Research Article, Issue 4
Analytical Methods in Environmental Chemistry Journal
Journal home page: www.amecj.com/ir
AMECJ
------------------------
Ahmad Riahi a, Elham Mosafayian Jahromyb and Bahareh Fahimirad C,*
a Department of Chemistry, Australian Community of Science, Hobart,Tasmania, Australia
b Islamic Azad University of Pharmaceutical Sciences (IAUPS), Medical Nano Technology Tehran, Iran
C,*Department of Chemistry, Semnan University, Semnan, Iran
Therefore, speciation and determination of arsenic
in human blood and water samples is very important
[3]. The toxicity of arsenic compounds is generally
linked to the soluble inorganic trivalent forms, which
is controlled by pH. Human exposure assessment in
workers to arsenic containing substances includes
short term (recent or acute exposure) and long term
(chronic exposure) tests that can be performed
to monitor detoxification efficiencies. Exposure
of arsenic can lead to progressive peripheral and
central nervous changes, such as, numbness and
muscle tenderness. Normal arsenic concentrations
in blood and urine are typically below 50 µg L−1
and 7 µg L−1, respectively [4]. Threshold limit value
Speciation of arsenic (III,V) based on
methyltrioctylammonium mercaptobenzoate and centrifuging
dispersive liquid-liquid microextraction in water and blood
1. Introduction
Analytical methods has important role for
determining hazardous heavy metal in different
matrixes such as human blood and environmental
samples. Analytical methods based on
nanotechnology and ionic liquids was used for
determination arsenic concentration in the blood,
urine and serum samples by different instruments
such as ICP-MS, ET-AAS and HG-AAS [1].
Inorganic arsenic compounds are toxic in human
body but organic arsenic is usually less harmful [2].
* Corresponding author: Bahareh Fahimirad
Email: bahareh.fahimi@yahoo.com
https://doi.org/10.24200/amecj.v2.i04.83
A R T I C L E I N F O:
Received 22 Aug 2019
Revised form 3 Nov 2019
Accepted 28 Nov 2019
Available online 27 Dec 2019
Keywords:
Arsenic speciation,
Water and human blood,
Task-specific ionic liquids,
Centrifuging dispersive liquid-liquid
microextraction
A B S T R A C T
A novel analytical method based on centrifuging dispersive
liquid-liquid microextraction (CD-LLME) procedure for pre-
concentration of As (III) has been developed prior to determine
by hydride generation atomic absorption spectrometry (HG-
AAS). In this method, 0.1 g of a task specific ionic liquids
(methyltrioctylammonium 2-mercaptobenzoate; TOMAS; TSIL)
as the extracting and complexing solvent and acetone as dispersant
solvent were rapidly added into the water and blood samples at pH
4.5. The As (V) is simply calculated by difference between total
concentration and inorganic forms As (III) in liquid samples. By
optimizing parameters, the enrichment factor (EF) was obtained
9.8 and 49.6 for blood and water samples, respectively. The limit of
detection (LOD) of 22.4 ngL-1 and 4.3 ngL-1 were achieved for 10
mL and 50 mL of As(III) in blood and water samples, respectively
(RSD<%5). The real samples were validated by certified reference
material (CRM) by proposed procedure.
Speciation of arsenic by TOMAS Bahareh Fahimirad et al
Analytical Methods in Environmental Chemistry Journal Vol 2 (2019) 39-48
40 Analytical Methods in Environmental Chemistry Journal; Vol. 2 (2019)
(TLV) of arsenic concentration in human blood is
less than 2.5 μg dL-1 [5].
So, the sensitive analytical techniques, such as;
high performance liquid chromatography coupled
to inductively coupled plasma mass spectrometry
(HPLC-ICP-MS)[6], inductively coupled plasma
atomic emission spectrometry (ICP-AES)[7],
Cold vapor/hydride generation atomic absorption
spectrometry (HG-AAS)[8], hydride generation
and atomic fluorescence spectrometry (HGAFS)[9]
and electro-thermal atomic absorption spectrometry
(ET-AAS)[10]. Gas Chromatography-Inductively
Coupled Plasma-Mass Spectrometry (GC-ICP-MS)
or Ion Chromatography Coupled to inductively
coupled plasma mass spectrometry (IC- ICP-MS)
was required for determination and speciation of
arsenic in blood and water samples. Among them,
HG-AAS is a conversional instrument which was
widely used for arsenic determination in human
biological samples and waters. But, sample
preparation was needed for preconcentration and
separation ions from real samples before using
analytical techniques. The ionic liquids (ILs)
as green solvent were used for separation and
determination metals in liquid phases. The different
hydrophobic/hydrophilic ILs can be extracted
ions from waters with ligand by spectrometry
methods [11-14]. The cadmium, chromium and
mercury were removed from water samples by
TSILs. The sample preparation procedures based
on ionic liquids (ILs) was used for this purposed.
Recently, the liquid–liquid extraction (LLE)[15],
cluod point extraction (IL-CPE)[16], ionic liquid
based on solid phase extraction (IL-SPE) [17] was
reported by previous papers. Arsenic speciation and
determination by GC-ICP-MS or IC- ICP-MS were
too much expensive. On the other hands, the arsenic
speciation with conversional instruments needs
to prepare difficult samples at low time. In this
study, a new analytical method based on TOMAS
(C32H59NO2S) was used for arsenic speciation in
water and human blood samples by CD-LLME
procedure. Based on results, many advantages such
as, low time, efficient extraction and high recovery
were obtained.
2. Experimental
2.1. Apparatus
The experiments were performed using a GBC-932
atomic absorption spectrometer equipped with a
cold vapor/hydride generation module (HG3000-
AAS -AUS). The operating parameters for the
metal of interest were set as recommended by the
manufacturer. Mercury and arsenic determined
by HGAAS respectively. Arsenic hollow cathode
lamp based on 8 mA, 193.7 nm and the spectral
bandwidth of 1 nm was used. The pH values of
the solutions were measured by a digital pH meter
(Metrohm 744). In all analysis the deuterium
background correction was turn on (Table 1). The
instrumental calibration curve was linear between
0.5 –30 μg L−1. All containers (quartz crucibles,
plastic tubes) were cleaned with detergent and
treated successively by the HNO3(2%) and rinsed
with de-ionized water(DW). The pure argon gas
(99.99%) was used as a carrier gas for HGAAS
analysis. The reduced flame was turn on by HG-
AAS.
2.2. Materials
All chemicals of analytical grade such as nitric
acid, hydrochloric acid, Polyoxyethylene octyl
phenyl ether (TX-100), sodium acetate, sodium
hydroxide, and sodium borohydride (NaBH4) were
from Merck Germany. Reducing agents (aqueous
solution of 0.6% sodium borohydride in 0.5%
sodium hydroxide) were prepared freshly and
filtered before use. Arsenic standard solutions were
prepared from a stock solution of 1000 mg L−1 as
ultra-trace in 2% nitric acid from Fluka Switzerland
(No; 39436). Working standard solutions were
prepared by dilution of stock and intermediate
standards. Buffer solutions were prepared from
1-2 mol L−1 sodium acetate and acetic acid for pH=
3-7. Ultrapure water was obtained from a Water
System of Iranian research Institute of Petroleum
Industry (Millipore RIPI). Alderich. The TSIL,
Ethyltrioctylammonium 2-mercaptobenzoate or
Trioctylmethylammonium thiosalicylate (TOMAS,
CAS Number 1027004-61-0) was purchased from
Sigma Aldrich.
41
Speciation of arsenic by TOMAS Bahareh Fahimirad et al
2.3. Sampling
For sampling, the clean glass tubes and container
were purchased from Iranian company. The 10
mL of human blood samples were collected from
industrial factory of Iran. For sampling, all glass
tubes were washed with a 0.5 mol L-1 HNO3
solution for at least 24 h and thoroughly rinsed 10
times with ultrapure water (UPW) before using.
As concentrations of arsenic in blood / serum are
very low, even minor contamination at any stage of
sampling, sample storage and handling, or analysis
has the potential to affect the accuracy of the
results. For analysis in blood 10 μL, pure heparin
(free metals) is added to a 10 mL blood sample.
The human blood sample was maintained at –20 °C
in a cleaned glass tube. The water prepared in 250
mL of polyethylene bottle (PEB) based on ASTM
for sampling and storage by acidifying.
2.4. General procedure
The developed method based on centrifuging
dispersive liquid-liquid microextraction (CD-
LLME) was used for arsenic speciation in human
blood and water samples at pH=4.5. By proposed
procedure, the concentrations of As (III, V) in
range of 1-5.8 µg L-1 were determined by HG-AAS
in human blood and water samples. As (III) can be
extracted with TOMAS in liquid phase without any
chelating agent at optimized pH. Flame condition
tuned based on 1.2 L min-1 of fuel with low air
flowrate for As by HG-AAS. By CD-LLME
procedure, 0.12 g of TOMAS diluted with 0.2 mL
of acetone and injected into 10 mL of blood and
standard samples which was included the arsenic
3. Results and Discussion
In proposed method, for increasing higher
sensitivity, selectivity and precision, of determining
and speciation arsenic (As) in blood and water
samples, we studied and optimized thoroughly,
the effect of the main parameters, like the type of
disperser and extraction solvent, sample volume,
sample acidity, amount of TOMAS as chelating
agent, and extraction time.
Table 1. Instrumental Conditions for arsenic
Parameter Arsenic
Wavelength (nm) 193.7
Lamp current (mA) 8.0
Slit (nm) 1.0
LOD (µg L-1) 0.22
Linear Range (µg L-1) 0.5-58
Mode Peak area
Fig. 1. The schema of TSIL (TOMAS)
concentration of 1-5.8 µg L-1. Then, the pH was
adjusted to 4.5 with buffer solution, shaking for
5 min and then transferred to a centrifuge tube.
Arsenic (III) was complexed with TSIL (As-
TOMAS) and then, the TSIL were separated from
liquid phase by centrifuging of turbid solution at 3
min with 3500 rpm. The upper phase of TOMAS,
with olive green color layer, was removed with a
transfer pipette to PEB (5 mL). The As(III) was
back-extracted from TOMATS at acidic pH by
0.5 mL of hydrochloric acid solution (2 M) which
was shaken for 1.0 min and diluted with ultrapure
water up to 1mL. Then, the TOMAS phase was
removed by centrifuging and pipette and aqueous
phase was determined by HG-AAS. The same
procedure was done on sample blank for water and
human serum/blood samples without As(III,V).
Finally, the As (V) was reduced to As (III) with
KI (1M) and ascorbic acid, the total arsenic (TAs)
was determined. In addition, the concentration of
As (V) was calculated by subtracting the content of
As (III) from total arsenic content. The extraction
conditions based on TOMAS were explained in
Table 2.
Human sampling based on ethical rules was
confirmed by the Ethical Committee of Islamic
Azad University, Tehran Medical Sciences
(Ethical Code: R.IAU.PS.REC.1399.106)
42 Analytical Methods in Environmental Chemistry Journal; Vol. 2 (2019)
metal hydride is formed and then passed through
a gas-liquid separator where the hydride vapor is
removed from the bulk liquid using an inert carrier
gas. The hydride is then fed into a fused quartz
absorption cell. For arsenic determination the cell
is mounted over a burner and heated by an air-
acetylene flame (HGAAS). Flame conditions were
with 1.2 Lmin-1 fuel and minimum flow air.
3.2. Effect of pH range
The complexation phenomenon is strongly
conditioned by the pH of solutions and subsequently
affects the extraction efficiency of the As(III) by
complexing of TOMAS. As previously research,
ionic liquids such as TOMAS was decomposed in
lower pH (less than pH=3). Therefore, the effect of
pH was studied and evaluated in the pH range of 3
–11 as a lower limit of quantification (LLOQ) and
upper limit of quantification (ULOQ) for 0.05-5.0
μg L−1 for As(III). The results show that the high
extraction efficiency for As (III) were achieved in
pH=4.5 and As(V) had no extraction in optimized
pH (less than 5%). So, the procedure was applied
to speciation of arsenic in water and blood samples
(Fig. 2).
3.1. Instrumental
The repeatability of results was investigated for
speciation and determination arsenic in blood
and water samples by hydride generation atomic
absorption spectrometer (HGAAS) in present of
flame. After mixing reagents and samples, the
mixture solution moved to reaction coil where the
Fig. 2. The effect of pH on As(III) extraction based on TOMAS by CD-LLME method
Table 2. The extraction conditions of As(III) based on
TOMAS by CD-LLME method
Features (Human blood) Value As
Mean RSD% (blood, n=10) 3.2
LOD of CD-LLME(blood, μg L-1) 0.022
Enrichment factor(blood) 9.8
Volume of blood (mL) 10
Linear range of blood, PA (μgL-1)0.05 –5.9
Correlation coefficient of DLLME R = 0.9965
Features (Water) Value As
Mean RSD% (water, n=10) 2.8
LOD of CD-LLME(water, μg L-1) 0.004
Enrichment factor(water) 48.6
Volume of water(mL)
Linear range of water, PA (μgL-1)
50
0.01-1.1
Correlation coefficient of DLLME R = 0.9983
PA = Peak Area
43
Speciation of arsenic by TOMAS Bahareh Fahimirad et al
3.3. Optimization of amount of TSIL and
extraction time
The variation of extraction efficiency upon
TOMAS amount as TSIL was examined within
the range of 0.02-0.2 g for arsenic concentration
from 0.05 to 5.0 μg L−1 in blood samples. It was
observed that the extraction efficiency of the
system was remarkably affected by the TSIL
amount. Quantitative extraction of As(III) based
on TOMAS was observed more than 0.08 g and
0.1 g for 10 mL and 50 mL of blood and water
samples, respectively. So, 0.12 g of TOMAS was
selected as optimum amount of TSIL for arsenic
speciation in both samples (Fig.3). Triton X-100,
an emulsifier and anti-sticking agent, was added
to the solution in order to raise the efficiency of
the extraction procedure. After added TX-100 [1%
(w/v)] the quantitative extraction was observed
for arsenic by TOMAS in human blood samples.
The effectiveness of As(III) extraction under the
influence of shaking and centrifugation time was
studied. The different shaking and centrifuging
times (3500rpm) were studied and optimized by
CD-LLME procedure. The results showed us, the
5.0 min of shaking and 3.0 min of centrifuging had
efficient extraction for proposed method.
3.4. Effect of sample volume
Sample volume is one of the most important
parameter to be studied when real samples are
analyzed by a pre-concentration technique,
since it conditions the sensitivity enhancement
of the method. The effect of sample volume was
examined in a range of 1–100 mL for 5.0 μg L−1 and
1.0 μg L−1 As(III) ions in blood and water samples,
respectively. It was found that the As(III) could
be quantitatively extracted in blood samples for
12 mL of the sample solution. At higher a volume
the recoveries are decreased. It was also noticed
that higher sample volumes partially solubilized
the TOMAS in liquid phase and lead to non-
reproducible results. Therefore sample volume of
10 mL was selected for further experiments for
human blood samples. Also, the results showed, the
As(III) was efficient extracted based on TOMAS
in 60 mL of water samples. So, 50 mL of water
samples selected for further study (Fig. 4).
Fig. 3. The effect of amount of TOMAS on As(III) extraction by CD-LLME method
44 Analytical Methods in Environmental Chemistry Journal; Vol. 2 (2019)
3.5. Interferences study.
TOMAS is a TSIL with thiol (HS) group
which was acted as a chelating agent for many
transition metals. Thus, for extraction of As(III)
with TOMAS, the interferences coexisting ions
such as mercury, lead, copper, zinc, vanadium,
and silver should be considered. The effect of
potential interfere occurring in blood and water
samples on the determination of As(III) were
tested in optimized conditions by CD-LLME
procedure. The extraction recovery of TOMAS
for 0.05-5.9 μg L−1 and 0.01-1.0 μg L−1 of
As(III,V) was tested in blood and water samples
with individual ions interferences. The results
showed that many ions could be tolerated up to
at least 1-3 mg L−1. Mercury and silver had low
tolerated up to at least 80-400 μg L−1 by using
TOMAS in water and blood samples. High
concentrations of alkali metals, alkaline earth
metals, CO3
2- and PO4
3- which are usually found
in blood samples, were tested by 0.5-1.0 mg
L−1 and did not effect on extraction recovery of
As(III) by CD-LLME procedure (Table 3).
3.6. Method validation
For validation of proposed method, 10 mL and
Fig. 4. The effect of sample volume for As(III) extraction by CD-LLME method
Table 3. The effect of interferences coexisting ions on
extraction of As(III) in human blood and water samples by
CD-LLME method
Interfering Ions in blood(M)
Mean ratio
(C M/C As(III))
Recovery
(%)
As(III) As(III)
Cr
3+
, Al
3+
, Mn
2+
, Cd
2+
, V
3+
, Pb
2+
750 98.8
Zn
2+
, Cu
2+
, Ni
2+
, Co
2+
, Mo
2+
500 95.9
I
-
, Br
-
, F
-
, Cl
-
1000 98.5
Na
+
, K
+
, ,Ca
2+
, Mg
2+
900 99.1
CO
3
2-
, PO
4
3-
, HCO3
-
700 96.7
Ag
+
300 98.2
Hg
2+
80 96.6
NO3
-
, SO
4
2-
800 97.5
Interfering Ions in water (M)
Mean ratio
(C M/C As(III))
Recovery
(%)
As(III) As(III)
Cr
3+
, Al
3+
, Mn
2+
, Cd
2+
, V
3+
, Pb
2+
900 97.7
Zn
2+
, Cu
2+
, Ni
2+
, Co
2+
, Mo
2+
650 97.2
I
-
, Br
-
, F
-
, Cl
-
1200 97.4
Na
+
, K
+
, ,Ca
2+
, Mg
2+
1000 98.6
CO
3
2-
, PO
4
3-
, HCO3
-
950 96.6
Ag
+
400 99.2
Hg
2+
150 97.3
NO3
-
, SO
4
2-
1000 98.1
45
Speciation of arsenic by TOMAS Bahareh Fahimirad et al
50 mL of blood and water samples were used.
Results showed that there are no interferences from
major consistent of blood samples, therefore we
have explored the feasibility of the methodology
using proposed method for the determination of
As(III) ions in different matrices. Validation of the
methodology was performed by standard reference
material (NIST SRM 2670) with certified values
for arsenic speciation (Table 4). Also, the spiked of
standard arsenic solutions with real human blood
and water samples were done to demonstrate the
reliability of the method for determination and
speciation of As (III) and As (V) (Table 5). In
addition, the ability of different methods compared
to CD-LLME method in Table 6. The TOMAS
based on CD-LLME-HGAAS technique can be
used for determination and speciation of arsenic
(As3+, As5+) in human samples as compared to
HG-AAS or ET-AAS (project Ethical Code:
R.IAU.PS.REC.1399.106).
3.7. Comparing to other methods
The figures of merit of the CD-LLME method
compared to the alternative methods for arsenic
speciation (III, V) in different matrixes (Table 7).
Recently, the different techniques for extraction/
separation/detemination arsenic spcies in human
biological fluids and waters have been reported.
Some techniques such as dispersive liquid–liquid
microextraction (DLLME), cloud point extraction,
and solid phase extraction have already used
for extraction and speciation arsenic [18-21]. In
this work, the TSIL (TOMAS) based CD-LLME
combined with CV-AAS for speciation and
determination of As (II, V) in human blood and
water samples. The LOD, RSD and linear range
values compared to other published method. Wen
et al. used cloud point extraction with ICP-optical
emission spectrometry for speciation of AS (III,
V) with LOD of 0.72 and RSD of 3.5 which was
higher than CD-LLME procedure [18]. Based on
Table 5. Evaluation of accuracy and precision of results in human blood and water samples by spiking of arsenic
standard (III, V) based on CD-LLME method
Sample
Added Found aRecovery (%)
As(III) As(V) As(III) As(V) Total As As(III) As(V) Total As
CRM* ------- ------- 2.45 ± 0.14 1.42 ± 0.11 3.87± 0.21 98.0 94.6 96.7
2.0 ------- 4.41 ± 0.23 1.44 ± 0.12 5.85± 0.28 98.1 ------- 99.0
------- 1.5 2.43 ± 0.15 2.95 ± 0.16 5.38± 0.25 ------- 102 100.6
Water ------- ------- 0.88 ± 0.04 0.59 ± 0.02 1.47 ± 0.07 ------- ------- -------
1.0 ------- 1.85 ± 0.09 0.61 ± 0.03 2.46 ± 0.13 97.0 ------- 98.8
------- 0.5 0.87 ± 0.05 1.07 ± 0.05 1.94 ± 0.11 ------- 95.7 94.5
Blood ------- ------- 1.77± 0.08 ND 1.77± 0.08 ------- ------- -------
1.5 ------- 3.24± 0.14 ND 3.24± 0.14 98.0 ------- 98.0
------- 1.5 1.74± 0.08 1.48± 0.07 3.22± 0.18 ------- 98.6 96.5
Urine ------- ------- 1.15± 0.06 1.06± 0.05 2.21± 0.11 ------- ------- -------
1.0 ------- 2.17± 0.08 1.02± 0.05 3.19± 0.15 102 ------- 97.9
------- 1.0 1.13± 0.05 2.03± 0.10 3.16± 0.16 ------- 97.0 95.0
aMean value ± standard deviation based on three replicate measurements
*NIST SRM 2670, arsenic in frozen dried urine, pH 4.5,-20oC
Table 4. Validation of the methodology was performed by standard reference material (NIST SRM 2670)
Recovery
As(V)
Recovery
As(III)
Found a
As(V)
Found a
As(III)As(V) As(III)SRM
96.6%100.8 %1.45 ± 0.112.52 ± 0.181.50 ± 0.22.50 ± 0.2Urine b
-----95.7%-----1.98 ± 0.12-----2.07 ± 0.63Blood C
a Mean value ± standard deviation based on three replicate measurements
bNIST, SRM 2670, arsenic in frozen dried urine, pH 4.0 ,-20oC
C NIST, SRM 955c, Caprine Blood, Level 1
46 Analytical Methods in Environmental Chemistry Journal; Vol. 2 (2019)
Table 7, the sensitivity of the developed method is
similar to other reported methods. The linear range
was perfectly adequate for the analyzed human
blood samples. Lower LOD values are related with
higher sensitivity of proposed method which was
used in this study. Also, some methods have higher
PF that analyzed by ICP in water or human blood
samples with large sample volume. TSIL (TOMAS)
based CD-LLME combined with CV-AAS showed
a rapid and easy extraction and speciation of As
(III,V) using a user-friendly instruments.
4. Conclusions
The procedure here studied takes advantage of
the combination of a very simple, reliable way of
pre-concentrating in sea water and blood samples
for arsenic determination and speciation with
the sensitive TOMAS@HG-AAS technique.
The increase in sensitivity resulting of sample
pre-concentration, good sample frequency and
possibility of speciation of As (III), As (V) forms
of these analytes, means the procedure can be
considered an alternative to high-performance
liquid chromatography (HPLC) in combination
with inductively coupled plasma mass
spectrometry (ICP-MS) , Ion Chromatography
Coupled to inductively coupled plasma mass
spectrometry (IC- ICP-MS) and ICP-MS. The
results showed that the quantitative extraction
(QE) and enrichment factor (EF) for water
samples were more than 95% and 49.6,
respectively (RSD<5%). Linear range of arsenic
in blood and water samples was obtained 0.05 –5.9
and 0.01-1.1μgL-1, respectively by CD-LLME
method. By proposed procedures, the satisfactory
results of ultra-trace analysis for arsenic species in
blood and water samples were achieved.
5. Acknowledgements
The authors thank from the Islamic Azad
University of Pharmaceutical Sciences (IAUPS)
Table 6. Comparing of different techniques with CD-LLME method for determination and speciation of arsenic (III,
V) in real samples
LC-MS/MS*CD-LLME/HG-AAS*HG-AAS*SampleAs species
0.296 ± 0.0120.304 ± 0.016-----As (V)Water
0.201 ± 0.0080.197 ± 0.011----- As (III)
± 0.015 0.497± 0.024 0.501± 0.027 0.485Total
0.844 ± 0.0320.865 ± 0.043-----As(V)Blood
2.702 ± 0.0962.641 ± 0.127-----As (III)
3.546 ± 0.1213.486 ± 0.1663.317 ± 0.175 Total
*Mean value ± standard deviation based on three replicate measurements (N=5, P= 0.95)
Table 7. Comparison of the published methods with the proposed method in this work
ReferencesRSD%DL*LR*
MatrixesSeparationMethod
[18]3.50.722-50Snow waterAPDC-CPE b
ICP-OES a
[19]8.00.121-50Hair waterHF-LPMEC
ETAAS
[20]2.980.811-2000wine1-octyl-3-methylimidazolium chloride(IL)LC-HG-AFSD
[21]4.0- 5.70.03-0.050.1-50plasma urineDDTP -CLLMEH
ET-AAS
This work3.20.0220.05 – 5.9BloodTOMAS- CD-LLME HGAAS
This work2.80.0040.01 –1.1WaterTOMAS/ CD-LLMEHGAAS
*Linear rang (LR, μg L−1); Detection limit (DL, μg L−1)
a inductively plasma-optical emission spectrometry(ICP-OES)
b Ammonium 1-pyrrolidinedithiocarbamate(APDC) - Cloud point extraction (CPE)
C Hollow fiber liquid phase microextraction combined
D liquid chromatography - hydride generation atomic fluorescence spectrometry
H Diethyldithiophosphoric acid (DDTP)-Centrifuging liquid-liquid microextractio
47
Bahareh Fahimirad et al
Speciation of arsenic by TOMAS
Iran. (EthicalCode:R.IAU.PS.REC.1399.106)
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