Research Article, Issue 1
Analytical Methods in Environmental Chemistry Journal
Journal home page: www.amecj.com/ir
AMECJ
systems, atmospheric deposition is a significant
source of formaldehyde [1], and in drinking water
formaldehyde arises mainly from the oxidation
of natural organic matter during ozonation [2]
and degradation of oxygenates such as methyl
tert-buthyl ether (MTBE) and dimethyl carbonate
(DMC) [3]. It also enters drinking water via
leaching from polyacetal plastic fittings in which
the protective coating has been broken [4].
Formaldehyde is a very toxic compound and has
been classified as a human carcinogen by the
international agency for research on cancer (IARC),
and also as a probable human carcinogen by the
US. Environmental Protection Agency [5].The
Biochemistry Method: Simultaneous determination of formaldehyde
an d methyl tert-buthyl ether in water samples using static headspace
gas chromatography mass spectrometry
Ali Akbar Miran Beigia,*, Mojtaba Shamsipurb
a Oil Rening Research Division, Research Institute of Petroleum Industry (RIPI), Tehran, Iran
b Faculty of Chemistry, Razi University, Kermanshah, Iran
1. Introduction
Formaldehyde (HCHO) is the most widespread
carbonyl compound in the atmosphere. It enters
the environment from natural sources (including
forest fires) and from direct human sources such
as fuel combustion, industrial on-site uses, off
gassing from building materials and consumer
products. Although formaldehyde is a gas at
room temperature, it is readily soluble in water.
Formaldehyde is very active, and is transported
in air, water and contaminated soils. In aqueous
* Corresponding Author:A. A. Miran Beigi
E-mail: amiranbeigi@yahoo.com
https://doi.org/10.24200/amecj.v2.i01.40
:A R T I C L E I N F O
Received 5 Dec 2018
Revised form 30 Jan 2019
Accepted 15 Feb 2019
Available online 18 Mar 2019
------------------------
Keywords:
Formaldehyde
MTBE
Static headspace-GC/MS
Oil refining
Wastewaters and Water
A B S T R A C T
The present study describes a method based on static
headspace extraction (HS) followed by gas chromatography/
mass spectrometry (GC/MS) for the qualitative and quantitative
analysis of methyl tert-buthyl ether (MTBE) and formaldehyde
(HCHO) in water samples. Cytochrome P4502A6 has important
role for converting of MTBE to tert-butyl alcohol (TBA) and
HCHO. To enhance the extraction capability of the HS, extraction
parameters such as extraction temperature, extraction time, the
ratio of headspace volume to sample volume and sodium chloride
concentration have been optimized. Wide linearity range was
verified in a range of 5-10000 µgL-1 for MTBE (r2=0.9998), while
those for HCHO was 5-500 µg L-1 (r2=0.9996). Detection limits
for MTBE and HCHO was 1.0 µg L-1 and 1.3 µg L-1, respectively.
Best results were obtained when the analyzed oily water samples
were heated to 70 C for 20 min, with the sample volume 10
mL in 20 mL vial, and NaCl 30% (w/v) was used to saturate the
samples. The proposed analytical method was successfully
used for the quantification of analytes in water and wastewater
samples.
Determination of MTBE and HCHO in human; Ali Akbar Miran Beigi, et al
Analytical Methods in Environmental Chemistry Journal Vol 2 (2019) 33-42
34 Analytical Methods in Environmental Chemistry Journal; Vol. 2 (2019)
national institute for occupational safety and health
(NIOSH) considered formaldehyde as immediately
dangerous to life and health at 24 mgm-3 (20 µgmL-
1) [6]. It can damage the persons nerve system, lung
and liver, and cause irritation of eyes, nose, throat
and skin. Therefore, formaldehyde is one of the
analytical interesting substances as a marker of fuel
additive degradation. Its determination becomes
also a hot spot of the research especially in oily
wastewater matrices. A variety of methods for the
determination of formaldehyde have been reported,
including spectrophotometry [7-13], flow-injection
catalytic method [14], high performance liquid
chromatography [15], gas chromatography [16,
17], isotope dilution mass spectrometry [18],
fluorimetry [19, 20], chemiluminescence [21,22],
polarography [23], Fourier Transform Infrared
Absorption [24] and sensors [25-28]. MTBE is also
a volatile organic compound (VOC) produced from
natural gas. It is primarily used for the oxygenation
of fuel to enhance octane number and to improve
the combustion process, in order to reduce
carbon monoxide emissions [29]. MTBE readily
dissolves in water, and moves rapidly through
soils and aquifers. It is resistant to microbial
decomposition and difficult to remove in water
treatment. Its occurrence in the environment is of
a great concern because of the toxicity of MTBE
and its degradation products [30]. Since MTBE is
highly volatile and very soluble in water, it can be
easily found both as airborne pollutants of living
and working environments and as contaminants
of drinking water [31]. To date limited data are
available on the effects of MTBE on health.
Notwithstanding this, USEPA has concluded that at
high doses, MTBE is a potential human carcinogen
and recommended that MTBE levels in drinking
water be kept below a range of 20-40 ppb [32].
MTBE and other oxygenates in ground waters
are frequently measured using standard US EPA
approved methods (e.g., EPA 8021B, EPA 8260B,
ASTM D 4815). These procedures usually perform
gas chromatographic separation coupled with
photo ionization detector (PID), flame ionization
detector (FID) or mass detector (MS). The
introduction of analytes in the chromatographic
apparatus is performed either via direct injection
of water samples (DAI) [33,34], or using sampling
techniques as dynamic headspace (P&T), static
headspace [35], solid phase microextraction
(SPME) [36-44], and solvent microextraction
(SME) [45,46]. The DAI technique presents some
difficulties to be coupled with capillary GC, due to
the large expansion volume of water. Direct water
injections are prone to back flush in the injector
port, which can cause loss of analyte response
as well as injection port contamination. MTBE
oxidation can generate tert-buthyl alcohol (TBA)
and formaldehyde (Fig.1). Our previous study
demonstrated that human cytochrome P450 2A6
is able to metabolize MTBE to tert-butyl alcohol
(TBA) and formaldehyde, a major circulating
metabolite and markers for exposure to MTBE [3].
CYP2A6 plays a significant role in metabolism of
gasoline ethers in liver tissue. The purpose of this
present study is to develop a simple, sensitive and
selective method for simultaneous determination
of trace amounts of formaldehyde and MTBE in
environmental and water matrices. To our
knowledge, no method was found in the literature
for this case.
2. Experimental
2.1. Chemicals and Standard Solutions
In this work, analytical grade of chemicals and
reagents were purchased from Merck, Germany.
3HC
CH3
CH3
COCH3 3HC C OH
CH3
CH
3
HCHO
MTBE
Formaldehde
+
+
TBA
Fig. 1. MTBE oxidation reaction
35
Determination of MTBE and HCHO in water Ali Akbar Miran Beigi, et al
with a heatable CTC agitator for incubation and
shaking, and a robotic arm. To prevent the carry over
of analytes, we used a heated flushing station for
conditioning of the HS needle and reconditioning
after each analysis. Both the gas station and the
heated flushing station were flushed with nitrogen.
The syringe body was held in the syringe adapter
heater. 20 mL vials sealed with screw top caps
with PTFE/silicon septa were used. Parameters of
the instrument are shown in Table 1. A salt content
of 30 (% w/v) was chosen for the quantitative
determination of target analytes in
environmental and water samples.
The GC–MS analysis was performed using a Varian
(CP-3800 series) gas chromatograph equipped
with a mass-selective detector (Varian, quadrupole
1200) and a factor-four, VF-5ms fused-silica
capillary column with a 30m × 0.25 mm i.d. and
250 um film thickness (Varian) was used. The GC
conditions were as follows: inlet temperature, 250
◦C; inlet mode, split operation with split ratio 1:25.
The oven temperature was set at 50 C and raised to
100 ◦C at 5C/per min, and raised to 275 C at 20 C
per minute. The final temperature was maintained
for 1.75 min and the total run time was 20 min.
Helium, at a constant flow rate of 1.5 ml/min was
used as the carrier gas. Mass spectra were obtained
at 70eV in the electron impact ionization mode; the
spectrometer was operated in the full scan mode
over the mass range from 75 to 110(m/z). The
source, transfer line and quadrupole temperatures
were maintained at 200C, 250 C and 200 C,
respectively. Total ion current chromatograms were
acquired and processed using Workstation data
analysis software (Varian). To increase sensitivity,
the selected ion monitoring (SIM) mode was
applied in quantitative analysis. The most abundant
ion was used as the quantified ion. In Table 2, some
Double distilled water (DDW) was used for
preparation and dilution of samples. Helium and
nitrogen (ultrapure carrier grade) were obtained
from Roham gas Company (Tehran, Iran). An
aqueous formaldehyde stock solution, 1000 gm
L−1, was prepared by diluting 2.5mL of 37%
w/v stock formaldehyde solution (Merck) to 1 L
with deionized distilled water (DDW) and was
standardized by the sulfite method [47]. Working
solutions of formaldehyde were subsequently
prepared by appropriate dilution of the stock
solution with DDW. MTBE Calibration stock
solutions were prepared by adding 10 µL of pure
MTBE (99.5%, Merck) to 10 ml of MeOH (Merck)
in a 10ml vial with a PTFE-silicon septum. The
mixture was manually agitated for 5 min. The
first dilution steps were performed with methanol
whereas further preparation of the standard
solutions was carried out with DDW. The standard
solutions used within 4 weeks. All sample and
standard vials were completely filled to eliminate
headspace. Individual and cumulative working
standard solutions were obtained by appropriate
dilution of the stock in 50 ml of methanol and
further diluted in ultrapure Milli-Q water to prepare
solutions containing MTBE and formaldehyde at
the nanogram per milliliter level. The method was
optimized with MTBE and formaldehyde solutions
of 50 µg/L-1 concentration. It should be noted that in
this work Methyl ethyl ketone (MEK) (50 ng mL-1)
was used as internal standard in environmental
and water samples.
2.2. Apparatus and Procedure
Static headspace analysis was performed using
a CTC-CombiPAL autosampler (Bender and
Holbein, Zurich, Switzerland) mounted on top of
a GC-MS system. The autosampler was equipped
Table 1. Headspace conditions
Plunger fill speed: 100 µLper secSyringe Temperature : 71ºC
Pre-injection delay: 4 secAgitator Temperature : 70ºC
Plunger injection speed:250 µLper secSample incubation time: 20 min
Syringe flush time:120 secAgitator speed: 500 rpm
sample volume, 10 ml in 22 ml vialAgitation cycle: 2 sec on, 4 sec off
Analytical Methods in Environmental Chemistry Journal; Vol. 2 (2019)
analytical conditions of MTBE, formaldehyde and
methyl ethyl keton by GC-MS with SIM mode
are shown. All quantifications made in this study
were based on the relative peak area of analytes
to the internal standard from the average of three
replicate measurements in environmental and
water samples.
3. Results and discussion
Various parameters were evaluated during the
method development. In the present study, the
evaluation of individual parameters was carried
out while all other method parameters were kept
constant.
3.1. Extraction temperature
The temperature of sample affects on evaporation
of analyte into the headspace. We expected that
an increase in sample temperature will result in
improved the extraction efficiency, because of the
increased evaporation of the analyte concentration
in the headspace. The effect of sample temperature
was studied by changing the sample temperature
from 40 to 80 C. As can be seen in figure 2, the
amount of extracted analyte (into the headspace)
increases with increasing temperature up to 80 C.
In headspace analysis, it is recommended not to
use high temperatures (in order to avoid the over-
pressurization of the vial sample, and so avoid
accidents) and, therefore, an extraction
temperature of 70C was selected in environmental
and water samples. The syringe temperature of
5C above vial temperature was selected to avoid
the analytes condensation.
3.2. Extraction time
The time required for the extraction process was
an important parameter to be investigated. The
most adequate time for the HS extraction was
considered to be the time reaching the equilibrium
of the analytes between the vapor phase and
aqueous phase. Extraction time between 5 and 30
min were tested for the samples of 50 µg L-1 at
70°C, and the heating-time profile for the MTBE
and formaldehyde mixture is shown in figure 3.
An increasing efficiency was observed for both
36
Table 2. Analytical conditions of MTBE, formaldehyde and methyl ethyl ketone by GC-MS with SIM
Quantification ions (m/z)Retention time (min)Molecular weightCompound
301.3930
Formaldehyde
731.4588MTBE
431.9073Methyl ethyl keton
Fig. 2. Influence of the extraction temperature on
the relative peak areas of 50 µgL-1 MTBE and
formaldehyde in water.
1750
1770
1790
1810
1830
1850
1870
1890
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
020 40 60 80 100
Peak area (×1000 counts)
Peak area (counts)
Temperature (oC)
MTBE
Fig. 3. Effect of extraction time on peak areas of 50
µgL-1 MTBE and formaldehyde in water at 70 oC.
0
5000
10000
15000
20000
25000
30000
35000
40000
45000
50000
010 20 30 40
Time (min)
Peak area (counts)
830000
850000
870000
890000
910000
930000
950000
970000
Peak area (counts)
HCHO
MTBE
M TBE
HCHO
37
Determination of MTBE and HCHO in water Ali Akbar Miran Beigi, et al
compounds when the longer extraction time
was used until 20 min, and then an increase in
extraction time caused a decrease in the efficiency.
A reason for this phenomenon was the transfer of
water molecules to headspace which diluted the gas
phase and decreased extraction amounts. So the
extraction time of 20 min was considered for the
subsequent experiments.
3.3. Ionic strength influence
Because the ionic strength of the solution
influences the partition coefficient between the
gas and liquid phase (K) the effect of salt amount
on extraction efficiency was also checked. The
effect of the salt on the extraction efficiency was
investigated by comparing the extraction efficiency
of samples which contained different amounts of
sodium chloride (NaCl) from 0 to 40 (%w/v), and
its influence, as the salting out agent, on the ion
abundance of GC-MS chromatogram for MTBE
and formaldehyde is shown in figure 4. As can be
seen the addition of salt does not have the same
effect for both target analytes: the addition of NaCl
led to better results in the case of MTBE, while for
the HCHO no favorable, and sometimes unfavorable
effects (when more than 30% (w/v) of sodium
chloride were employed ) were observed. In human
blood, the effect of different ions on extraction
of Formaldehyde and MTBE based on proposed
procedure was investigated. The interference of
some coexisting ions in blood, serum and urine
samples on the recovery of Formaldehyde and
MTBE was studied under optimized condition. The
proposed procedure was performed using a 10 mL
sample containing 5-500 µgL-1 of formaldehyde
and MTBE and 2 mg L-1 of different concentration
of matrix ions such as, Zn2+, Cu2+, Mn2, Na+, K+,
Ca2+ and Mg2+. The tolerate amounts of important
ions and biological matrix (albumin and proteins)
were tested that caused less than 6% of the head
space extraction alteration. In optimized conditions,
the ions and biological matrix do not interfere to
formaldehyde and MTBE extraction by procedure
(less than 5%). The results showed us, the most of
the probable water matrix concomitant have no
0
100000
200000
300000
400000
500000
600000
700000
800000
900000
010 20 30 40 50
NaCl content (w/v%)
Peak area (counts)
30000
35000
40000
45000
50000
55000
60000
65000
70000
Peak area (counts)
HCHO
MTBE
M TBE
HCHO
Fig. 4. Effect of NaCl additives on detector
response areas of 50 µgL-1 MTBE and formaldehyde
in water produced by HS for 20 min at 705 oC and
sample volume 10 mL in 20 mL vial
considerable effect on the recovery efficiencies of
formaldehyde and MTBE.
For MTBE the headspace extraction efficiency is
increased with increasing concentration of salt in
environmental samples and it reached the peak
yield when NaCl (30%, w/v) was used to saturate
the samples. The reason was considered to be the
increase of ionic strength in aqueous samples by
adding salt, therefore the solubility of analytes
was decreased and more analyte was released into
the headspace. For HCHO the observed behavior
could be explained on account of its high solubility
in water (37%) and strong interaction by solvent
molecules (water) through hydrogen bonding
that cause a greater affinity for water samples.
Therefore, 30 % (w/v) salt content was chosen
for the quantitative simultaneous determination of
both target analytes.
3.4. Sample volume
The ratio of sample volume to headspace volume
is an important parameter that affects the extraction
efficiency of HS. An increase in sample volume and,
consequently, a decrease in headspace volume enhance
the extracted amount of analyte, which improves the
sensitivity. The optimal ratio of the aqueous volume
to the headspace volume for headspace analysis in
20 mL vials was determined by varying the sample
38 Analytical Methods in Environmental Chemistry Journal; Vol. 2 (2019)
volume from 5 mL (1/4 vial volume ) to 15 mL
(3/4 vial volume ). The results are also shown in
Figure 5. The extracted amounts of analytes increase
continuously with increasing sample volume reach a
maximum at an aqueous volume of 10 ml and then
decrease because of the decreased volume of the
headspace. In the work, sample volume of 10.0 mL
(in 20.0 mL vial) was used.
3.5. Evaluation of the method performance
Figure 6 shows a typical total ion chromatogram
(TIC) of a standard solution containing, 100 µg
L-1 of MTBE and HCHO after its headspace
extraction under optimal experimental conditions
in water/wastewater and environmental samples.
The linearity, limits of detection and precision
were calculated when the optimum conditions for
the HS-GC–MS procedure were established. The
linearity of the method was examined by spiking
DDW with MTBE and HCHO in a concentration
range from 5 to 10000 µg L-1 in water samples
and 5 to 500 µg L-1 in waste biological samples.
Each solution was submitted to the HS-GC-MS
analysis three times. The Figures of merit of the
calibration graphs are summarized in Table 3. A
plot of the peak areas against the concentrations of
standards was obtained (Fig.7). Lack-of fit test was
performed to check the goodness of fit and linearity
[48]. Lack-of-fit test demonstrated that the linear
models were adequate because the whole p values
were more than 0.05 at significance level of 95%.
(Table 4).The linear range experiments provided
the necessary information to estimate LODs, based
on the signal that differed three times from the
blank average signal, was 2 and 5 µg L-1 for MTBE
and HCHO, respectively. Analytical accuracy was
assessed from the recovery of analyte spiked to
various of water and environmental samples
(Table5). The repeatability expressed as the
relative standard deviation (R.S.D.) was
obtained by carrying out five replicate assays on
each water samples (Table 2), and gave a value
less than 4.8% and 2.6% in water and
environmental samples, respectively. Therefore,
this method is deemed acceptable for determining
of trace level of µg L-1 in water and
wastewater matrix.
Fig. 6. Total ion chromatogram (TIC) in SIM mode
of an ultrapure water solution contaminated with
MTBE (50 µgL-1) and formaldehyde (50 µgL-1),
extracted using static headspace. Extraction conditions:
Extraction time: 20 min, Extraction temperature: 70
oC, sample volume 10 mL in 20 mL vial and NaCl
30% (w/v).
0
10000
20000
30000
40000
50000
60000
0 5 10 15 20
Volume (mL)
Peak area (counts)
745000
750000
755000
760000
765000
770000
775000
780000
Peak area (counts)
MTBE
HCHO
HCHO
M TBE
Fig. 5. Effect of solution volume in 20 ml vial on
peak areas of 50 µgL-1 MTBE and formaldehyde in
water produced by HS for 20 min at 70 oC.
39
Determination of MTBE and HCHO in water Ali Akbar Miran Beigi, et al
Samples 2 and 3 are also the same
synthetic sample 1 that are treated by 20
picomol of human cytochrome P450 (2A6),
prepared from Sigma-Aldrich Co., at 37 oC
for 13 and 30 minutes, respectively.
Cytochrome P450 (2A6) is known as one of the
most effective enzymes in metabolism
alkoxyethers. In order to control enzyme
activity and termination of reaction time, it was
need to a deactivator such as 100 µL of 0.10 M
perchloric acid. Formaldehyde was also a mainly
byproduct of enzymatic degradation reaction of
MTBE and was detected by developed method as
given in Table 6. In the case of formaldehyde,
although the calculated values can be estimated
stoichiometrically.
Fig. 7. Standard calibration curves of peak areas against the concentrations of MTBE () and HCHO (). MTBE: y
= 14.90x + 28.32 (r = 0.996), HCHO: y = 61.07x + 88.88 (r = 0.998).
Table 3. Analytical figures of merit of the determination of MTBE and HCHO (µg L-1)
Compound Regression Equation aLinear Range LOD
RSD
(%, n = 5)
0.1 40
MTBE y =513.24x+0.319 5-10000 2 4.8 6.8
formaldehyde y = 1.759x + 27.53 5-500 5 1.9 7.8
a y: analyte area-to-internal standard area, x: concentration (µg
L-1).
3.6.Analysis
The proposed method was firstly used to
quantify MTBE and HCHO in water and
wastewater of Tehran oil refinery. The obtained
results in Table 5, showed good recoveries, and the
method was ideally suited for these matrices. The
synthetic biological samples were also
analyzed by the develop method (Table 6).
Here, blank is containing 500 µL mixture of 50
mM tris-HCl buffer (pH=7.4), 1mM NADPH (as
inducer), 10 mM MgCl2 and 150 mM KCl (as
electrolytes). Synthetic sample 1 is prepared by
addition of 5.02 µg ml-1 MTBE in the blank
solution.
Table 4. Evaluation of the goodness of fit and linearity of calibration graphs
Compound Correlation coefficient, r Determination coefficient, R2Lack-of-fit, pa
MTBE 0.9998 0.9993 0.089 > 0.05
Formaldehyde 0.9996 0.9984 0.078 > 0.05
a Confidence interval, 95%.
40
Analytical Methods in Environmental Chemistry Journal; Vol. 2 (2019)
5. References
[1] R.J. Kieber, M.F. Rhines, J.D. Willey, Rainwater
formaldehyde: concentration, deposition and
photochemical formation, Atmos. Environ., 33 (1999)
3659-3667.
[2] J. K. Fawell, Formaldehyde in Drinking-water,
Background document for development of Guidelines
for drinking-water quality, World Health Organization
(WHO), UK, 2005.
[3] M. Shamsipur, A. A. Miran Beigi, M. Teymouri,
T. Poursaberi, S.M. Mostafavi, P. Soleimani,
Biotransformation of methyl tert-butyl ether by
human cytochrome P450 2A6, Biodegradation, 23
(2012) 311-318.
[4] R.G. Liteplo, R. Beauchamp, M. E. Meek, R. Chenier,
Concise international chemical assessment document
40: formaldehyde, World Health Organization
(WHO), Geneva, 2018.
[5] U.S. Environmental Protection Agency (USEPA),
report to congress on indoor air quality, assessment
and control of indoor air pollution, Volume 2, 2017.
[6] National Institute for Occupational Safety and Health
(NIOSH), Manual of analytical methods, 4th ed.,
department of health and human services, Cincinnati,
OH, USA, 2018.
[7] G. Nael, Y. H. S. Maha, A. Mosallb, Spectrophotometric
determination of formaldehyde based on the
telomerization reaction of tryptamine, Arabian J.
Table 5. Determination of HCHO and MTBE in water and Human samples at optimum extraction conditions (µg L-1)
Well water c
Tap water
Water Recovery (%)Found
aAddedConc.Recovery (%)Found
aAddedConc.
95.623.9 ± 4.225.0NDb
100.825.2 ± 2.825.0NDb
HCHO
97.036.2 ± 3.125.012.097.624.4 ± 4.825.0NDb
MTBE
PetrochemicalOil company
Wastewater Recovery (%)Found
aAddedConc.Recovery (%)Found
aAddedConc.
97.022.5 ± 4.210.012.896.541.4 ± 2.320.022.1HCHO
96.019.3 ± 3.110.09.7103.136.9 ± 1.520.016.3MTBE
a Mean of triplicates with percent R.S.D (n=5).
b Not found.
c Well water nearby Tehran oil refinery.
The standard method based on derivatization
with 2, 4-dinitrophenylhydrazine and HPLC
detection was used to assay the values[49]. An
average recovery of 65.5 and 91.7 % was obtained
for degradation process of MTBE after passing 13
and 30 min from course of the reaction,
respectively. The SD of measurements at ppm
levels was not greater than 2.6%.
4. Conclusions
An automated and simple method has been
developed for simultaneous determination of MTBE
and formaldehyde in water and human matrices.
It was based on the use of HS device coupled
with a GC–MS instrument. The no necessity of
consumables or reagents for sample treatment made
HS-GC–MS to be considered as the best extraction
option of the studied ones. The analysis required
20 min of sample incubation or extraction time and
less than 5 min for chromatographic determination
programming the MS detector in SIM acquisition
mode. Good precision and the simple sample
preparation enable to use this procedure for
routine investigations. This proposed method was
then applied to the analysis of human biological
and environmental samples (synthetic biological
samples).
Table 6. Simultaneous determination of MTBE and Formaldehyde in synthetic biological samples
Formaldehyde / µgml-1
MTBE / µg ml-1
SampleNo.
FoundCalcd.FoundCalcd.
--4.915.02Synthetic sample 11
1.141.091.73-Synthetic sample 22
1.531.480.415-Synthetic sample 33
41
Determination of MTBE and HCHO in water; Ali Akbar Miran Beigi, et al
Chem., 8 (2015) 487-494.
[8] N. Jaman, Md. S. Hoque, S.C. Chakraborty, Md. E.
Hoq, H.P. Seal, Determination of formaldehyde
content by spectrophotometric method in some fresh
water and marine fishes of Bangladesh, Int. J. Fish.
Aqu. Studies 2 (2015) 94-98.
[9] L. Bolognesi, E. J. dos Santos, G. Abate, Determination
of formaldehyde by flow injection analysis with
spectrophotometric detection exploiting brilliant
green–sulphite reaction, Chem. Papers, 69 (2015)
791–798.
[10] N. Teshima, S. K. M. Fernández, M. Ueda, H.
Nakai, T. Sakai, Flow injection spectrophotometric
determination of formaldehyde based on its
condensation with hydroxylamine and subsequent
redox reaction with iron(III)-ferrozine complex
Talanta, 84 (2010) 1205-1208.
[11] A. Afkhami, H. Bagheri, Preconcentration of trace
amounts of formaldehyde from water, biological
and food samples using an efficient nanosized solid
phase, and its determination by a novel kinetic
method Microchim. Acta, 176 (2012) 217-227.
[12] A. Blondel, H. Plaisance, Screening of formaldehyde
indoor sources and quantification of their emission
using a passive sampler, Build. Environ., 46 (2011)
1284-1291.
[13] S. Abbasi, M. Esfandyarpour, M. A. Taher, A.
Daneshfar, Catalytic-kinetic determination of trace
amount of formaldehyde by the spectrophotometric
method with a bromate-Janus green system,
Spectrochim. Acta, 67 (2007) 578-581.
[14] Zh.Q. Zhang, H.T. Yan, X.F. Yue, Catalytic
determination of trace formaldehyde with a flow
injection system using the indicator reaction between
crystal violet and bromate, Microchim. Acta, 146
(2004) 259-263.
[15] M.K.L. Bicking, W.M. Cooke, F.K. Kawahara, J.E.
Longbottom, The effect of pH on the reaction of
2,4-Dinitrophenylhydrazine with formaldehyde and
acetaldehyde, J. Chromatogr., 455 (1988) 310-314.
[16] X.Y. Sui, X.M. Li, Z.Y. Zhang, Y. Song, L. Chen, H.Zh.
Zhang, Analysis of free formaldehyde in textiles by
gas chromatography, Chin. J. Anal. Chem. 30 (2002)
1333-1336.
[17] L. Nondek, R.E. Milofsky, J.W. Birks, Determination
of carbonyl compounds in air by HPLC using on-
Line analyzed microcartridges, fluorescence and
chemiluminescence detection, Chromatographia, 32
(1991) 33-39.
[18] R.T. Rivero, V.J. Topiwala, Volatile organic
compounds(VOCs) in marine water at the ng
concentration level, J. Chromatogr. A 1029 (2004)
217-222.
[19] Q. Li, M. Oshima, S. Motomizu, Flow-injection
spectrofluorometric determination of trace amounts
of formaldehyde in water after derivatization with
acetoacetanilide. Talanta, 72 (2007) 1675-1680.
[20] F. Santos de Oliveira, E.T. Sousa, J.B. De Andrade,
A sensitive flow analysis system for the fluorimetric
determination of low levels of formaldehyde in
alcoholic beverages. Talanta, 73 (2007) 561-566.
[21] B.X. Li, M.L. Liu, Z.J. Zhang, C.L. Xu, Flow-injection
chemiluminescence determination of formaldehyde
with a bromate-rhodamine 6G system. Anal. Sci., 19
(2003) 1643-1646.
[22] Z.H. Song, S.A. Hou, On-line monitoring
of formaldehyde in water and air using
chemiluminescence detection. Int. J. Environ. Anal.
Chem., 83 (2003) 807-817.
[23] Z.Q. Zhang, H. Zhang, G.F. He, Preconcentration
with membrane cell and adsorptive polarographic
determination of formaldehyde in air, Talanta, 57
(2002) 317-322.
[24] J.H. Tang, X.M. Wang, G.Y. Sheng, J.M. Fu, The
progress of the analysis of formaldehyde and other
carbonyls in atmosphere, Chin. J. Anal. Chem., 1
(2005) 134-140.
[25] C. Zhao, M. Li, K. Jiao, Determination of formaldehyde
by staircase voltammetry based on its electrocatalytic
oxidation at a nickel electrode, J. Anal. Chem., 61
(2006) 1204-1208.
[26] K. Toda, K. Yoshioka, K. Mori, S. Hirata, Portable
system for near-real time measurement of gaseous
formaldehyde by means of parallel scrubber stopped-
flow absorptiometry, Anal. Chim. Acta, 531 (2005)
41-49.
[27] K. Kawamura, K. Kerman, M. Fujihara, N. Nagatani,
T. Hashiba, E. Tamiya, Development of a novel hand-
held formaldehyde gas sensor for the rapid detection
of sick building syndrome, Sens. Actuators B, 105
(2005) 495.
[28] L. Campanella, M. Battilotti, R. Dragone, I. Mevola,
Suitable solid state chemical sensor for HCHO
42
Analytical Methods in Environmental Chemistry Journal; Vol. 2 (2019)
determination. Int. J. Environ. Pollut., 27 (2006) 313-
323.
[29] EFOA, European Fuel Oxygenates Association, Fuel
ethers and gasoline, available at http://www.efoa.org
(Accessed May 26, 2016).
[30] B. Allen, MTBE friend or foe, Green Chem., (1999)
142-151.
[31] D.A. Cassada, Y. Zhang, R.F. Spalding, Trace analysis
of ethanol, MTBE, and related oxygenate compounds
in water using solid phase microextraction and gas
Chromatography/Mass spectrometry, Anal. Chem., 72
(2000) 4654-4658.
[32] United States Environmental Protection Agency
(USEPA), Office of research and development,
oxygenates in Water: critical information and research,
EPA/600/R-98/048, Washington, DC, 2018.
[33] C.D. Church, L.M. Isabelle, J.F. Pankow, D.L. Rose,
P.G. Tratnyek, Method for determination of methyl
tert-Butyl ether and its degradation products in water,
Environ. Sci. Technol., 31 (1997) 3723-3726.
[34] L. Zwank, T.C. Schmidt, S.B. Haderlein, M. Berg,
Simultaneous determination of fuel oxygenates
and BTEX using direct aqueous injection gas
chromatography mass spectrometry (DAI-GC-MS).
Environ. Sci. Technol., 36 (2002) 2054-2059.
[35] B. Nouri, B. Fouillet, G. Touissaint, R. Chambon, P.
Chambon, Complementarity of purge-and-trap and
head-space capillary gas chromatographic methods
for determination of methyl-tert.-butyl ether in water,
J.Chromatogr., A 726 (1996) 153-159.
[36] C. Achten, W. Püttmann, Determination of methyl
tert-Butyl Ether in surface water by use of solid phase
microextraction. Environ. Sci. Technol., 34 (2000)
1359-1364.
[37] C. Achten, K. Axel, W. Püttmann, Sensitive method for
determination of methyl tert-butyl ether (MTBE) in
water by use of HS-SPME/GC-MS. Fresenius J.Anal.
Chem., 371 (2001) 519-525.
[38] L. Black, D. Fine, High levels of monoaromatic
compounds limit the use of solid phase microextraction
of methyl tert-butyl ether and tert-butyl alcohol.
Environ. Sci. Technol., 35 (2001) 3190-3192.
[39] D,A. Cassada, Y. Zhang, R.F. Spalding, Trace analysis
of ethanol, MTBE, and related oxygenate compounds
in water using solid phase microextraction and gas
Chromatography/Mass spectrometry. Anal.Chem., 72
(2004) 4654.
[40] I. Arambarri, M. Lasa, R. Garcia, E. Millán,
Determination of fuel dialkyl ethers and BTEX in
water using headspace solid-phase microextraction
and gas chromatography–flame ionization detection,
J.Chromatogr., A 1033 (2004) 193-203.
[41] F. Fang, C.S. Hong, S. Chu, W. Kou, A. Bucciferro,
Reevaluation of headspace solid-phase microextraction
and gas chromatography–mass spectrometry for the
determination of methyl tert-butyl ether in water
samples, J.Chromatogr., A 1021 (2003) 157-164.
[42] J. Dron, R. Garcia, E. Millan, Optimization of
headspace solid-phase microextraction by means of an
experimental design for the determination of methyl
tert.-butyl ether in water by gas chromatography–
flame ionization detection, J. Chromatogr., A 963
(2002) 259-264.
[43] F.L. Cardinali, D.L. Ashley, J.C. Morrow, D.M. Moll,
B.C. Blount, Measurement of trihalomethanes and
methyl tertiary-butyl ether in tap water using solid-
phase microextraction GC-MS, J. Chromatogr. Sci.,
42 (2004) 200-206.
[44] S. Nkamura, S. Daishima, Simultaneous determination
of 22 volatile organic compounds, methyl-tert-butyl
ether, 1,4-dioxane, 2-methylisoborneol and geosmin
in water by headspace solid phase microextraction-
gas chromatography–mass spectrometry, Anal. Chem.
Acta, 548 (2005) 79-85.
[45] A.S. Yazdi, H. Assadi, Determination of trace of methyl
tert-butyl ether in water using liquid drop headspace
sampling and GC, Chromatographia, 60 (2004) 699-
702.
[46] N. Bahramifar, Y. Yamini. S. Shariat-Feizabadi,
M. Shamsipur, Trace analysis of methyl tert-butyl
ether in water samples using headspace solvent
microextraction and gas chromatography–flame
ionization detection, J. Chromatogr., A 1042 (2004)
211-217.
[47] M.P. Munoz, F.J.M. De Villena Rueda, L.M.P.
Diez, Determination of formaldehyde in air by flow
injection using pararosaniline and spectrophotometric
detection, Analyst, 114 (1989) 1469-1471.
[48] L. Kirkup, M. Mulholland, Comparison of linear
and non-linear equations for univariate calibration, J.
Chromatogr., A 1029 (2004) 1-11.
[49] Standard test method (ASTM D5197) for determination
of formaldehyde and other carbonyl compounds in air,
Philadelphia, USA, 2018.