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Formaldehyde from production to application

Conference Paper · November 2013

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Formaldehyde from production to application

A.Talaiekhozani1& 2 * ,M.A. Fulazzaky1* , M. Ponraj 1 , Z.M. Abd Majid3

1- Institute of Environmental and Water Resources Management, Water Research Alliance, Department of Environmental
Engineering, Faculty of Civil Engineering, Universiti Teknologi Malaysia, UTM Skudai, 81310 Johor Bahru, Malaysia

2- Department of Civil and Environmental Engineering,, Jami Institute of Technology, Isfahan, Iran

3- Construction Research Alliance, Faculty of Civil engineering, UniversitiTeknologi Malaysia, UTM Skudai,
81310 Johor Bahru, Malaysia

Abstract
Formaldehyde has been categorized as toxic, suspected carcinogen, teratogen and mutagen compound and
widely applied in various industries. Millions ton of formaldehyde is yearly released into environments.
Therefore, having enough information about this compound to control its environmental problems is
necessary. Although, many articles about formaldehyde production, properties, removal and applications
have been published, but access to all of this information in different data bases is not easy and a
comprehensive review paper in this area is yet to be published. The aim of this paper is collecting
information about toxicology, resources, production and applications of formaldehyde. Formaldehyde can be
emitted into atmosphere from natural sources such as atmospheric reactions, fire forest,and biological
metabolism. Anthropogenic sources are other important sources of formaldehyde emission. Collecting
enough knowledge about common pollutants such as formaldehyde that have been frequently released into
environment can make significant contributions to improving environmental quality.

Keywords:Formaldehyde, sources, removal, properties, toxicology.

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1.Introduction
The development of technologies has made this world a better place to live in than before.But the use of
new technologies has also damaged the environment by producingpollutants like waste gases. Formaldehyde
vapor is a waste gas thatis released in the air worldwide from chipboard production, burning processes,
synthesis of resin production and chemical factories. Some researchers have estimated a global emission of
thirty-two million tons of formaldehyde in 2006 and it keeps increasing year by year [1].
Michailowitsch Butlerow discovered formaldehyde in 1855. Then, a German chemist "August Wilhelm
von Hofmann" achieved technical synthesis of formaldehyde using dehydration of methanol in 1867. The
versatility that makes formaldehyde suitable for use in wide number of factories applications was soon
recognized, and it was soon indexed by CAS (Chemical Abstracts Service). During the first 30 years (1900
to 1930), formaldehyde was one of the basic parts of adhesives for wood and wood composite. Germany and
Britain were the first countries that had made some factories for producing of commercial particle boards
since 1939. Use of particle boards has been became an attractive building material for the manufacture of
furniture and partition construction for housing since 1950. Adverse health effects duo to release of
formaldehyde in houses, such as irritation of the eyes, was reported in the 1960s. Formaldehyde emission
from urea-formaldehyde resin (UFR) was recognized by researchers as the cause of adverse health effects.
As a result, in the some countries such as Germany, Denmark, and the United States of America a Criteria
was proposed to limit human exposure to formaldehyde in houses during 1981 to 1985. In 1985, first
regulations were issued in the USA. In USA and Germany, a lot of actual scale tests were performed on the
study of formaldehyde emissions. For evaluation of formaldehyde in this study, chamber method was used.
The method of chamber is exceedingly accurate, but this method is expensive and too time-consuming. For
these reasons, there was urgency for simple and reliable laboratory test method for measuring of
formaldehyde. Discussion about the dangers of formaldehyde dangers started in 1980 by reports about the
carcinogenicity of formaldehyde in rats and mice. Consequences of studies on animals and humans about
formaldehyde exposure triggered an avalanche of scientific studies. Although the authors had a good
electronic databases and a lot of review papers, but reviewing all articles in the medical and technical
journals was difficult. The review confirmed formaldehyde is one of the best-known pollutants of air. Over
the years, by finding new environmental friendly components, formaldehyde release from produced
materials such as particle board has been decreasing. On the other hand, concentration of formaldehyde
emitted in outdoor air is increasing, especially in the urban centers or industrial areas. For this reason,
formaldehyde has slipped out of the primary focus of air pollution studies. However, discussions about
formaldehyde were taken up again in 2004, when it was recognized as a matter carcinogen. As a result, new
air guidelines have been proposed and a prioritized listing of chemicals matters and exposures that cause
concern has been stated. In this prioritized ranking formaldehyde is a compound of concern in the air and
that is why knowledgeabout formaldehyde is very important. The aim of this study is to collect all
characteristics of formaldehyde to have a better strategy to control this pollutant.

2. General description of formaldehyde

2.1. Formaldehyde properties
Formaldehyde is soluble in water and some other chemical solutions. Rapid absorption of formaldehyde
in the respiratory and gastrointestinal systems is because of its high solubility in water. Formaldehyde is
generally known as formalin. Formalin is 37% formaldehyde solution in water. For preventing
polymerization of formaldehyde, it is mixed with ten percent of methanol as a stabilizer. In the table 1 the
characteristics of formaldehyde are shown.

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Table 1: the main Characteristic of formaldehyde

Parameter Characteristic References
molecular
HCHO or CH2O
formula
molecular
30.03 g mol-1
weight
melting point -92 °C
boiling point -21 °C
dipole moment 2.33 D
Solubility soluble in water, ethanol, ether, acetone
Constant of
2.5 × 103 M atm-1 (25 °C)
Henry’s law
calculated
octanol/water [2,3,4, 5, 6]
partition -0.83
coefficient
log( )
9.37 × 10-12 cm3 molecule-1 s-1 (24.85 degrees Celsius)
2.09 × 10-24 cm3 molecule-1 s-1 (24.85 degrees Celsius)
5.80 × 10-16 cm3 molecule-1 s-1 (24.85 degrees Celsius)
CAS registry
50-00-0
no.
Solubility in
400 g dm−3
water

Nowadays, factories producing formaldehyde usecatalytic oxidation of methanol and methane. At room
temperature, formaldehyde gas is flammable, extremely reactive, and colorless. Formaldehyde has a typical
electrophile molecule because of its dipolar resonance structure. In the following Figure 1, the formaldehyde
structure is shown.

Figure 1: Formaldehyde molecule structure

32,000,000 tons of formaldehyde was releasedinto the atmosphere in 2006,of which 56% was released by
Germany, the United States, and China. Nearly 65% of produced formaldehyde is used to synthesize resins
[1]. One form of formaldehyde is paraformaldehyde that describes a polymeric structure with 8 to 100
monomers per molecule. The formaldehyde in the form of C3H6O3 is named 1,3,5-trioxane. Tang et al.
(2006) reported the most important reactions apart from polymerization are as follows [1]:

Following is formaldehyde reaction with ammonia and producing hexamethylene tetramine:

4 +6 →( ) +6 (Eq. 1)

1- Reaction of cannizzaro:

2 + → + (Eq. 2)

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2- Reaction of aldol:

2 → (Eq. 3)

3- Reaction of tischenko:

2 → (Eq. 4)

According to table 1, the formaldehyde constant of Henry’s law is 2.5×103 M atm-1 at 24.85 degrees
Celsius[5]. Although some scientists and organizations believe that octanol/water partition coefficient (Kow)
is equal -0.83, some others such as world health organization (WHO) believe that it is equal -1[2]. The
reaction rate constant with the OH- radical is named KOH and it is for formaldehyde equal 9.3×10-12 cm3
molecule-1 s-1 at 24.85 degrees Celsius[4]. With these formaldehyde characteristics and estimate an OH-
concentration of 10 million molecules per cm3are present in the free air.The life time of formaldehyde in the
atmosphere is 31 hours. Spectrum among of 260 nm to 360 nm can be absorbed by formaldehyde vapor [7].
The lifetimes against the photolytic processes with two below reactions were calculated for the latitude of 50
degree Celsius, equals 6.9 and 2.1 h, respectively.

Formaldehyde → H2 + CO (Eq. 5)

Formaldehyde → H + HCO (Eq. 6)

Formaldehyde lifetimes in the air has been calculated with respect to photolysis reaction, reaction with the
hydroxyl radical, reaction with the nitrate radical, and reaction with Ozone equal 4 hours, 1.2 days, 80 days
and more than 4.5 years, respectively [4]. Braslavsky and Heicklen have performed a study on the reaction
of ozone with formaldehyde vapor and found some similar results [8].

2.2. Formaldehyde toxicology

Formaldehyde is soluble in water and this is reason for its rapid absorption in respiratory and gastrointestinal
systems of humans and animals. Formaldehyde can be changed to Formate and after that carbon dioxide by
oxidation of formaldehyde in human body metabolisms. The biological half-life of formaldehyde in human
and animal bodies is exceedingly short at about 60 seconds [9]. Also nucleophilic biogenic compounds in the
body can be destroyed by reacting with formaldehyde [10].
Enzyme alcohol dehydrogenase is produce by organisms. It is the cause of formaldehyde produced in small
amounts from methanol [11, 12] which is a human metabolite [13, 14]. According to Health Canada's report,
mucosa of the upper respiratory tract and irritation of the eyes are some major effects of acute exposure to
formaldehyde [15].
RD50 is identified as exposure concentration producing a 50% respiratory rate decrease as an indication of
respiratory tract irritation. According to Kuwabara's report, for an exposure time of 5 to 10 minutes, the RD50
values of male mice are 3.1 to 5.3 ppm [16]. Also the lowest observable adverse effect levels (LOAEL) for
human sensory irritation range from 0.4 ppm (rhinitis) to 3 ppm (eye, nasal, and throat irritation). Some
studies on formaldehyde effects and sensory irritation in humans showed that eye irritation is the most
sensitive parameter. A no observed effect level of 0.5 ppm was recognized in the case of constant exposure
[17].
Different scientists have identified various threshold values for the odor perception of formaldehyde.
According to Devos et al. report, standardized human olfactory threshold of formaldehyde is 1.07
mg/m3[18]. Another odor unit is named absolute odor thresholds that it defined as the concentration of
compound at which 50% of the panel detects the odor. The WHO has estimated absolute odor thresholds of
formaldehyde among 0.06 to 0.22 mg/m3 (WHO, 1989). In some reports, researchers could recognized very
low odor thresholds of between 0.03 to 0.035 mg/m3[10,19].

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European Union, USA, and the International Agency for Research on Cancer classified Formaldehyde as a
suspected carcinogen [20]. This decision is based on some evidences regarding the relationship between
nasopharyngeal cancer and leukemia related to the exposure to formaldehyde in respiratory air.

2.3. Formaldehyde application

In a lot of industrial processes formaldehyde is used as chemical feedstock. It is used as a biocide,
disinfectant, and preservative as applications of formaldehyde. One of the main components in thermosetting
adhesives is formaldehyde. Aminoplasts or adhesives that make base urea-formaldehyde are generally used
in the wood-based industries due to their low price. By combining urea and formaldehyde (Mannich
reaction) monomethylolurea, trimethylolurea and, dimethylolurea will be produced. This reaction is shown in
figures2 and 3. Urea-formaldehyde adhesives are not resistant against water. Urea-formaldehyde adhesives
in presence of water will be hydrolyzed and as a consequence, formaldehyde will be released [2].

Figure 2: combining of urea and formaldehyde (Mannich reaction)

Figure 3: combining of urea and formaldehyde (Mannich reaction)

Adhesive base on Melamine-urea-formaldehyde (MUF) are exceedingly similar to UF adhesives. Industrials

produce MUF adhesives using mix UF and melamine-formaldehyde (MF). Figure 4 shows the first step of
the melamine-formaldehyde reaction. In all the above explained reactions, formaldehyde vapor can be
released into the air [2].

Figure 4: the first step of the melamine-formaldehyde reaction

A category of adhesives is Phenoplasts adhesives that called Phenol-formaldehyde adhesives. To produce of

Phenol-formaldehyde, methylol phenol are produced according to the figure 5. The result of this reaction is
one of the most stable and water-resistant adhesives that have a good adherence to some materials like wood.
Bakelite is a kind of plastic base on Phenol-formaldehyde resins that was used in the past as casings for
telephones, radios, etc [2].

Figure 5: Methylol phenol reaction

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Melamine-urea-phenol-formaldehyde (MUPF) adhesives were developed to produce moisture-proof wood.

Production of MUPFs adhesives is similar to MUF adhesives. Table 2 provides an overview of formaldehyde
applications.

Table 2: Overview of formaldehyde applications

Particleboard, Fiberboard, Plywood, Paper treatment, Textile
Formaldehyde base production

Urea formaldehyde resins

treatment, Molding compounds, Surface coatings, Foam
Phenolic resins Wood adhesives, Insulation, Foundry
Melamine resins Surface, Molding compounds, Laminates, Wood adhesives
Hexamethylenetetramine Phenolic thermosetting, Curing agents, Explosives
Trimethylopropane Urethanes, Lubricants, Alkyd resins, Multifunctional acrylates
1, 4-Butanediol Tbutyroalacetone, etahydrofuran, polybutglene terephtalate
Polyacetal resins Auto applications, Fuel components
Alkyd resins, Synthethic lubricants, Tall oil esters, Foundry
Pentaerythritol
resins, Explosives
Urea formaldehyde
Controlled released fertilizers
concentrates

A number of authors such as Godish and Pluschke in the their reports, have described some formaldehyde
applications in the past and present [21, 22]. A list of these applications is given below:
Oriented-strand board (OSB), Particle board, flooring materials, high-density fiber board (HDF),
mediumdensity fiber board (MDF), plywood, cork products, Insulation materials made of UF foam, mineral
wool, coating materials, glass wool, paper products, paints, lacquers containing formaldehyde as
preservative, textiles, cleaning, photoprocessing chemicals, caring products, disinfectants, preservatives,
cosmetics, etc.

3. Formaldehyde Sources
3.1. Outdoor formaldehyde sources
3.1.1. Formaldehyde as a Natural Compound
Some synthetic and natural formaldehyde sources are known [23]. Formaldehyde is a biogenic compound.
During physiological activities of some plants formaldehyde is released into the atmosphere [24]. A study
was conducted by Mu¨ller et al. the results of this study showed that formaldehyde is produced by coniferous
trees [25]. Similar study in Portugal showed that formaldehyde was produced by degradation of isoprene in a
eucalyptus forests [26]. Harder (1927) reported that formaldehyde has the ability for lignin decomposing.
Formaldehyde was detected within a remote forest in the Amazon too [27]. Other researchers have been able
to detect formaldehyde within or above forests [28, 29]. A report about formaldehyde emission has shown
that it can be released by solid wood [30]. Although some researchers believe that formaldehyde can be
produced by bio-reaction of OH and NO, some others such as Carter and Atkinson believe that formaldehyde
can be produced by methanol oxidation [31, 32]. Other scientists proposed some possible mechanisms for
formaldehyde production by plants like reactions of oxidative demethylation, dissociation of 5,10-
methylenetetrahydrofolate or decarboxylation of glyoxylate [33]. Although a number of studies was
conducted about natural source of formaldehyde, unfortunately exact mechanisms of formaldehyde
production within plants still remains unclear. Marine environments are another natural formaldehyde source
[34].

3.1.2. Atmospheric Reactions

Biogenic resources emit a lot of organic matters into the atmosphere. Isoprene, sesquiterpenes,
monoterpenes, and a number of oxygenated compounds are produced by biogenic resources [4]. These kinds

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of organic materials react with nitrate, hydroxyl, and ozone radicals. Results of these reactions can play an
important role in chemistry of atmosphere (Figure 2-14).

Figure 6: Reaction between alkene and ozone, to produce carbonyl compounds

(Finlayson, 2000, Criegee, 1975)

"The gas-phase reaction of ozone with unsaturated hydrocarbons is known to produce aldehydes, ketones,
and acids as main components" [2]. Formaldehyde has been identified in a number of reaction between
alkenes and ozone [35]. Oxidation reaction of some hydrocarbons in the gas phase have been studied by
Grosjean et al. the results of this study show that formaldehyde was formed after completing reaction
between ozone and cyclohexane [36]. Formaldehyde production from reaction between ozone and carvone,
carveol, citral, and geraniol has been proven[37]. A study has been performed using NMR spectroscopy on
the byproducts of ozone and terpenes reaction by Griesbaum et al. (1998). In this study formaldehyde has
been identified as one of byproducts of reaction between ozone and terpenes in the gas-phase [38]. Due
todirectreleaseformaldehydeorphotochemicalreactionsin the atmosphere, high concentration of formaldehyde
has been found in the megacities air. High relationship between concentration of ozone and formaldehyde in
the air, has been observed. In an episode of ozone in the China (Beijing), high concentration of formaldehyde
has been detected (36 µgr/m3) in the air [39]. Reaction between methane and hydroxyl radical has a low rate
constant. For this reason, formation of formaldehyde from reaction between methane and hydroxyl radical is
only important in remote areas.

3.1.3. Outdoor Combustion

Burning of wood can produce formaldehyde this is another source of natural formaldehyde. Some studies on
wood combustion show that the rate of formaldehyde emission is between 180 to 1156 mg/kg wood [40, 41].
High concentration of formaldehyde can be detected in wildfire activities [42]. "Reisen and Brown could
measure levels up to 0.57 part per million for the personal exposure of Australian firefighters" [43].
Formaldehyde can also be released by fuel combustion in engines. Unfortunately one cannot find a lot of
information about formaldehyde production by biodiesel fuel combustion. According to Correra and Arbilla
(2008) the biodiesel ester molecules are probably the source of these carbonyls[44]. Generally, low
formaldehyde concentration has been emitted in comparison to conventional diesel fuel combustion [45].

3.1.4. Formaldehyde Release into the Atmosphere

According to the world health organization (WHO), formaldehyde release is accrued in industries during all
stages of production, use, storage, disposal, or transportation of products with residual formaldehyde.
Releasing of formaldehyde has been detected from various industries such as: wood processing factories,
chemical factories, coal processing, pulp and paper mills, forestry product plants, tire and rubber plants,
textile factories, automotive manufacturing plants, and the metal products industry. According to a report,
70% of formaldehyde emission in Canada is related, because of vehicles traffic aircraft (11%), shipping
(7%), the formaldehyde processing industry (10%), and power plants and waste incineration (1%).

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Determination of global formaldehyde emission is difficult. According to the WHO report, 8960 t/a of
formaldehyde was released into the atmosphere by USA in 1992 [2].

3.2. Indoor Sources

The number of articles on indoor pollution with formaldehyde is more as compared to outdoor. This high
number of articles is because of the various resources of formaldehyde and also low air exchange rates in the
indoor environment[2]. A relation between wood based products and formaldehyde emission was recognized
by scientists during 1960 to 1970. Particle board, could release high concentration of formaldehyde into the
homes and offices because of reversibility of reaction between urea and formaldehyde. These reactions are
elaborated in equations 1 and 2. Formaldehyde emission from particle boards decrease within time [46].
Throughout the world, due to stricter government regulation emission of formaldehyde from wood base
materials was decreased after 1970. Use of environmental friendly adhesives instead of urea-formaldehyde
resins also helped in decrease of formaldehyde emission.

3.3. Measuring methods of formaldehyde

A lot of studies can be found about measurement of formaldehyde. Formaldehyde measurement methods are
divided into the following three categories: (1) In-Situ Methods; (2) Derivatization Methods; and (3) using of
Sensors.

3.3.1. In-Site methods

Spectroscopic techniques are common methods to measure formaldehyde in outdoor environments.
following methods were described to measure formaldehyde in outdoor environments [2]:Differential optical
absorption spectroscopy (DOAS), Fourier transform infrared absorption (FTIR), Laser induced fluorescence
spectroscopy (LIFS), Infrared diode laser spectroscopy (IDLS), Photoacoustic spectroscopy (PAS), Proton-
transfer-reaction mass spectrometry (PTR-MS), Selected ion flow tube mass spectrometry (SIFT-MS) and
Tunable diode laser spectroscopy (TDLS).
Unfortunately In-suit techniques take a long time to performed. For this reason they are not suitable for
routine applications. To detect formaldehyde in concentration less than 100 part per billion (ppb) a
combination with photacoustics, FTIR, and diode lasers was developed[47]. Although some scientists
believe PTR-MS can be used to determine formaldehyde concentration in outdoor environments, other one
such as Gouw and Warneke (2007) believe detection of formaldehyde by this method faces problems [48].

3.3.2. Derivatization methods

Both of the batch and continues sampling methods are useable to take samples of air polluted with
formaldehyde. Sometimes formaldehyde is adsorbed on the absorber and after that, adsorbed formaldehyde
is extracted by solvent to measure. Extracted formaldehyde can be analyzed by spectrophotometrically or
other methods such as gas chromatography (GC). Except GC other methods are not specific for
formaldehyde. Several review article can be found about formaldehyde measurement methods [49]. In all of
these articles derivatization methods has been described. The most important of derivatization methods are:
(a) Chromotropic acid method, (b) Acetylacetone mrthod and (c) 2,4-Dinitrophenylhydrazine (DNPH)
method.
Some tirimetric methods such as Pararosaniline method has been described in article reviews. A magenta dye
will appear by reaction between formaldehyde and Pararosaniline in presence of sodium sulfite. The final
solution has a strong absorbance at 570 nm [50, 51]. Under pH more than one other aldehyde can interfere in
this reaction, but in pH of less than 1 this reaction is specific only for formaldehyde. Hg(II) can be also used
to prevent of SO2 interfere. In the past Pararosaniline method was used frequently but today we have better
methods for formaldehyde measurement.

3-methyl-2-benzothiazolinonehydrazone called MBTH is the name of method to measure aliphatic

aldehydes. Azide is result of reaction between MBTH and aldehydes. The color of final solution is blue. This
solution has a strong absorbance in 628 nm. Pararosaniline method is more sensitive than MBTH method.
Other aldehydes can participate in this reaction but the reaction rate is generally lower.

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Toda et al. described a method to detect formaldehyde online [52]. 4-amino-3-hydrazino-5-mercapto-4H-

1,2,4-triazole (AHMT) can react with aldehydes in high pH. The result of this reaction is detectable using
wavelength of 550 nm.
Formaldehyde can react with chromotropic acid in present of concentrated sulfuric acid. The result of this
reaction is a red-violet hydroxydiphenylmethane. This reaction is shown in Figure 7.

Figure 7: Red-violet hydroxydiphenylmethane production

In this reaction concentrated sulfuric acid is as catalyst. This solution can be calibrated to measure
formaldehyde spectrophotometrically.
Another method to detect formaldehyde is acetylacetone method that is described by [53]. This method is a
standard method to measure formaldehyde emitted from wood based materials in Europe and Japan [54-57].
Figure 8 shows the procedure of Nash method.

Figure 8: The procedure of Nash method

Determination of formaldehyde can be performed spectrophotometrically at 412 nm. Sampling is first step to
determine formaldehyde by Nash method. To sample formaldehyde the air passes through of a column of
distillated water to absorb formaldehyde into water (Figure 9). By adding ammonium acetate and 2,4-
pentanedione and waiting for 10 minutes at 40°C the reaction of Nash will be completed. Nowadays, some
portable equipments are available for formaldehyde detectionusing this reaction [58, 59].

Pure air
Air contaminated by
formaldehyde

Pure Pure Pure

Air pump water water water

Figure 9: Method of formaldehyde solving in pure water

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Today some digital tools to measure of formaldehyde have been made that can measure formaldehyde
concentration in air or aquatic environment very fast and with high accuracy.

4. Removal of Formaldehyde

Although, removal of formaldehyde from wastewater is not very difficult and can be carried out using all
type of suspended and attached growth reactors, removal of this pollutant from air is so difficult [64].
Therefore, focus of this part of paper is on formaldehyde removal from air. Many methods have been
developed to treat polluted air such as wet scrubber, incinerator, adsorption on active carbon, biofilters, and
biotrickling filters. Wet Scrubbersare effective air pollution control devices for removing particles and/or
gases from industrial exhaust streams. Wet scrubbers operate by introducing dirty polluted air stream with a
scrubbing liquid – typically water. Particulate or gases are collected in the scrubbing liquid. Wet scrubbers
are generally one of the most appropriate air pollution control device for collecting both particulate and gas
in a single system. Wet scrubbers can also be used for heat recovery from hot gases. Removal efficiency of
pollutants is improved by increasing residence time in the scrubber or by the increase of surface area of the
scrubber solution by the use of a spray nozzle or packed towers. Wet scrubbers have suitable removal
efficiency. However, wet scrubbers generate significant amounts of wastewater that it need to treatment
again and that is why researchers are looking for new methods to treat polluted air. Another method to treat
polluted air is using of incinerators. Incinerators operate by introducing the air contaminated with organic
pollutants. Organic pollutants can be completely converted to carbon dioxide and water due to high
temperature. Usually, high temperatures between 870 and 1200 °C are used in incinerators to complete
removal of pollutants from air. Incinerators are effective to remove odor and organic pollutants from polluted
air. However, they are very energy consuming and they generate significant amounts of new waste products
such as carbon dioxide. Adsorption of pollutants using activated carbon is another method to treat polluted
air. Activated carbon is the universal standard applied for purification and removal of trace organic
contaminants from liquid and vapor streams. Carbon adsorption uses activated carbon to control and/or
recover gaseous pollutant emissions. In carbon adsorption, the gas is attracted and adheres to the porous
surface of the activated carbon. Removal efficiencies of 95 percent to 99 percent can be achieved by using
this process. Carbon adsorption is used in cases where the recovered organics are valuable. For example,
carbon adsorption is often used to recover perchloroethylene, a compound used in the dry cleaning process.

Due to high operational cost of formaldehyde removal by these methods researchers havedeveloped
biological methods. Microorganisms can absorb formaldehyde and convert it into carbon dioxide and water.

Biological methods do not have negative byproducts. Due to the high toxicity of formaldehyde for
microorganisms, its biological treatment faces many problems. Biological air pollution control technologies
such as biofilters (BFs), bioscrubbers (BSs), biotrickling filter reactors (BTFRs) and suspended-growth
reactors (SGRs) can be cost-effective alternatives to treat polluted gas [60].Formaldehyde with aerobic and
anaerobic conditions can be removed by microorganisms. Different pathways have been proposed to explain
the anaerobic biodegradation of formaldehyde according to the intermediate products observed. For example,
based on Gonzalez et al. (1999), firstly, formaldehyde is biologically converted into formic acid and
methanol (Eq. 7 and 8). Secondly, based on Eq. 9 and 10 formic acid and methanol are biologically
converted to methane and carbon dioxide by microorganisms [61].

HCHO + H O → H + HCOOH (Eq. 7)

HCHO + H → CH OH (Eq. 8)
!"# $%$
HCOOH &'''''''''''( CH + CO (Eq. 9)

١٠
 92 16

!"# $%$
CH OH &'''''''''''( CH + CO (Eq. 10)

Another pathway for anaerobic removal of formaldehyde was proposed by Oliveira et al. (2004). Based on
this pathway formaldehyde is converted into volatile fatty acids, especially as formic acid. These acids are
then converted to acetic acid. Finally, acetic acid was biologically converted to methane and carbon dioxide
under anaerobic condition (Eq. 11 to Eq. 13) [62].

)* "#"+ ,
% !"# $%$
2HCHO &'''''''''''( HCOOH + Volatile Fatty Acids (Eq. 11)
GHIJIKL MNO
PNOL LQIJNRPR
+ :;<=>?<@A=>>BCD?EF &''''''''''''( (Eq. 12)
GHIJIKL MNO
PNOL LQIJNRPR
&''''''''''''( + (Eq. 13)

Aerobic formaldehyde removal can accrue by two possible pathways that are shown in the Eq. 14 to Eq. 17.
The first pathway to aerobic formaldehyde removal is based on converting the formaldehyde to methanol and
formic acid by formaldehyde dismutase enzyme (Eq. 14). This pathway occurs if the microorganisms have a
formaldehyde dismutase enzyme. The second pathway is based on converting the formaldehyde to formic
acid by formaldehyde dehydrogenase enzyme (Eq. 15). This pathway occurs if the microorganisms have the
enzymes formaldehyde dehydrogenase [63]. Both methanol and formic acid can be biologically converted to
water and carbon monoxide (see Eq. 16 and Eq. 17).

S %"TU+V*U+
U $%WX"$+
2HCHO &'''''''''( CH OH + HCOOH(Eq. 14)

S %"TU+V*U+
U+V*U !+#"$+
HCHO &''''''''''( HCOOH(Eq. 15)

!"# $%$
CH OH &'''''''''''( +H O + CO (Eq. 16)

!"# $%$
HCOOH &'''''''''''( +H O + CO (Eq. 17)

4. Conclusion
Formaldehyde has always had an exceptional position due to its special characteristics and wide application
in our life. Formaldehyde is a suspected carcinogen, mutagen and teratogen compound which is widely used
in petrochemical industries. Formaldehyde can be released into atmosphere or water resources during
production processes in industries.This compound can be frequently appeared as an indoor pollutant. Many
chemical, physical and biological processes can be used to remove formaldehyde from water and
air.Although, operation of biological processes is complex, they arecheaper and more reliable than physical
or chemical processes. Anthropogenic sources are other important sources of formaldehyde emission.
Collecting enough knowledge about common pollutants such as formaldehyde that have been frequently
released into environment can make significant contributions to improving environmental quality.

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References

[1] Tang, X., Bai, Y., Duong, A., Smith, M. T., Li, L., Zhang, L., 2009. Formaldehyde in China: Production,
consumption, exposure levels, and health effects. Environ. Int, 35, 1210–1224.

[2] Salthammer, T., Mentese, S., & Marutzky, R. (2010). Formaldehyde in the indoor environment.
Chemical Reviews, 110(4), 2536.

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