Requirements 100 V - 120 V, 50 - 60 Hz, 100 - 240 V AC solution was supplied by Merck Millipore (Darmstadt,
Optical System Split Beam
Germany). All reagents used to perform the calometric method
and by means of Hach DR 5000 UV-Vis Spectrophotometer
For calibration, the standard additional (sample spike) and
was obtained from Hach Company (Colorado, USA). All
standard solution samples were prepared and measured by
glassware and plastic materials used were soaked into 10% of
HACH DR5000 UV-Vis Spectrophotometer. The brief
nitric acid for 24 hours and rinsed with double distilled water
procedures for calibration can be referred in HACH Company
and then with deionized water.
[16]. The analytical descriptions such as detection limits and
wavelengths were presented in Table IV while the precision
and sensitivity analysis were presented in Table V. D. Acid Wet Digestion
The wet digestion of soil samples was conducted using
TABLE IV
The Analytical Characteristics of Heavy Metals
HACH Digesdahl Digestion Apparatus [21]. This method was
by HACH DR 5000 UV-Vis Spectrophotometer introduced by Jones and Case [22] and later prescribed by
Element Method Detection Wave References Brayton [3] as Piranha Clean Method (also known as Vigreux
Limit length Method) where a mixture of sulphuric acid and hydrogen
(mg/L) (nm)
Cd Dithizone 0 to 80.0 µg/L 515 [8] peroxide were initiated [4, 23].This procedure was performed
Cr 1, 5- 0.010 to 0.700 540 [8] after preparation of samples. After oven-dried at 70 oC for 48 h
Diphenylcarboh to remove all moisture, soil samples were ground became the
ydrazide
Co 1-(2- 0.01 to 2.00 620 [17]
fine powder by using a mortar and pestle. The samples were
Pyridylazo)-2- later sieved and passed through 2 mm mesh sieve.
Naphthol (PAN)
Cu Bicinchoninate 0.04 to 5.00 560 [18]
Fe FerroVer® 0.02 to 3.00 510 [8]
Then, 0.25 to 0.5 g of each soil samples were accurately
Pb Dithizone 3 to 300 µg/L 515 [8] weighted by analytical weighing balance (A & D Company
[19] Limited, Tokyo Japan) into 100 mL digesdahl digestion flask
Mn 1-(2- 0.006 to 0.700 560 [20] Then, 4 to 6 mL of concentrated sulphuric acid was added to
Pyridylazo)-2-
Naphthol (PAN) the digestion flask. The sample was then heated and boiled at
Ni 1-(2- 0.006 to 1.000 620 [17] 440 oC (825 oF) for 4 minutes. Afterwards, 10 to 20 mL of 50
Pyridylazo)-2- % hydrogen peroxide was added to the flask via the funnel.
Naphthol (PAN)
Zn Zincon 0.01 to 3.00 620 [8] The sample was then continued heated for one more minute.
After that, the digested sample was diluted to approximately
70 mL with 18 Ω demonized water. After cooling, the sample
was filtered through a Whatman No.41 filter paper into a 100
mL volumetric flask pre-washed with 10 % concentrated

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HNO3. Later, samples were further filtered through a 0.5 μm highest in FSTW at 0.024 mg/L and 0.023 mg/L. The contents
polytetrafluoroethylene (PTFE) membrane (Whatman Ltd, of Zn were detected at 0.197 mg/L in FSTW and 1.122 mg/L
UK). in BSTW as lowest and highest. In general, most of
characteristics of FSTW and BSTW were found within the
allowable limit regulated by Malaysia Environmental Quality
E. Statistical Analysis
Act 2009 [26], World Health Organization [27], Food and
The data were statistically analyzed using the SPSS version Agriculture Organization of the United Nations [28] and
17 software with a significance level of P <0.05. All collected United States Environmental Protection Agency [29].
data carried out were subjected to one way analysis of variance
(1 Way - ANOVA). The concentrations of heavy metals in both FSTW and
BSTW were resulted from the used of cleaning products
III. RESULTS AND DISCUSSION together with personal and body care products as well as pipes
A. A Comparison of Heavy Metals Characteristics of and fittings [30, 31, 32]. The low range of Cd in secondary
Secondary Treated Wastewater by Using ICP-OES and HACH treated wastewater resulted from an impurity in galvanized
DR5000 UV-Vis Spectrophotometer pipes and fitting along with contaminant used of phosphate in
The heavy metals characteristics of FSTW and BSTW detergent and washing powder. Besides, shampoos and
studied with ICP-OES and UV-Vis spectrophotometer are cosmetics product along with hand wash also contributed to
presented in Table VI. In general, the heavy metals the sources of Cd in wastewater. The low concentrations of Co
concentrations of secondary treated wastewater were in wastewater were caused from the availability of Co in
significantly higher in FSTW as compared to BSTW suggested sewage sludge (biosolids) as well as food products.
that seasonal variations and efficiency of the treatment system Meanwhile, the low concentrations of Cr found in wastewater
affected the wastewater quality. Al-Absi et al. [24] explained were due to corrosion of welded metals and stainless steel in
that treated wastewater contained lower levels of the mineral piping systems, fittings and taps. The Cu concentrations
during rainfall due to dilution effect. The failure to properly availability in secondary treated wastewater was determined
treat and manage wastewater for irrigation purposes may from the corrosion of copper pipes and leaching of plumbing.
generate adverse health effects [25]. Moreover, cosmetics and shampoo products had also added the
Cu concentrations in secondary treated wastewater. Iron pipes
TABLE VI contributed to the high sources of Fe in wastewater. Besides,
Heavy Metals Characteristics of FSTW and BSTW by Means of ICP-OES and cleaning and personal products, including toothpaste had also
UV-Vis Spectrophotometer
contributed to high level of Fe in wastewater. The sources of
Element ICP-OES UV-Vis
(mg/L) Spectrophotometer Mn in wastewater are usually derived from sewage sludge as
FSTW BSTW FSTW BSTW well as cast iron and steel objects such storage tanks, piping
Cd ND ND 0.005±0.001 0.006±0.001 and pumps. Low concentrations of Ni were resulted from
Co ND ND 0.040±0.013 0.100±0.013
Cr 0.011±0.004 0.010±0.001 0.042±0.001 0.039±0.002 rechargeable batteries, metal coated and galvanized pipes and
Cu 0.103±0.007 0.027±0.008 0.855±0.049 0.565±0.012 fittings. Besides, Ni concentrations found in wastewater were
Fe 0.260±0.047 0.465±0.031 1.026±0.012 1.197±0.091 due to the used of deodorants, toothpaste, conditioners, hand
Mn 0.078±0.002 0.069±0.008 0.073±0.002 0.064±0.001
Ni 0.007±0.001 0.006±0.001 0.024±0.001 0.013±0.002 wash, body wash and shampoo. The lower level of Pb in
Pb 0.019±0.005 0.011±0.003 0.023±0.002 0.016±0.001 secondary treated wastewater was resulted from toilet paper,
Zn 1.029±0.134 1.122±0.058 0.197±0.010 0.230±0.026 toilet refreshers, dishwashing tablets, personal care products
Note: Each data represents the mean of 6 values ± the standard deviation. ND=
for instance mouthwash, hair conditioner and toothpaste,
none detected
detergent as well as laundry. High concentrations of Zn in
wastewater were resulted from galvanized iron pipe and
The lowest and highest of Cd concentrations were found at fitting, personal and body care product such as deodorant,
0.005 mg/L for FSTW and 0.006 mg/L for BSTW. Meanwhile, shampoo as well as cosmetic.
the lowest and highest levels of Co were found at 0.04 mg/L
for FSTW and 0.1 mg/L for BSTW. The lowest of Cr contents The analysis of variance (ANOVA) performed at 95%
was found at 0.01 mg/L for BSTW whereas the highest contest confidence intervals indicated all of the F-value and P-value to
of Cr was found at 0.042 mg/L for FSTW. The concentrations determine if there was any significant difference between
of Cu were found at 0.027 mg/L for FSTW and 1.197 mg/L for means of heavy metals concentrations for both secondary
BSTW as lowest and highest values. Besides, the lowest and treated wastewater effluents studied. Most of the parameters
highest values of Fe were recognized at 0.26 mg/L for FSTW demonstrated the p-value was less than 0.05 which rejected the
and 1.197 mg/L for BSTW. The concentrations of Mn were null hypothesis of the study as shown in Table 7. Thus, the
found at 0.064 mg/L for BSTW as the lowest and 0.078 mg/L quality of both secondary treated wastewater effluents was
for FSTW as the highest. Both Ni and Pb concentrations were found to be relatively significant in most of heavy metals
found lowest in BSTW at 0.006 mg/L and 0.011 mg/L while studied.

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TABLE VII (XRD), ICP and HACH colorimetric analysis and discovered
Analysis of Variance at 95% Confidence Intervals for Secondary Treated
Wastewater
the concentration of Pb ranges from 0.004 to 10.8 weight
Element Analysis of Variances (ANOVA) percent by HACH colorimetric analysis while varies between
F P
Significance Level 1.05 to 2.67 weight percent by means of XRD. It was
ns= PValue>0.05 suggested that Pb paint weathers it hydrates and transformed
Value Value
* = PValue<0.05
Cd 260.862 0.000 * from Pb oxides and carbonates to hydrated Pb compounds.
Co 111.667 0.000 * However, Pearson's correlation coefficient performed for the
Cr 382.160 0.000 * data indicates good correlation (r2=0.97) between analysis by
Cu 1374.486 0.000 *
Fe 414.458 0.000 * HACH colorimetric and ICP and suggested that HACH
Mn 11.892 0.000 * colorimetric provides a rapid digestion method for Pb analysis
Ni 255.611 0.000 * of the field-test study.
Pb 14.744 0.000 *
Zn 270.304 0.000 *
Note: *=statistically significance, ns= statistically not significance Thus, multielement analytical capabilities of ICP-OES make
it ideal tools for processing multiple analysis of large numbers
Meanwhile, the heavy metals characteristics for both of samples quickly and efficiently. The combination of low
secondary treated wastewater effluents were found to be higher detection limits and wide analytical concentrations make it
in the analysis of sampling by means of HACH method as well suitable to analyze of the low to moderate concentrations
compared to ICP-OES. The percentage difference between of many elements, particularly for water sample analysis [39].
results obtained from HACH method and ICP-OES analysis Therefore, it was suggested that the uses of ICP-OES for
for Cr 73.809% to 74.359 %, Cu 87.953% to 95.221%, Fe analysis of wastewater samples particularly for analysis of
61.153% to 74.659%, Mn 6.410% to 7.246%, Ni 53.846% to heavy metals characteristics while HACH DR5000 Uv-Vis
70.833%, Pb 17.391% to 31.250%, and Zn 79.501% to Spectrophotometer could be used for analysis of
80.855%. However, there was no percentage difference macronutrients characteristics such N, P and K.
between results obtained from HACH method and ICP-OES
for Cd and Co since these elements were not detected in
B. A Comparison of Heavy Metals Characteristics of
samples by ICP-OES. Different Sample of Soil Irrigated with Secondary Treated
Wastewater by Using ICP-OES and HACH DR5000 UV-Vis
In general, HACH method is based on the reaction of gases Spectrophotometer
with some chemical agents to form a coloured complex, the
The heavy metals characteristics of the soil before and after
intensity of the colour is measured electronically to calculate
irrigated with FSTW and BSTW are presented in Table 8. In
the concentrations of macronutrients and trace elements in
most cases, the heavy metals levels in soil irrigated with
wastewater samples [33]. Meanwhile, the ICP technique uses
FSTW and BSTW were found to be relatively higher in SPS as
the plasma to ionise components, whereby the sample is
compared to SEPS suggesting that cross sectional area of soil
acidified and sprayed into the plasma, then the high
affected the accumulation of macronutrients and trace
temperature of the plasma atomises and ionises all forms of
elements. SPS was likely to accumulate a greater level of
element so that the response does not vary within species, and
heavy metals in soils due to the smaller cross sectional area as
mostly used in conjunction with other analytical techniques
compared to the SEPS. Besides, the accumulation of heavy
such OES, AES and MS [34].
metals was slightly higher on the top and reduced as it went
deeper. However, the concentrations of Cr, Fe, Mn, Ni, Pb and
Previously, Wellborn [35] conducted the study on the
Zn in soils were decreased after irrigated with FSTW and
comparison between HACH and ICP-MS for detection of As
BSTW. Only Cd, Co and Cu levels were increased in soils
levels in water samples and discovered that higher trends of As
after irrigated with FSTW and BSTW.
concentrations obtained with the HACH method as compared
to ICP-MS. Most ions and elements in HACH method were
The lowest and highest concentrations of heavy metals in
believed to interfere with S2-, Se, antimony (Sb), tellurium
soil irrigated with FSTW and BSTW were found at 0.002
(Te), CaCO3 and Fe and resulted in inconsistency values by
mg/L and 0.03 mg/L for Cd; 0.03 mg/L and 0.04 mg/L for Co;
HACH method as compared to ICP-MS.
0.03 mg/L and 0.18 mg/L for Cr; 0.05 mg/L and 2.21 mg/L for
Cu; 0.55 mg/L and 105.84 mg/L for Fe; 0.04 mg/L and 0.24
Besides, Geen et al. [36] compared the characteristics of AS
mg/L for Mn ; 0.01 mg/L and 0.03 mg/L for Ni; 0.01 mg/L and
obtained from groundwater with HACH method and ICP-MS
0.08 mg/L for Pb ; and 0.09 mg/L and 0.58 mg/L for Zn.
and discovered the inconsistencies of HACH method as
However, most of the parameters were recognized to meet the
compared to ICP-MS. The inconsistencies in the HACH
maximum permissible limits as reported in Pedrero and
method mainly underestimate in the range of 50 to 100µg/L
Alarcon [25].
[36, 37]. In addition, Tyrell et al. [38] examined the
concentrations of Pb in paint by means of X-Ray Diffraction

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TABLE VIII
Heavy metals characteristics of soil before and after irrigated with FSTW and BSTW
Element (mg/L) ICP-OES UV-Vis Spectrophotometer
Before FSTW BSTW Before FSTW BSTW
SEPS SPS SEPS SPS SEPS SPS SEPS SPS
Cd 0.003 ±0.002 0.02±0.00 0.03±0.002 0.03±0.00 0.03±0.00 0.002±0.0 0.02±0.00 0.03±0.00 0.03±0.00 0.03±0.00
Co ND ND ND ND ND 0.03±0.01 0.04±0.01 0.04±0.01 0.04±0.01 0.04±0.01
Cr 0.18±0.03 ND 0.04±0.04 ND ND 0.18±0.02 0.03±0.00 0.06±0.01 0.03±0.00 0.08±0.00
Cu 0.05±0.02 1.46±0.02 2.01±0.63 1.45±0.01 2.21±0.42 0.08±0.01 1.10±0.05 1.83±0.41 1.07±0.03 1.79±0.52
Fe 105.84±14.35 0.55±0.02 44.82±16.34 0.56±0.01 1.88±0.82 6.85±0.26 3.70±0.02 6.18±0.07 3.49±0.03 5.83±0.08
Mn 0.21±0.06 ND 0.04±0.05 ND ND 0.24±0.01 0.09±0.01 0.12±0.01 0.09±0.01 0.09±0.01
Ni 0.03±0.01 0.01±0.00 0.02±0.00 0.01±0.00 0.01±0.00 0.03±0.00 0.01±0.00 0.03±0.00 0.02±0.00 0.03±0.00
Pb 0.08±0.01 ND 0.01±0.01 ND ND 0.08±0.01 0.02±0.00 0.03±0.00 0.02±0.00 0.02±0.00
Zn 0.58±0.31 0.15±0.00 0.26±0.11 0.09±0.00 0.06±0.02 0.31±0.05 0.13±0.02 0.28±0.07 0.13±0.02 0.13±0.04
Note: Each data represents the mean of 6 values ± the standard deviation. ND= none detected

In general, Co, Cr, Cu, Fe, Mn, Ni and Zn are considered as TABLE IX
Analysis of Variance at 95% Confidence Interval of Soil Before and After
micronutrients required for plants growth and development. Irrigated with Secondary Treated Wastewater
Thus, most of micronutrients in soil absorbed instantly for Parameter Analysis of Variances (ANOVA)
plant growth and metabolism and decreased in soils [40, 41]. F Value P Value Significance Level
The concentrations of Cd in soils were increased after ns=PValue>0.05
*=PValue<0.05
irrigation with FSTW and BSTW as CD is not required during Cd 343.318 0.000 *
growth and development of plants. The concentration of Co in Co 52.388 0.000 *
soil is not numerous and absorbed by plants from the soil Cr 106.681 0.000 *
Cu 32.802 0.000 *
solution through passive transport [41]. Meanwhile, McLean Fe 142.522 0.000 *
and Bledsoe [42] discovered that Cr tends to oxidize in soils Mn 69.454 0.000 *
and resulted in lower levels in soil while Pb reacted with clays, Ni 96.473 0.000 *
Pb 243.547 0.000 *
phosphates, sulphates, carbonates, hydroxides and organic Zn 12.519 0.000 *
matters in soils. The augmentation of Cu concentration in soil Note: *=statistically significance, ns= statistically not significance
is believed to be due to the excessive level of Cu in secondary
treated wastewater. Besides, the soil obviously retained Cu Similarly to the secondary treated wastewater, the values of
though the exchanges and the adsorption mechanism processes heavy metals characteristics in soil, which was obtained by
as documented earlier by McLean and Bledsoe [42]. High HACH method was slightly higher as compared to those
level of Fe in the soil was due to the oxidation process in soil. acquired by ICP-OES method. The percentage difference
Previously, Briat and Lobréaux [43] together with Schmidt between results obtained from HACH method and ICP-OES
[44] discovered that Fe that appeared in oxidation form in soil analysis for Cd 3.030% to 33.333%, Cr 3.804% to 37.931 %,
with higher pH which is copious elements on earth. The lower Cu 9.037% to 28.947%, Fe 67.788% to 93.528%, Mn 12.605%
concentrations of Mn proved by Marschner [41] as Mn only to 64.655%, Ni 8.824% to 61.290%, Pb 0.000% to 68.000%,
formed in soil solution with lower pH. Meanwhile, the lower and Zn 5.495% to 55.639%. However, there was no percentage
level of Ni was due to the absorption by clays, iron, difference between results obtained from HACH method and
manganese oxides and organic matter, while Zn is absorbed by ICP-OES for Co since this element was not detected in
clay minerals, carbonates and hydrous oxides [42]. samples by ICP-OES.

The analysis of variance (ANOVA) performed at 95% The ICP technique uses the plasma to ionise components,
confidence intervals indicated all of the F-value and P-value to whereby the sample is acidified and sprayed into the plasma,
determine if there was any significant difference between then the high temperature of the plasma atomises and ionises
means of heavy metals concentrations in soils before and after all forms of element so that the response does not vary within
irrigated with FSTW and BSTW. Most of the parameters species, and mostly used in conjunction with other analytical
demonstrated the p-value was less than 0.05 which rejected the techniques such OES, AES and MS [34]. In general, ICP-OES
null hypothesis of the study as shown in Table 9. Thus, the is useful for measuring higher concentrations, especially
concentrations of heavy metals were found to be relatively nutritional and high concentration elements [45]. The ICP-
significant in soils after irrigated with FSTW and BSTW. OES is normally applied for a comparison and more accurate
for a multi-element sample analysis and Hung et al. [34]

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 International Journal of Civil & Environmental Engineering IJCEE-IJENS Vol: 14 No: 01 14

discovered that determination of low concentrations of As in study. Besides, the use of ICP-OES was found suitable for
real samples suffers from low sensitivity due to the poor analysis of elements in soils with good accuracy due to high
ionization efficiency in ICP. Besides, the determination of all sample throughput capacity, rapid multielement
the elements by ICP-OES was not possible because of the characteristics, varies detection limits makes it suitable for this
limits of detection limitations [46]. In addition, selected kind of application while HACH DR5000 UV-Vis
parameters for determination by ICP-OES can influence the Spectrophotometer was suggested to have better functionality
signal intensities and the sensitivity of the method [47]. towards water than soil and plant analysis.
However, Aydin [48] recognized ICP-OES with ability to
analyze a larger number of elements simultaneously with low ACKNOWLEDGMENT
detection limits of the investigated trace elements. Similarly, A special thanks to the Faculty of Civil Engineering,
Rodushkin et al. [49] proved that ICP-OES is a convenient Research Management Institute (RMI) of UiTM, FRGS
technique, capacity for simultaneous, rapid, precise funding , the Faculty of Plantation and Agrotechnology, the
determination with wide analytical range and low detection Faculty of Chemical Engineering and the Facility Management
limits. Besides, Grosser et al. [50] revealed that interferences Office, UiTM Shah Alam for providing facilities.
and analytes interact differently with the gas, resulting in
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