Analytica Chimica Acta 1062 (2019) 94e101

Contents lists available at ScienceDirect

Analytica Chimica Acta

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

Multifunctional microchip-based distillation apparatus I - Steam

distillation for formaldehyde detection
Sheng-Yen Hsu a, 1, Chan-Chiung Liu b, 1, Chia-En Yang c, Lung-Ming Fu d, e, *
a
Department of Mechanical and Electro-Mechanical Engineering, National Sun Yat-sen University, Kaohsiung, 804, Taiwan
b
Department of Food Science, National Pingtung University of Science and Technology, Pingtung, 912, Taiwan
c
Office of Physical Education, National Pingtung University of Science and Technology, Pingtung, 912, Taiwan
d
Graduate Institute of Materials Engineering, National Pingtung University of Science and Technology, Pingtung, 912, Taiwan
e
Department of Engineering Science, National Cheng Kung University, Tainan, 701, Taiwan

h i g h l i g h t s g r a p h i c a l a b s t r a c t

A rapid microchip-based distillation

apparatus for distilled CH2O is
proposed.

CH2O distillation efficiency as high as
98% at optimal distillation conditions.

CH2O concentrations of 21 commer-
cial food samples are measured.

System detection limit is around
0.5 ppm and deviation is less than
4.3%.

a r t i c l e i n f o a b s t r a c t

Article history: A multifunctional microchip-based distillation apparatus for distilling and detecting formaldehyde
Received 25 November 2018 (CH2O) in food products is developed. The presented apparatus comprises a disposable microchip, a
Received in revised form steam supply system, and a recirculating cooling water supply. The microchip is formed on PMMA
26 January 2019
substrates by laser ablation and includes a sample zone, a flash distillation zone, a cooling zone, a
Accepted 4 February 2019
Available online 19 February 2019
condensation zone, and a collection zone. In the presented method, the CH2O sample is placed in the
microchip and is vaporized by the high-throughput vapor supply and driven through the condensed
zone. The condensed CH2O liquid is guided into the collection zone of the microchip. Finally, the distilled
Keywords:
Steam distillation
CH2O solution is determined using an AHMT spectrometry method and a paper-based RGB (red, green
Microchip and blue) intensity analysis method. A distilled efficiency is as high as 98%, when a vapor stream rate is
Formaldehyde 0.4 ml/min and a distilled time is 10 min. Moreover, both detection methods show linear relationships of
AHMT spectrometry the corresponding CH2O concentrations. The actual sample suitability of the presented multifunctional
Paper-based device microchip-based distillation apparatus is confirmed by analyzing the CH2O concentrations of 21
commodities.
© 2019 Elsevier B.V. All rights reserved.

1. Introduction

Formaldehyde (CH2O) is an endogenous reactive carbonyl spe-

cies (RCS) produced through the enzyme-assisted oxidation of
* Corresponding author. Department of Engineering Science, National Cheng certain amino acids and carbohydrates [1]. CH2O exists at low levels
Kung University, Tainan, 701, Taiwan.
E-mail address: loudyfu@mail.ncku.edu.tw (L.-M. Fu).
in most organisms and occurs naturally as a metabolic intermediate
1
These authors contributed equally to this work. in many vegetables, fruits, seafood, meat and dairy products [2].

https://doi.org/10.1016/j.aca.2019.02.016
0003-2670/© 2019 Elsevier B.V. All rights reserved.
 S.-Y. Hsu et al. / Analytica Chimica Acta 1062 (2019) 94e101
Furthermore, CH2O is often used as a food preservative to maintain
the original color and odor of the food and prolong its shelf life.
However, CH2O is a toxic and carcinogenic substance [1,3], and is
associated with various diseases when present in excessive quan-
tities, including cancer, asthma, and neuron disorders [4,5].
Consequently, the WHO (World Health Organization) has stipu-
lated a maximum indoor CH2O concentration of 80 ppb averaged
over 30 min [6], while the OSHA (Occupational Safety and Health
Administration) in the USA has set a PEL (Permissible Exposure
Limit) of 750 ppb for CH2O and an IDLH (Immediately Dangerous to
Life and Health) limit of 20 ppm [7].
Accurate measures for analyzing CH2O concentration in com-
modity foods are essential in safeguarding human health. Accord-
ingly, many CH2O detection methods have been proposed,
including colorimetric detection [8,9], fluorescent quantitative
detection [10,11], AHMT spectrometry [12,13], electrochemical
biosensors [14e16], gas chromatography (GC) [17,18], liquid chro-
matography [19e21], Raman spectroscopy [22,23], infrared spec-
troscopy [24,25], microfluidic systems [26e30], paper-based
devices [31e33], and others [34e38]. Most of analytical methods
demand a distilled procedure and formed CH2O complex for
measuring objectives. However, traditional distillation systems
generally involve the huge and heavy instrument. Accordingly, the
CH2O analysis procedure is always processed in a laboratory
setting. Consequently, the use of miniaturized systems to perform
CH2O distillation has attracted significant attention in the pub-
lished literature.
Chip-based microfluidic systems offer the advantages of low
sample and reagent volumes, a short reaction time, and the po-
tential for integration with other miniaturized systems to realize
sophisticated Lab-on-a-Chip (LoC) devices and can be completed
analysis on a single device [39e45]. As a result, many microfluidic
devices for chemical and medical applications in the fields of
environmental surveillance, food safely analysis, and drug devel-
opment have been developed in recent years [46e52].
Many researchers have presented proposals for reducing the
distillation process to the microscale [53,54]. However, in the
micro-distillation process, the surface tension of the liquid mixture
dominates gravitational and hydrodynamic effects. Therefore,
achieving a continuous liquid-vapor interface for mass exchange,
and driving the flow of liquid reflux in the distillation process,
represents a significant challenge. Nonetheless, many methods
have been proposed for separating miscible fluid mixtures in the
micro-distillation process using such techniques as carrier gas/va-
por flows [55e58], vacuum membranes [59e61], centrifugal/
gravitational forces [62], bubble [63] and capillary forces [64,65],
and others [53]. Lam et al. [64] developed a microflow distillation
chip in which the liquid flow was guided by the capillary force
induced by micro-pillars arranged along the two sides of the
channel. The study presented a satisfactory separation function for
both watereacetone and tolueneemethanol mixtures given
appropriate settings of the heating and cooling temperatures,
respectively. In a later study [65], the same group performed a
parametric study on the effects of the key operating parameters on
the performance of the proposed device, containing the tempera-
ture of the heating and cooling regions, the flow rate and compo-
sition of the feed solution, and the flow rate of the bottom stream.
The same group [66] also developed an in-situ study of the sepa-
ration of benzaldehydeetoluene mixtures utilizing a microfluidic
distillation chip containing a serpentine microchannel with
micropillars. The results revealed that separation was constrained
to only a limited section of the chip and hydrodynamic effects
resulted in slug formation, which further affected the separation
process. Most of the previous researches on micro-distillation
processes focused on designing microfluidic distillation chips
95
rather than the entire apparatus. As a result, microfluidic distilla-
tion chips are successfully miniaturized, but detection and associ-
ated devices are still large instruments. It can only be used in
laboratories or inspection centers and cannot be used for on-site
detection and inspectors must have relevant training. The pro-
posed microchip-based distillation apparatus can solve this prob-
lem, and possess the features of rapid reaction time, low cost,
excellent portability, convenient operation and on-site detection.
The study presents a rapid PMMA microchip-based distillation
apparatus for CH2O distillation and quantification purposes. The
apparatus incorporates a high-temperature vapor supply, a low-
temperature water supply, and a microchip. The microchip is
formed on PMMA substrates by laser ablation and involves a
sample inlet and vaporization zone, a distillation zone, a cooling
zone, a condensation zone, and a collection zone. In the presented
distillation procedure, the CH2O sample (acidified with 20% phos-
phoric acid) is placed in the microchip, evaporated and driven
through a flash distillation zone under the high-throughput vapor
stream. The CH2O vapor is cooled to a temperature below the vapor
point by the cooling water stream, and then the condensate enters
the collection zone. Finally, the CH2O concentration of the
condensate is detected using either an AHMT spectrometry method
or a paper-based RGB (red, green and blue) intensity analysis
method.
2. Experimental details
2.1. Fabrication of PMMA-based disposable microchip
The proposed microchip was designed using commercial soft-
ware (AutoCAD, 2016) and formed on PMMA substrates utilizing
the CO2 laser ablation system described in Ref. [67]. The authors
had once used 3D printing to make PMMA microchips. However,
fabricating the PMMA microchip by CO2 laser ablation is faster than
3D printing, also the surface roughness via CO2 laser ablation
method is superior to 3D printing. In Fig. 1(a)~(c), the microchip
had a total size of 115  42  24 mm3 and included a sample zone, a
distillation and condensation zone, a water cooling channel and a
collection zone. The microchip consisted of a total of ten layers,
including three layers (Layers #1e3) for the flash distillation zone
(thickness of 2 mm), three layers (Layers #4e6) for the sample zone
and collection zone (thickness of 4 mm), two layers (Layers #7e8)
for the condensation zone (with size of 150  5  2 mm3) and two
microchannels, two layers (Layers #9e10) for the cooling zone
(with a depth of 2 mm) and a covering aluminum film (thickness
0.5 mm). (Note that in the condensation zone sample stream
changes from a vapor phase to a liquid phase, but in the cooling
zone always exist a coolant stream.) Following the fabrication
procedure, the ten substrates were precisely aligned and bonded
utilizing a thermal-compression method. In short, the substrates
were held by a fixed pressure of 0.6 kg/cm2 as the temperature was
raised to above 98  C in 5 min. Then, the pressure was raised to
1.5 kg/cm2 and kept at a constant temperature for 15 min. At last,
the pressure was liberated and the microchip was naturally cooled
at room temperature. Fig. 2 shows front- and rear-view photo-
graphs of the completed chip, including the rapid couplers used to
combine the high-temperature vapor stream and cooling water
flow (see Fig. 2(b)), respectively. For the PMMA-based disposable
microchip, there is exclusively no chemical attack of the PMMA
substrate. The material cost of PMMA microchip is extremely low,
but the design is very complex including ten layers structure, five
zones, flow and stream channels, and two microchannels. The
PMMA microchip can also be reused, but it needs high pressure
stream to clear the microchannels. In order to avoid pollution, the
microchip is designed as disposable.
96 S.-Y. Hsu et al. / Analytica Chimica Acta 1062 (2019) 94e101
Fig. 1. The structure and dimensions of microchip: (a) front section, (b) rear section, (c) front section with cutaway view showing sample, and (d) separating elements between front
and rear sections.
Fig. 2. Photographs of presented microchip: (a) front view, and (b) rear view.
2.2. Standard CH2O samples and reagents
A standard solution of formaldehyde with a concentration of
100 ppm was prepared by diluting of 37% aqueous CH2O solution
(Taiwan Hipoint Co., Taiwan) with distilled water. The stock solu-
tion was then further diluted with distilled water to produce
standard CH2O samples with concentrations ranging from 0.2 to
10 ppm. The AHMT (4-Amino-3-hydrazino-5-mercapto-1,2,4-
triazole, C2H6N6S) reagent solution used in the AHMT spectrom-
etry detection method, was prepared by mixing 0.5 g AHMT solu-
tion (99%, Showa Chemical Co., Ltd; Tokyo, Japan) with 100 ml of
0.5 N HCl. In performing the AHMT detection process, the absor-
bance of the CH2O-AHMT reaction mixture was measured at
550 nm using a commercial UV/VIS spectrophotometer (LK-5200,
Shan Shui Tech. Ltd., Taiwan). Meanwhile, in the paper-based
detection method, the CH2O concentration was inferred from the
UV light-induced fluorescence intensity of the formaldehyde-
Acetoacetanilide complex (dihydropyridine derivative) produced
in a Hantzsch reaction. (Note that complete details of the paper-
based detection method based on Hantzsch reaction are available
in Ref. [32].)
2.3. Food samples
The practical feasibility of the presented distillation apparatus
was evaluated by distilling and analyzing the CH2O concentrations
of 21 commodity foods, namely Test #1 (Dried mushroom 1,
Taiwan); Test #2 (Dried mushroom 2, China); Test #3 (Dried shrimp,
Taiwan); Test #4 (Dried fungus, China); Test #5 (West ginseng,
Taiwan); Test #6 (Shrimp bran, Taiwan); Test #7 (Candiedmelon,
Taiwan); Test #8 (Ginseng, China); Test #9 (Black olive, Taiwan); Test
#10 (Shreddle ginger, Taiwan); Test #11 (Dried dioscoreae rhizoma,
Taiwan); Test #12 (Flammulina velutipes, Taiwan); Test #13 (Rice
 S.-Y. Hsu et al. / Analytica Chimica Acta 1062 (2019) 94e101
flour, Taiwan); Test #14 (Sprouts, Taiwan); Test #15 (Dried lemon,
Taiwan); Test #16 (Dried fig, Taiwan); Test #17 (Dried orange peel,
Taiwan); Test #18 (Jujube beans, Taiwan); Test #19 (Dried pineapple,
Taiwan); Test #20 (Panax quinquefolius, Taiwan); and Test #21
(Korean red ginseng, Korean). To evaluate the accuracy of the anal-
ysis results, the CH2O concentrations of the 21 commodity samples
were also analyzed by the CAAPIC (Center for Agricultural and
Aquacultural Product Inspection and Certification at National
Pingtung University of Science and Technology (NPUST) in Taiwan,
ISO/IEC 17025 certified laboratory) utilizing an official macroscale
distillation method, followed by AHMT detection method (detec-
tion limit: ~2 ppm).
2.4. Distillation apparatus structures and distillation procedures
Fig. 3(a) presents the main parts in the proposed distillation
apparatus with size of 35  25  25 cm3. The distillation apparatus
was connected to a DI water tank (500 ml) for steam distillation.
The water tank may be changed to a carrier gas cylinder for aeration
distillation. A PMMA-based microchip can be quickly connected to
the distillation apparatus through a chip holder by rapid couplers.
The distillation apparatus was also inserted with a touch panel
(using self-written software) to program and control the distillation
process. Fig. 3(b) shows internal components of the distillation
apparatus, including a chip holder, a distilled water tank and steam
generator, a DC power supply, a heating module, a temperature
control module, a cooling module, a Programmable Logic Controller
(PLC), and a Human Machine Interface (HMI). The procedures in the
distillation and detection process were as follows: (1) 0.2 ml CH2O
solution (2 g CH2O added to 20% phosphoric acid (H3PO4) solution)
is placed in the sample zone of the microchip. (2) The steam inlet of
the microchip is joined to the high-throughput vapor generator
module and the temperature control module was actuated such
that the distilled water in the vapor generator reaches the boiling
temperature (100  C) after about 5 min. (3) The vapor stream rate
control valve is then opened, allowing the high-temperature vapor
to flow through the sample zone for 10 min. The vapor stream
mixes with the CH2O sample to partially evaporate. The sample
solution/evaporated CH2O gas is then passed through the distilla-
tion and condensation zone by vapor stream, where its tempera-
ture was reduced to a point lower than the vapor point by a low-
temperature cooling stream with an entrance temperature of
about 5  C. (Note that both temperatures of inlet (sample zone) and
Fig. 3. Photographs of: (a) presented multifunction microchip-based distillation apparatus, (b) main ancillary components in multifunction distillation apparatus.
97
outlet (collection zone) will be detected by thermocouples (TK-
6200, Rixen Technology Co., Taiwan)) Eventually, the condensed
CH2O liquid was guided into the collection zone of the microchip,
where it would be retrieved for subsequent concentration detec-
tion. (4) The CH2O detection process was performed using two
different methods, namely (i) an AHMT spectrometry method
performed using Official Method No. 1041901505 issued by TFDA,
Taiwan; and (ii) a paper-based colorimetric method based on
Hantzsch reaction [32].
3. Results and discussion
3.1. Temperature distribution in microchip
Three-dimensional (3-D) computational fluid dynamics
(ANSYS-FLUENT) are executed to observe the steam temperature
contours and flow field in the distillation and condensation zones
of the microchip. The detailed illustration of the governing equa-
tions and computational process was represented in the previous
study [68].
Fig. 4 shows the simulation results obtained for a vapor stream
rate of 0.5 ml/min. As shown in Fig. 4(a), the entrance of the gas
stream into the microfluidic chip through two separate micro-
channels results in the formation of a flow vortex structure within
the sample zone and distillation zone, which prompts the rapid
vaporization of the CH2O sample. Moreover, as shown in Fig. 4(b),
the gaseous sample entering the condensation zone is cooled from
100  C at the inlet to 17  C (i.e., liquid phase) at the outlet. Mean-
while, the temperature of the cooling stream rises from 8  C at the
inlet to around 17  C at the outlet. The average temperatures of the
inlet (sample zone) and outlet (collection zone) were measured by
thermocouples to be 100.82  C and 17.35  C, respectively. The
measurement results deviate by no more than 2.0% from those
obtained using a numerical method.
3.2. Effects of vapor stream rate and distilled time
In the presented instrument, the rate at which the CH2O sample
is evaporated and delivered pass the flash distillation and
condensation zones depends on the vapor stream rate and distilled
time. As a result, both parameters have a key effect on the distilled
efficiency of the system, defined in this study as
98 S.-Y. Hsu et al. / Analytica Chimica Acta 1062 (2019) 94e101
Fig. 4. Simulation results for: (a) vapor distribution in sample and flash distillation
zones, and (b) sample vapor and cooling water stream fields in condensation and
cooling zones.
Distilled efficiency ¼ [Distilled CH2O con. (ppm) / Reference CH2O
con. (ppm)] (1)
The working steam flowrate is governed by the steam pressure.
In addition, it is used to vaporize the formaldehyde and carry it. In
order to obtain the optimum vapor stream rate, the steam is in
contact with the sample only after reaching 100  C and high-
pressure (>2 bar). Fig. 5(a) shows the variation of the distilled ef-
ficiency with the vapor stream rate (0.1e0.7 ml/min) utilizing a
fixed CH2O concentration of 8 ppm and a constant distillation time
of 15 min. For each sample, there are 5 individual measurements at
Fig. 5. Variation of distilled efficiency with: (a) vapor stream rate, and (b) distilled time.
the same conditions to get the average values. It can be seen that
the distilled efficiency rises approximately linearly as the vapor
stream rate is risen from 0.1 to 0.4 ml/min, but then decreases
slightly as the flow rate is further risen to 0.7 ml/min. Accordingly,
the optimal vapor stream rate was chosen as 0.4 ml/min. Fig. 5(b)
shows the change of the distilled efficiency with the distilled time
at a value of the vapor stream rate of 0.4 ml/min. As shown, the
maximum distilled efficiency (~98%) is obtained after a distilled
time of 10 min. Thus, the distilled time was set as 10 min in all of the
distillation and mensuration experiments. The proposed distilla-
tion apparatus utilizes a microchip to integrate the conventional
distilled columns. Since the microchip has larger surface-area-to-
volume ratio in channel, obviously causes the excess shear stress
effect of the flow, which consequently increase reaction and sep-
aration efficiency. Because the targets of micro-distillation method
are different in the literature. It is difficult to compare the distilla-
tion efficiency between the proposed distillation apparatus and
micro-distillation methods in the literature. However, the proposed
distillation apparatus can compare distillation efficiency with
conventional distillation methods having the same target. The
distillation time of proposed distillation apparatus is only 1/6
(10 min: 60 min of each sample) compared to the conventional
distillation method.
3.3. Calibration of AHMT and paper-based methods
For measuring concentration methods, two methods were used
to analyze the absorbance intensity (AHMT detection method) and
B (blue) intensity (paper-based detection method) of standard
CH2O samples ranging from 0.2 to 8 ppm. Fig. 6(a) indicates the
linear relationship results acquired by the AHMT detection method
for CH2O samples of 0.5e8 ppm. For each sample, there are 5 in-
dividual mensuration at the same conditions to get the average
values. Using a linear regression manner, the relative results of
CH2O concentration (X) and absorbance value (Y), where the linear
regression function is Y ¼ 0.2638 X þ 0.0199 and linear relationship
factor (R2) is 0.9971. In order to confirm the limit-of-detection
(LOD) of the presented distillation apparatus, a control CH2O
samples with concentration of 0.5 ppm was distilled by presented
microchip-based distillation apparatus and CH2O concentration
measured by AHMT method. The results showed that 0.486 ppm
 S.-Y. Hsu et al. / Analytica Chimica Acta 1062 (2019) 94e101 99

Fig. 6. (a) Variation of absorbance value with CH2O concentration in AHMT spectrometry detection method, and (b) variation of B (blue) fluorescence intensity value with CH2O
concentration in paper-based detection method. (For interpretation of the references to color in this figure legend, the reader is referred to the Web version of this article.)

was obtained by the proposed method. Fig. 6(b) presents the B 3 (CAAPIC analysis method) as a benchmark, the accuracy (%) is
  
(blue) fluorescence values acquired under the paper-based analysis  
defined as ¼ 1  Microdistillation methodmacroscale method  100%.
method with CH2O concentrations ranging from 0.2 to 3 ppm. The
linear regression function is Y ¼ 30.971 X þ 117.782 and linear
relationship factor (R2) is 0.9938, where the Y is the fluorescence
value and the X is the CH2O concentration. Overall, the two figures
show that both detection methods have a linear function and a high
linear relationship factor over the respective CH2O concentration
ranges. Consequently, the validity of the presented distillation
apparatus and detection procedure (AHMT or paper-based) is
confirmed.
3.4. CH2O distillation and concentration detection in real-world
food samples
The feasibility of presented microchip-based distillation appa-
ratus for real-sample CH2O analysis applications was evaluated by
analyzing the CH2O concentrations of the 21 food samples listed in
Section 2.3. For comparison purposes, the CH2O concentration was
analyzed under four analysis methods. In the Case 1 analysis
method, the CH2O solution was distilled utilizing the presented
distillation apparatus and detection was accomplished using the
AHMT spectrometry method according to the Official Method No.
1041901505 laid down by the Taiwan TFDA. In the Case 2 analysis
method, the distilled CH2O solution was again distilled utilizing the
presented distillation apparatus, but the detection procedure was
accomplished using the paper-based detection method. (Note that
full details of the detection procedure are presented by the present
group in Ref. [32].) In the Case 3 analysis method, the distilled CH2O
solution and detected CH2O concentration procedure were entirely
completed by the CAAPIC at NPUST in Taiwan. In the Case 4 analysis
method, the CH2O solution was distilled utilizing the presented
distillation apparatus and the detection procedure was completed
by CAAPIC.
The detection results obtained under the four analysis methods
are presented in Table 1. For each sample of Case 1 and 2, there are 5
individual mensuration at the same conditions to get the average
values. It can be seen that none of the methods provide a result for
Tests #17 to #21. It is clear that CH2O is not included in any sample
or contains only very slight (undetectable) amounts. Based on Case
macroscale method 
Results show that the accuracy was achieved the variety between
95.7% (Test #3) and 98.9% (Test #4) of the analysis results which
utilized the presented distillation apparatus and paper-based
platform. The Case 3 (CAAPIC) analysis method is built on a large-
scale official distillation equipment with a sample volume larger
than 50 g. By contrast, the distillation apparatus presented in the
study requires a total sample volume of just 0.5 ml. Moreover, the
detection limit for analyzing CH2O using the CAAPIC method is
approximately 2 ppm. Consequently, Tests #11 to #16 are unde-
tectable by the CAAPIC analysis method (as shown in Case 3). In
contrast, the presented distillation apparatus successfully analyzes
the CH2O concentrations of six samples (as shown in Case 1, Case 2
and Case 4). Thus, the presented microchip-based distillation
apparatus has the capability to distill and analyze CH2O concen-
trations below than 2 ppm. The LOD of the presented distillation
apparatus is approximately 0.5 ppm.
4. Conclusion
This study has developed a microchip-based distillation appa-
ratus for CH2O distillation and analysis in commodity foods. The
presented distillation apparatus comprises a microchip, a high-
temperature vapor generator module, a cooling water flow, and
associated heating/cooling and control modules. The microchip is
manufactured on a total of 10 PMMA substrates by a commercial
CO2 laser ablation system, and consists of a sample zone, a distil-
lation zone, a condensation channel and a collection zone. In the
presented analysis procedure, the CH2O solution is placed into the
microchip and is evaporated and delivered continuously through
the microchip under the high-throughput vapor stream. When
entering the condensation region of the microchip, the CH2O vapor
is cooled under a low temperature (~8  C) distilled water stream,
and then the CH2O solution enters the collection zone. The CH2O
concentration of the collected solution is then measured using two
different colorimetric detection methods, namely AHMT spec-
trometry and paper-based RGB intensity analysis. The results show
that the presented distillation apparatus achieves a distilled
100 S.-Y. Hsu et al. / Analytica Chimica Acta 1062 (2019) 94e101

Table 1
Comparison the analyzed CH2O concentration of 21 commodity samples under four different analytical methods.

Samples No. Case 1 ppm (AC) Case 2 ppm (AC) Case 3 ppm Case 4 ppm (AC)

1 Dried mushroom (1) 27.9 (98.5%) 27.8 (98.9%) 27.5 28.0 (98.1%)
2 Dried mushroom (2) 26.8 (97.7%) 26.6 (98.5%) 26.2 26.6 (98.5%)
3 Dried shrimp (1) 21.1 (98.1%) 21.6 (99.5%) 20.7 21.3 (97.1%)
4 Dried fungus 8.9 (98.9%) 9.0 (98.9%) 9.1 9.1 (100%)
5 West ginseng 7.1 (97.2%) 7.2 (98.6%) 7.3 7.2 (98.6%)
6 Shrimp bran 7.1 (100%) 7.0 (98.6%) 7.1 7.0 (98.6%)
7 Candied melon 6.8 (98.5%) 7.0 (98.5%) 6.9 7.0 (98.5%)
8 Ginseng 6.3 (96.7%) 6.2 (98.4%) 6.1 6.1 (100%)
9. Black olive 5.2 (98.1%) 5.2 (98.1%) 5.3 5.3 (100%)
10 Shreddle ginger 2.2 (95.2%) 2.2 (95.2%) 2.1 2.2 (95.2%)
11 Dried dioscoreae rhizoma 1.7 1.8 N.D. 1.8
12 Flammulina velutipes 1.4 1.3 N.D. 1.3
13 Rice flour 1.3 1.3 N.D. 1.3
14 Sprouts 1.2 1.2 N.D. 1.2
15 Dried lemon 0.7 0.8 N.D. 0.8
16 Dried fig 0.7 0.7 N.D. 0.7
17 Dried orange peel N.D. N.D. N.D. N.D.
18 Jujube beans N.D. N.D. N.D. N.D.
19Dried pineapple N.D. N.D. N.D. N.D.
20 Panax quinquefolius N.D. N.D. N.D. N.D.
21 Korean red ginseng N.D. N.D. N.D. N.D.

N.D.: Non-Detectable; AC: Accuracy (%) compared with Case 3.

Case 1: By the presented microchip-based distillation apparatus for distillation and CH2O concentration measured by AHMT method.
Case 2: By the presented microchip-based distillation apparatus for distillation and CH2O concentration measured by paper-based method.
Case 3: The official method including distillation and measurement was provided by CAAPIC at NPUST.
Case 4: By the presented microchip-based distillation apparatus for distillation and CH2O concentration measured by CAAPIC.

efficiency as high as 98.2% when using a vapor stream rate of 0.4 ml/
min and a distilled time of 10 min. Moreover, the CH2O concen-
tration analyses gotten by the presented distillation apparatus for
21 commodity samples deviate by no more than 4.3% that
compared with a commercial large-scale equipment. In addition,
the presented microchip-based distillation apparatus achieves a
distillation and detection limit of approximately 0.5 ppm.
Declaration of interests
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
The authors declare the following financial interests/personal
relationships which may be considered as potential competing
interests:
Acknowledgement
This research was supported by the Ministry of Science and
Technology of Taiwan (107-2622-B-006-007-CC2, 106-2221-E-
006-253-MY3, and 106-2314-B-006-085-MY3)
References
[1] K. Uchida, Role of reactive aldehyde in cardiovascular diseases, Free Radic.
Biol. Med. 28 (2000) 1685e1696.
[2] M. Hauptmann, P.A. Stewart, J.H. Lubin, L.E. Beane Freeman, R.W. Hornung,
R.F. Herrick, R.N. Hoover, J.F. Fraumeni Jr., A. Blair, R.B. Hayes, Mortality from
lymphohematopoietic malignancies and brain cancer among embalmers
exposed to formaldehyde, J. Natl. Cancer Inst. 101 (2009) 1696e1708.
[3] J. Chiou, A.H.H. Leung, H.W. Lee, W. Wong, Rapid testing methods for food
contaminants and toxicants, J. Integr. Agr. 14 (2015) 2243e2264.
[4] D. Zhang, D. Liu, M. Li, Y. Yang, Y. Wang, H. Yin, J. Liu, B. Jia, X. Wu, A simple
pyrene-based fluorescent probe for highly selective detection of formalde-
hyde and its application in live-cell imaging, Anal. Chim. Acta 1033 (2018)
180e184.
[5] W.H.O, Air quality guidelines for Europe, in: European Series, 91, second ed.,
World Health Organization Regional Publications, Switzerland, 2000.
[6] S.J. Armour, International Task Force 40: Toxic Industrial Chemicals (TICs)-
Operational and Medical Concerns, U.S. Government Printing Office, Wash-
ington, DC, 2001.
[7] International Agency for Research on Cancer (IARC), Monographs on the
Evaluation of Carcinogenic Risks to Humans Volume 88: Formaldehyde, 2-
Butoxyethanol and 1-Tert-Butoxypropan-2-ol, 2006.
[8] M. Guglielmino, A. Allouch, C.A. Serra, S.L. Calve , Development of microfluidic
analytical method for on-line gaseous formaldehyde detection, Sensor. Actu-
ator. B Chem. 243 (2017) 963e970.
[9] V. Fauzia, Nurlely, C. Imawan, N.M.M.S. Narayani, A.E. Putri, A localized surface
plasmon resonance enhanced dye-based biosensor for formaldehyde detec-
tion, Sensor. Actuator. B Chem. 257 (2018) 1128e1133.
[10] C. Liu, C. Shi, H. Li, W. Du, Z. Li, L. Wei, M. Yu, Nanomolar fluorescent quan-
titative detection of formaldehyde with a 8-hydroxyquinoline derivative in
aqueous solution and electrospun nanofibers, Sensor. Actuator. B Chem. 219
(2015) 185e191.
[11] F. Wu, Y. Zhang, L. Huang, D. Xu, H. Wang, A fluorescence-enhanced probe for
rapid detection of formaldehyde and its application for cell imaging, Anal.
Methods 9 (2017) 5472e5477.
[12] Z.Y. Lv, L.P. Mei, W.Y. Chen, J.J. Feng, J.Y. Chen, A.J. Wang, Shaped-controlled
electrosynthesis of gold nanodendrites for highlyselective and sensitive SERS
detection of formaldehyde, Sensor. Actuator. B Chem. 201 (2014) 92e99.
[13] P. Ma, F. Liang, D. Wang, Q. Yang, Y. Ding, Y. Yu, D. Gao, D. Song, X. Wang,
Ultrasensitive determination of formaldehyde in environmental waters and
food samples after derivatization and using silver nanoparticle assisted SERS,
Microchim. Acta 182 (2015) 863e869.
[14] E. Menart, V. Jovanovski, S.B. Hocevar, Novel hydrazinium polyacrylate-based
electrochemical gas sensor for formaldehyde, Sensor. Actuator. B Chem. 238
(2017) 71e75.
[15] G. Premaratne, S. Farias, S. Krishnan, Pyrenyl carbon nanostructures for ul-
trasensitive measurements of formaldehyde in urine, Anal. Chim. Acta 970
(2017) 23e29.
[16] Z. Bo, M. Yuan, S. Mao, X. Chen, J. Yan, K. Cen, Decoration of vertical graphene
with tin dioxide nanoparticles for highly sensitive room temperature form-
aldehyde sensing, Sensor. Actuator. B Chem. 256 (2018) 1011e1020.
[17] L.O. Lago, K.P. Nicolli, A.B. Marques, C.A. Zini, J.E. Welke, Influence of ripeness
and maceration of the grapes on levels of furan and carbonyl compounds in
wine e simultaneous quantitative determination and assessment of the
exposure risk to these compounds, Food Chem. 230 (2017) 594e603.
[18] Y.H. Kim, P. Kumar, E.E. Kwon, K.H. Kim, Metal-organic frameworks as su-
perior media for thermal desorption-gas chromatography application: a
critical assessment of MOF-5 for the quantitation of airborne formaldehyde,
Microchem. J. 132 (2017) 219e226.
[19] F.B. de Freitas Rezende, A.M. de Souza Santos Cheibub, A.D. P.a Netto, F.F. de
Carvalho Marques, Determination of formaldehyde in bovine milk using a
high sensitivity HPLC-UV method, Microchem. J. 134 (2017) 383e389.
[20] C.F. Nascimento, P.M. Santos, E.R. Pereira-Filho, F.R.P. Rocha, Recent advances
on determination of milk adulterants, Food Chem. 221 (2017) 1232e1244.
[21] T. Zhou, J. Ding, Z. He, J. Li, Z. Liang, C. Li, Y. Li, Y. Chen, L. Ding, Preparation of
magnetic superhydrophilic molecularly imprinted composite resin based on
multi-walled carbon nanotubes to detect triazines in environmental water,
Chem. Eng. J. 334 (2018) 2293e2302.
 S.-Y. Hsu et al. / Analytica Chimica Acta 1062 (2019) 94e101
[22] Z. Chen, G. Li, Z. Zhang, Miniaturized thermal-assisted purge-and-trap tech-
nique coupling with surface-enhanced Raman scattering for trace analysis of
complex samples, Anal. Chem. 89 (2017) 9593e9600.
[23] J. Qiao, J. Chang, H. Wang, T. Sun, C. Dong, Determination of formaldehyde
with a platinumepalladiumegraphene nanocomposite glassy carbon elec-
trode, Anal. Lett. 50 (2017) 80e90.
[24] S.N. Azizi, S. Ghasemi, F. Amiripour, Nickel/P nanozeolite modified electrode: a
new sensor for the detection of formaldehyde, Sensor. Actuator. B Chem. 227
(2016) 1e10.
[25] D. Gu, M. Zou, X. Guo, P. Yu, Z. Lin, T. Hu, Y. Wu, Y. Liu, J. Gan, S. Sun, X. Wang,
C. Xu, A rapid analytical and quantitative evaluation of formaldehyde in squid
based on Tri-step IR and partial least squares (PLS), Food Chem. 229 (2017)
458e463.
[26] L.M. Fu, Y.N. Wang, C.C. Liu, An integrated microfluidic chip for formaldehyde
analysis in Chinese herbs, Chem. Eng. J. 244 (2014) 422e428.
[27] L.M. Fu, W.J. Ju, Y.N. Wang, R.J. Yang, Rapid prototyping of glass-based
microfluidic chips utilizing two-pass defocused CO2 laser beam method,
Microfluid. Nanofluidics 14 (2013) 479e487.
[28] C.C. Liu, Y.N. Wang, L.M. Fu, Micro-distillation system for formaldehyde con-
centration detection, Chem. Eng. J. 304 (2016) 419e425.
[29] M. Guglielmino, P. Bernhardt, C. Trocquet, C.A. Serra, S.L. Calve , On-line
gaseous formaldehyde detection by a microfluidic analytical method based on
simultaneous uptake and derivatization in a temperature controlled annular
flow, Talanta 172 (2017) 102e108.
[30] A. Allouch, M. Guglielmino, C.A. Serra, S. Le Calve , Optofluidic fluorescence cell
for the detection of low concentration toxic gases, Sensor. Actuator. B Chem.
255 (2018) 3441e3446.
[31] X. Wang, Y. Li, X. Li, J. Yu, S.S. Al-Deyab, B. Ding, Equipment-free chromatic
determination of formaldehyde by utilizing pararosaniline-functionalized
cellulose nanofibrous membranes, Sensor. Actuator. B Chem. 203 (2014)
333e339.
[32] J.M.C.C. Guzmana, L.L. Tayoa, C.C. Liu, Y.N. Wang, L.M. Fu, Rapid microfluidic
paper-based platform for low concentration formaldehyde detection, Sensor.
Actuator. B Chem. 255 (2018) 3623e3629.
[33] C.C. Liu, Y.N. Wang, L.M. Fu, Y.H. Huang, Microfluidic paper-based chip plat-
form for formaldehyde concentration detection, Chem. Eng. J. 332 (2018)
695e701.
[34] Y. He, H. Li, X. Zou, N. Bai, Y. Cao, Y. Cao, M. Fan, G.D. Li, Platinum dioxide
activated porous SnO2 microspheres for the detection of trace formaldehyde
at low operating temperature, Sensor. Actuator. B Chem. 244 (2017) 475e481.
[35] G. Zilberstein, R. Zilberstein, S. Zilberstein, U. Maor, E. Baskin, S. Zhang,
P.G. Righetti, A miniaturized sensor for detection of formaldehyde fumes,
Electrophoresis 38 (2017) 2168e2174.
[36] L. Wang, Z. Wang, Q. Xiang, Y. Chen, Z. Duan, J. Xu, High performance form-
aldehyde detection based on a novel copper (II) complex functionalized QCM
gas sensor, Sensor. Actuator. B Chem. 248 (2017) 820e828.
[37] A. Bi, T. Gao, X. Cao, J. Dong, M. Liu, N. Ding, W. Liao, W. Zeng, A novel
naphthalimide-based probe for ultrafast, highly selective and sensitive
detection of formaldehyde, Sensor. Actuator. B Chem. 255 (2018) 3292e3297.
[38] X. Chang, X. Wu, Y. Guo, Y. Zhao, J. Zheng, X. Li, SnSO4 modified ZnO nano-
structure for highly sensitive and selective formaldehyde detection, Sensor.
Actuator. B Chem. 255 (2018) 1153e1159.
[39] L.M. Fu, Y.N. Wang, Detection methods and applications of microfluidic paper-
based analytical devices, Trends Anal. Chem. 107 (2018) 196e211.
[40] M. Sonker, V. Sahore, A.T. Woolley, Recent advances in microfluidic sample
preparation and separation techniques for molecular biomarker analysis: a
critical review, Anal. Chim. Acta 986 (2017) 1e11.
[41] J. Wu, Q. Chen, W. Liu, Z. He, J.M. Lin, Recent advances in microfluidic 3D
cellular scaffolds for drug assays, Trends Anal. Chem. 87 (2017) 19e31.
[42] P. Novo, D. Janasek, Current advances and challenges in microfluidic free-flow
electrophoresisdA critical review, Anal. Chim. Acta 991 (2017) 9e29.
[43] Z. Bai, H. Bao, Y. Yuan, X. Yang, Y. Xi, M. Wang, Real-time observation of
perturbation of a Drosophila embryo's early cleavage cycles with micro-
fluidics, Anal. Chim. Acta 982 (2017) 131e137.
[44] G. Peng, Q. He, Y. Lu, J. Huang, J.M. Lin, Flow injection microfluidic device with
101
on-line fluorescent derivatization for the determination of Cr(III) and Cr(VI) in
water samples after solid phase extraction, Anal. Chim. Acta 955 (2017)
58e66.
[45] C.Y. Lee, L.M. Fu, Recent advances and applications of micromixers, Sensor.
Actuator. B Chem. 259 (2018) 677e702.
[46] S. Dziomba, M. Araya-Farias, C. Smadja, M. Taverna, B. Carbonnier, N.T. Tran,
Solid supports for extraction and preconcentration of proteins and peptides in
microfluidic devices: a review, Anal. Chim. Acta 955 (2017) 1e26.
[47] R.J. Yang, H.H. Hou, L.M. Fu, Review and perspectives on microfluidic flow
cytometers, Sensor. Actuator. B Chem. 266 (2018) 26e45.
[48] R.E. Fernandez, A. Rohani, V. Farmehini, N.S. Swami, Review: microbial anal-
ysis in dielectrophoretic microfluidic systems, Anal. Chim. Acta 966 (2017)
11e33.
[49] J. Wu, Z. He, Q. Chen, J.M. Lin, Biochemical analysis on microfluidic chips,
Trends Anal. Chem. 80 (2016) 213e231.
[50] H. Liu, M. Jie, Z. He, H.F. Li, J.M. Lin, Study of antioxidant effects on malignant
glioma cells by constructing a tumor-microvascular structure on microchip,
Anal. Chim. Acta 978 (2017) 1e9.
[51] C.C. Liu, Y.N. Wang, L.M. Fu, K.L. Chen, Microfluidic paper-based chip platform
for benzoic acid detection in food, Food Chem. 249 (2018) 162e167.
[52] S.C. Chen, C.C. Liu, Y.N. Wang, L.M. Fu, S.H. Shih, An integrated microfluidic
loop-mediated isothermal amplification platform for koi herpesvirus detec-
tion, Chem. Eng. J. 334 (2018) 1828e1834.
[53] W.J. Ju, L.M. Fu, R.J. Yang, C.L. Lee, Distillation and detection of SO2 using
microfluidic chip, Lab Chip 12 (2012) 622e626.
[54] G.F. Giordano, L.C.S. Vieira, A.L. Gobbi, L.T. Kubota, R.S. Lima, Gravity-assisted
distillation on a chip: fabrication, characterization, and applications, Anal.
Chem. Acta 1033 (2018) 128e136.
[55] Z. Zhong, G. Li, B. Zhu, Z. Luo, L. Huang, X. Wu, A rapid distillation method
coupled with ion chromatography for the determination of total sulphur di-
oxide in foods, Food Chem. 131 (2012) 1044e1050.
[56] Y.N. Wang, C.C. Liu, R.J. Yang, W.J. Ju, L.M. Fu, Microfluidic distillation chip for
methanol concentration detection, Anal. Chem. Acta 912 (2016) 97e104.
[57] C.C. Liu, Y.N. Wang, L.M. Fu, C. Chieh, Micro-distillation system for formal-
dehyde concentration detection, Chem. Eng. J. 304 (2016) 419e425.
[58] L.D. Tijing, Y.C. Woo, W. Shim, T. He, J. Choi, S. Kim, H.K. Shon, Super hydro-
phobic nanofiber membrane containing carbon nanotubes for high-
performance direct contact membrane distillation, J. Membr. Sci. 502 (2016)
15 8e170.
[59] A. Lautenschleger, E.Y. Kenig, A. Voigt, K. Sundmacher, Model-based analysis
of a gas/vaporeliquid microchannel membrane contactor, AIChE J. 61 (2015)
2240e2256.
[60] P.H. Chao, J. Collins, J.P. Argus, W.Y. Tseng, J.T. Lee, R.M. van Dam, Automatic
concentration and reformulation of PET tracers via microfluidic membrane
distillation, Lab Chip 17 (2017) 1802e1816.
[61] J.M. MacInnes, J. Ortiz-Osorio, P.J. Jordan, G.H. Priestman, R.W.K. Allen,
Experimental demonstration of rotating spiral microchannel distillation,
Chem. Eng. J. 159 (2010) 159e169.
[62] D.A. Boyd, J.R. Adleman, D.G. Goodwin, D. Psaltis, Chemical separations by
bubble-assisted interphase mass-transfer, Anal. Chem. 80 (2008) 2452e2456.
[63] K.F. Lam, E. Cao, E. Sorensen, A. Gavriilidis, Development of multistage
distillation in a microfluidic chip, Lab Chip 11 (2011) 1311e1317.
[64] K.F. Lam, E. Sorensen, A. Gavriilidis, Towards an understanding of the effects of
operating conditions on separation by microfluidic distillation, Chem. Eng. Sci.
66 (2011) 2098e2106.
[65] R.J. Yang, C.C. Liu, Y.N. Wang, H.H. Hou, L.M. Fu, A comprehensive review of
micro-distillation method, Chem. Eng. J. 313 (2017) 1509e1520.
[66] M. Foerster, K.F. Lam, E. Sorensen, A. Gavriilidis, In situ monitoring of
microfluidic distillation, Chem. Eng. J. 227 (2013) 13e21.
[67] L.M. Fu, W.J. Ju, Y.N. Wang, R.J. Yang, Prototyping of glass-based microfluidic
chips utilizing two-pass defocused CO2 laser beam method, Microfluid.
Nanofluidics 14 (2013) 479e487.
[68] L.M. Fu, W.C. Fang, H.H. Hou, Y.N. Wang, T.F. Hong, Rapid vortex microfluidic
mixer utilizing double-heart chamber, Chem. Eng. J. 249 (2014) 246e251.