NATIONAL UNIVERSITY OF SINGAPORE

SH5110 Chemical Hazard Evaluation

Literature Review of
Monitoring Methods for
Formaldehyde

Executive Summary
Formaldehyde is a known human carcinogen, and yet there is the potential for this chemical
to be present at the workplace, retail spaces and even residential spaces due to its applications
in many building materials. The aim of this literature review is to improve our understanding
of the hazards of formaldehyde, how exposure to formaldehyde is being monitored and
regulated at the workplace and also to review the application of new technologies in
measuring airborne formaldehyde concentration.
The TWA and STEL for formaldehyde is at 0.75 ppm (8 hours) and 2 ppm (15 mins)
respectively. NEA recommends a maximum indoor air concentration of 0.1 ppm. Current
standardized methods for compliance measures airborne formaldehyde concentration and
neglects particulate-bound formaldehyde, which is a common occurrence in wood and textile
industries. The applicability and limitations of conventional laboratory methods and direct
reading instruments are discussed. Research into novel methods, which have several
advantages over the traditional methods for monitoring formaldehyde concentration in the
field, has also been reviewed.

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Contents
Executive Summary................................................................................................................................. 2
1.0

Introduction ................................................................................................................................ 4

1.1

Industrial applications ............................................................................................................. 4

1.2

Synthesis of Formaldehyde ..................................................................................................... 4

1.3

Safety ...................................................................................................................................... 5

2.0

Standardized Methods ................................................................................................................ 7

2.1

NIOSH 3500 ............................................................................................................................. 8

2.1.1

NIOSH Method 3500 for Formaldehyde Measurement ................................................. 8

2.1.2

Method Evaluation of NIOSH Method 3500 ................................................................... 9

2.2

OSHA 1007 ............................................................................................................................ 15

2.3

NIOSH 5700 ........................................................................................................................... 17

2.4

Other Methods...................................................................................................................... 18

2.4.1

Direct Reading Instruments .......................................................................................... 18

2.4.2

Emission testing standards ........................................................................................... 18

2.5

Novel Methods...................................................................................................................... 21

2.5.1

Biosensors ..................................................................................................................... 21

2.5.2

DNAzymes ..................................................................................................................... 22

2.5.3

Formaldehyde dehydrogenase ..................................................................................... 23

3.0

Conclusion ................................................................................................................................. 25

4.0

References ................................................................................................................................ 26

Abbreviations
CARB California Air Resources Board
DMC Dynamic Micro Chamber
FID Flame Ionization Detector
FLEC Field and Laboratory Emission Cell
GC Gas Chromatography
HPLC High Performance Liquid Chromatography
MS Mass Spectrometry
NPD Nitrogen-specific detector
UV Ultraviolet Detector
VAS Visible Absorption Spectrophotometry

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1.0 Introduction
Formaldehyde1 is an important precursor to many other materials and chemical compounds.
In 1996, the installed capacity for the production of formaldehyde was estimated to be 8.7
million tons per year. It is mainly used in the production of industrial resins, e.g., for particle
board and coatings. It is also used in pressed-wood products, such as particleboard, plywood,
and fibreboard; glues and adhesives; permanent-press fabrics; paper product coatings; and
certain insulation materials. In addition, formaldehyde is commonly used as an
industrial fungicide, germicide, and disinfectant, and as a preservative in mortuaries and
medical laboratories. Formaldehyde also occurs naturally in the environment. It is produced
in small amounts by most living organisms as part of normal metabolic processes.
In view of its widespread use, toxicity, and volatility, formaldehyde is a significant
consideration for human health. In 2011, the US National Toxicology Program described
formaldehyde as "known to be a human carcinogen".

1.1

Industrial applications

Formaldehyde is a common precursor to more complex compounds and materials. In

approximate order of decreasing consumption, products generated from formaldehyde
include urea formaldehyde resin, melamine resin, phenol formaldehyde resin,
polyoxmethylene plastics, 1,4-butanediol and methylene diphenyl diisocyanate.
The textile industry uses formaldehyde-based resins as finishers to make fabrics creaseresistant. Formaldehyde-based materials are key to the manufacture of automobiles, and used
to make components for the transmission, electrical system, engine block, door panels, axles
and brake shoes. The value of sales of formaldehyde and derivative products was over $145
billion in 2003.

1.2

Synthesis of Formaldehyde

Two steps in formation of urea-formaldehyde resin, which is widely used in the production of
particle board.

Formaldehyde,

World health Organization, 2002

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When treated with phenol, urea, or melamine, formaldehyde produces, respectively, hard
thermoset phenol formaldehyde resin, urea formaldehyde resin, and melamine resin. These
polymers are common permanent adhesives used in plywood and carpeting. It is used as
the wet-strength resin added to sanitary paper products such as (listed in increasing
concentrations injected into the paper machine headstock chest) facial tissue, table napkins,
and roll towels. They are also foamed to make insulation, or cast into moulded products.
Production of formaldehyde resins accounts for more than half of formaldehyde consumption.
Formaldehyde is also a precursor to polyfunctional alcohols such as pentaerythritol, which is
used to make paints and explosives. Other formaldehyde derivatives include methylene
diphenyl diisocyanate, an important component in polyurethane paints and foams,
and hexamine, which is used in phenol-formaldehyde resins as well as the explosive RDX.
Formaldehyde has been found as a contaminant in several bath products, at levels from 54
610 ppm: it is thought to arise from the breakdown of preservatives in the products, most
frequently diazolidinyl urea. Since 2006, formaldehyde (methylene glycol) is also used in
hair smoothing treatments in order to straighten wavy/curly hair and make hair less prone to
frizz under high humid weather. OSHA Oregon has reported these treatments as unsafe for
human health.

1.3

Safety

Formaldehyde is highly toxic to all animals, regardless of method of intake. Ingestion of 30

mL of a solution containing 37% formaldehyde has been reported to cause death in an adult
human. Water solution of formaldehyde is very corrosive and its ingestion can cause severe
injury to the upper gastrointestinal tract.
Occupational exposure to formaldehyde by inhalation is mainly from three types of
sources: thermal or chemical decomposition of formaldehyde-based resins, formaldehyde
emission from aqueous solutions (for example, embalming fluids), and the production of
formaldehyde resulting from the combustion of a variety of organic compounds (for example,
exhaust gases). Formaldehyde can be toxic, allergenic, and carcinogenic. Because
formaldehyde resins are used in many construction materials it is one of the more common
indoor air pollutants. At concentrations above 0.1 ppm in air formaldehyde can irritate the
eyes and mucous membranes, resulting in watery eyes. Formaldehyde inhaled at this
concentration may cause headaches, a burning sensation in the throat, and difficulty breathing,
and can trigger or aggravate asthma symptoms.
A 1988 Canadian study of houses with urea-formaldehyde foam insulation found that
formaldehyde levels as low as 0.046 ppm was positively correlated with eye and nasal
irritation. A recent review of studies has shown a strong association between exposure to
formaldehyde and the development of childhood asthma. The primary exposure concern is
for the workers in the industries producing or using formaldehyde.
The formaldehyde theory of carcinogenesis was proposed in 1978. In 1987 the U.S. EPA
classified it as a probable human carcinogen, and after more studies the WHO International

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Agency for Research on Cancer (IARC) in 1995 also classified it as a probable human
carcinogen. Further information and evaluation of all known data led the IARC to reclassify
formaldehyde as a known human carcinogen associated with nasal sinus cancer
and nasopharyngeal cancer. Recent studies have also shown a positive correlation between
exposure to formaldehyde and the development of leukaemia, particularly myeloid
leukaemia. Nasopharyngeal and sinonasal cancers are relatively rare, with a combined annual
incidence in the United States of < 4,000 cases. About 25,000 cases of myeloid leukaemia
occur in the United States each year. Workplace exposure to inhaled chemicals is among the
most important risk factors for sinonasal cancers. Professionals exposed to formaldehyde in
their occupation, such as funeral industry workers and embalmers, showed an increased risk
of leukaemia and brain cancer compared with the general population. Other factors are
important in determining individual risk for the development of leukaemia or nasopharyngeal
cancer.
In the residential environment, formaldehyde exposure comes from a number of different
routes; formaldehyde can off-gas from wood products, such as plywood or particle board, but
it is produced by paints, varnishes, floor finishes, and cigarette smoking as well.
Singapore National Environment Agency recommends that the maximum threshold level for
formaldehyde should not exceed 0.1ppm, based on Guidelines for Good Indoor Air Quality
in Office Premises.2
The purpose of this case study is to review the different methods to determine the
concentration of formaldehyde.

IAQ, Indoor Air quality website url: http://www.iaqsg.com/chemicalparameters/formaldehyde/ , accessed on 04/04/2016

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2.0 Standardized Methods

Several standards have been developed to provide guidelines for the sampling and analytical
methods for determining the concentration of formaldehyde in air. The majority of the
methods use a sorbent tube to collect formaldehyde in an active sampling train. Some
methods consider the use of a diffusive sampler to collect formaldehyde in the air passively;
one other method makes use of an impinger to collect formaldehyde in a liquid solution3.
High performance liquid chromatography (HPLC) using an ultraviolet detector is the
analytical method of choice for most of the standards. Other standards recommend gas
chromatography (GC) and visible absorption spectrophotometry (VAS) for the analysis of the
collected samples.
In addition to sampling formaldehyde direct from air, NIOSH has documented a method for
sampling formaldehyde-containing particulates. These particulates are a common occurrence
in the wood and textile industries. Legislations has focused on the gas-phase concentration of
formaldehyde based on established interpretation of results from epidemiological studies.
The concentration of formaldehyde-containing particulates at the workplace is not regulated
by either OSHA or the Singapore authorities4.
The list of approved methods for compliance sampling is presented in Table 1. The NIOSH
3500, OSHA 1007 and NIOSH 5700 methods are selected for further discussion below.
Table 1: Approved methods for compliance sampling of formaldehyde in air
Agency

Reference

Sampler

NIOSH

2016
2539

Sorbent Tube
Sorbent Tube

2541
3500
5700
52

Sorbent Tube
Glass Midget Impinger
IOM Particulate
Sampler
Sorbent Tube

1007
ID-205

Diffusive Sampler
Diffusive Sampler

HPLC-UV
VAS

IP-6A

Sorbent Tube

HPLC-UV

IP-6C

Diffusive Sampler

HPLC-UV

IP-11A

Sorbent Tube

HPLC-UV

D 5197

Sorbent Tube

HPLC-UV

OSHA

EPA

ASTM

3
4

Analytical
Method
HPLC-UV
GC-FID
GC-MS
GC-FID
VAS
HPLC-UV

Applications

GC-NPD

Use of formalin solutions

For screening only

Textile dust or wood dust

Not suitable for STEL

sampling
Environmental sampling
(indoor air)
Environmental sampling
(indoor air)
Environmental sampling
(ambient / outdoor air)

NIOSH, NOISH Manual of Analytical Methods, Fourth Ed., 1994

NEA, National Environment Agency website, url: www.nea.gov.sg, date retrieved: 29th March 2016

7 of 26

2.1

NIOSH 3500

2.1.1 NIOSH Method 3500 for Formaldehyde Measurement5

The NIOSH method 3500 is an active sampling approach which uses a sampler attached to a
pump. After collection of the sample, it is analysed through a visible absorption spectrometry
of wavelength 580nm.
Sampler:
The sampler consist of a filter with a PTFE membrane filter (1-3m pore size) supported by
an O-ring followed by 2 midget impingers (Fig 1). During sampling, the two impingers are
filled with 20ml, 1% sodium bisulfite solution. A cassette is attached to the impinger and
impinger to the sampling pump via a flexible inert tubing. The PTFE membrane is necessary
if the sampling is used in a dusty environment. The use of dual impingers in series is
recommended to ensure efficient collection of formaldehyde. After sampling, the contents of
the impingers will be transferred to a polyethylene bottle for shipping.

Figure 1: Midget Impinger

Figure 2: Midget Impinger with Sampling Flow Pump

Sample Preparation
When the impingers solution are brought back, the volume of the solution from the front and
back up impinger, Vf and Vb are recorded. 4mL of pipetted sampling solutions is transferred
to a 25mL glass stoppered flask. A 0.1mL 1% chromotropic acid can react with 40
micrograms of formaldehyde. Addition of 6mL of concentrated sulphuric acid is performed
slowly and a gentle swirl to mix. A colour develops as illustrated (Fig 3). The sample is then
5

Kennedy, E. R. (1994). FORMALDEHYDE: METHOD 3500, Issue 2. NIOSH Manual of Analytical Methods
(NMAM), Fourth Edition, 8/15/94. Retrieved April 12, 2016, from http://www.cdc.gov/niosh/docs/2003154/pdfs/3500.pdf

8 of 26

placed in a 1cm-cuvette into the spectrophotometer. The reading is recorded at visible

absorption spectrometry at 580nm. Effect of other aldehydes is minimal on this method.

Figure 3: Addition of Chromotropic Acid into Sample solution in Glass Stoppered Flask

Applicability: The working range is 0.02 to 4ppm for an 80L air sample. This is the most
sensitive method and is able to measure ceiling levels as low as 0.1ppm.
Inteferences: Oxidisable organic materials may give a positive interference.
Accuracy, bias and precision of Results
Method Bias should be less than 10% as required by the NIOSH Guidelines. For the NIOSH
Method 3500, there are none identified. The precision expected is 0.09
The accuracy which is determined by the intersections of the bias and precision estimates on
the parabolic grid (nomogram) is 18%

2.1.2 Method Evaluation of NIOSH Method 3500

NIOSH Guidelines for Air Sampling and Analytical Method Development and
Evaluation6
The NIOSH Guide suggest guidelines for the development and evaluation of sampling and
analytical methods for industrial hygiene monitoring For each method under consideration,
the objective of this protocol was to decide if the method would provide results, on the
average, over a concentration range of 0.1 to 2 times the exposure limit, to be within 25% of
the true concentration with a probability of 0.95 for an individual observation.

Kennedy, E. R., Fischbach, T. J., Song, R., Eller, P. M., & Shulman, S. A. (1996). Summary of the NIOSH
Guidelines for Air Sampling and Analytical Method Development and Evaluation. Analyst, 121. Retrieved
April 4, 2016, from http://www.ncbi.nlm.nih.gov/pubmed/8831274

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The sampling of a generated atmosphere is needed to more adequately assess the

performance of a method. The concentration range of the analyte should be at least 0.1 to 2
times of the exposure limit. If it is toxic or suspected to be carcinogenic, there could be a
concentration lower than that calculated which needs to be considered.
NIOSH Method 3500 was checked for reproducibility by having 3 different analysts in 2
different laboratories analysed standard samples containing between 1-20 micrograms of
formaldehyde. The results are approximately the same of 5%.
Evaluation from the sampling of a generated atmosphere determines the following:
1)
2)
3)
4)
5)

Capacity of the sampler

Efficiency of analyte collection
Repeatability
Bias
Interferences in the collection by the sampler

Generation of the Analyte

As part of the evaluation method, the collection of samples is needed from an environment
that is as close to the actual sampling conditions as possible. And to fulfil this, the impact of
environmental conditions such as temperature, pressure, humidity and interferences needs to
be in consideration.
Table 2: Effects of surrounding conditions on the analyte

S/N Changed conditions

Effect

Increased temperature on the

collection medium

Decreased capacity of sampler or decompose

the analyste

Reduced pressure

Reduced capacity of a sampler

High relative humidity

Reduced sampler capacity

After the generation of the analyte, its concentration will be verified by a

gravimetric/volumetric means. Ideally, this independent method of verification should not be
biased and should provide an accurate estimated of the concentration. Precision and bias is
also homogenous over the concentration ranges.
Capacity of the Sampler and Sampling Rate
To determine the applicability, the capacity of the sampler should be determined by the
function of flowrate and sampling time.

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Different flow rates typical of the media will be used. Sampling should be performed at 3
different flow rates. The amount of analyte collected at the lowest flow rate and shortest
sampling time should be greater than the limit of quantitation of the method. The generated
analyte should be at least 2 times the highest published exposure limit will be used to
determine the sample capacity to be used.
Sampling should be conducted at various temperatures and humidity to check on its effect of
these parameters on the capacity. 3 replicates at different flow rates should be used to verify
the capacities at each of the different humidity and temperature
Table 3: Temperature and humidity conditions

Parameters

High

Low

Temperature

Ambient

>35 C

<20

Humidity

Ambient

20%

80%

Breakthrough should also be checked. If 5% of the backup sampler totals 5% for the mass
found on the front sampler , breakthrough has occurred.
The Maximum Recommended Sampling Time (MRST) for a specific flow rate = the time at
which sampler capacity was reached *0.66 ( a measure of safety to this determination).
Sample Stability
When samples are shipped back to the laboratory for analysis, the integrity of the analyte on
the sampling media is very important. To assess the stability, 30 samples should be collected
from a generated atmosphere and stored under defined conditions (humidity and temperature
of the generator should be at the same level as the sample capacity). They are divided
randomly in groups of samples. Each group is measured at Day 0, Day 7, Day 10, Day 14,
Day 21, Day 30.
Sample is required to be stable for a minimum of 7 days under ambient conditions. If the
samplers analysed on day 7 differs from the day 0 by more than 10%, it does not meet the
sample stability criterion. For the NIOSH 3500 method, the sample stability criterion and
hence refrigeration is required. Sample stability is 30 days at 25 degrees.
Precision, Bias and Accuracy
Precision, bias and accuracy are parameters to assess if this method can produce accurate
result. Sampler results from the experiments can be combined to assess these parameters.
There are calculation formulas derived to estimate precision, SrT, . But before calculations,
the homogeneity of the precision over the range of the concentrations studied should be
checked using a Bartletts test. After which, the calculation of the estimated precision can be
performed.

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Bias is assumed to be homogenous across the evaluated concentration ranges. This

assumption should be evaluated to see if there is homogeneity. Bias is estimated at each
concentration. To fulfil the criterion, method bias should be 10%
Accuracy is the intersections of these points on the parabolic grid in the graph. If the both the
upper confidence limits on the accuracy are less than 25%, it fulfils the accuracy criterion.
Field Evaluation
Field Evaluation is not required in the NIOSH Guidelines for Air Sampling and Analytical
Method Development and Evaluation, as conditions which exist in the field are difficult to
reproduce in the laboratory.
The field evaluation is recommended to further study the performance of the method. Both
the collection of area samples and personal samples should be included in the field evaluation
of the method. Area samples can be used to see if there is field precision and bias. Personal
samples can be used to assess the utility of the method.
In the following is a field precision study extracted from the article, Field Precision of
Formaldehyde Sampling and Analysis using NIOSH Method 3500, the American Industrial
Hygiene Association Journal 58:9,657-6607 The study was designed to examine the field
precision by collecting and analysing a series of replicate samples over an extended period.
The field area is the gross anatomy laboratory during their normal activities. There is also
presence of interferences in the existing work environment (oxidisable organics) where
embalming solutions were used.
Method:
2-4 replicates of airborne samples are obtained in the middle of a gross anatomy lab on 29
days. The inlets of the flow pumps (Fig 5) were positioned upward all at the same level about
120cm from the floor which emulate the breathing zone of the workers during dissection.
Distance between each replicate is about 10cm, as shown below
3750cm
750cm

10 cm

350cm

120cm

Figure 4: Set up of the Experiment

Khanzadeh, F. A., & Park, C. K. (1997). Field Precision of Formaldehyde Sampling and Analysis Using
NIOSH Method 3500. American Industrial Hygiene Association Journal, 58(9), 657-660.
doi:10.1080/15428119791012450

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The room temperature and pressure were measured during every collection of the sample.
The sample air flow rate was also determined before and after each sampling by a flow meter,
and the target sampling volume was set to be 0.2-1 L/min. Air volumes are adjusted to 25 deg
Celsius and 760mmHg accordingly to 1-100L

Figure 5: SKC PCXR Constant Flow Pump used to collect replicates

It was decided that the Polytetrafluoroethylene filter would not be used as it is a not a dusty
environment. The assumption is derived due to the whole dissecting operations being
performed on moist tissues without any mechanical tools, there is no evident source of
particulate generation. Even if there is, their effects on the precision will be negligible.
Results & Discussion
A total of 98 air samples were collected. 13 samples did not fulfil the target sampling and
working ranges, 4 of them exceeding sample volume range limit of 100L and 9 samples show
flow rate fluctuations of 10%. Lastly, 7 samples out of the 85 remaining were single and not
replicates. Hence, the remaining samples left for data analysis is 78.
The data were entered into statistical analysis, using Statistical Package for Social Sciences.
The descriptive statistics were used to determine means, standard deviations (SD), and the
ranges of sampling parameters, concentrations and coefficients of variation (CV, precision)
of each set of replicates. A t-test was applied to see the difference between the means of 2
independent groups.
CV = Standard deviation/Mean. A pooled CV is to demonstrate the overall precision of each
sampling and analytical method.

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Table I: Sampling Parameters and Formaldehyde concentrations by Number of Sample

Replicates
Number of Replicates in Each Set

Number of

Overall

16

18

44

78

186(18)

147(26)

156(28)

160(29)

160-215

120-187

115-220

115-220

Samples
Sampling
Time (min)

Mean

Sampling

(SD)

0.4(0.1)

Flow (L/min)

Range

0.2-0.5

Sampling

66(2)

56 (21)

60(19)

60(19)

Volume (L)

39-89

26-99

27-100

26-100

Concentration

1.01 (0.48)

0.84(0.17)

0.97(0.28)

0.95(0.31)

(ppm)

0.05-1.71

0.62-1.25

0.59-1.72

0.05-1.72

From Table II, the precision of replicate samples ranged from 0.03 to 0.24 with an overall
precision of 0.09. This is equal to the precision of NIOSH Method 3500.
The results of the precision also improve as the number of samples in each case increased
from 2-4 replicates. Nevertheless, within the preset target sampling and working ranges, the
results did not demonstrate any significant relationship between the parameters of CV,
formaldehyde concentrations, flow rate, sampling time or sampling volume.
Table II: Coefficient of Variation (CV) by number of Sample Replicates Collected in a Gross
Anatomy Laboratory
Number of Replicates in Each Set

Number of sets
Range of CV
Pooled CV

Overall

11

25

0.035-0.241

0.026-0.108

0.026-0.201

0.026-0.241

0.116

0.079

0.092

0.093

Conclusion:
The overall precision of the field sampling and analysis was 0.09 which is equal to the
precision of Method 3500 as determined in the laboratory.

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2.2

OSHA 1007

The OSHA Method 1007 describes the validation of diffusive samplers that are meant to
provide an alternative to an existing method, ID-205. ID-205, which validates a diffusive
monitor from 3M (model 3721), is limited by the minimum sampling time of 4 hours, making
it unsuitable to measure STEL level which requires a sampling time of 15 minutes.
The OSHA 1007 method has evaluated and fully-validated three brands of diffusive samplers.
These samplers use 2,4-dinitrophenyl hydrazine (DNPH) to react with formaldehyde in the
presence of an acid to form a unique derivative. Supelcos sampler is found by the authors of
this report to have been replaced by a high efficiency (HE) model which is not suitable for
STEL measurement, and hence not suitable for comparison with the other two brands. Refer
to the Table 4 for other useful information about the samplers.
The laboratory analysis of field samples requires a liquid chromatograph equipped with a UV
detector (set at 365 nm wavelength). Refer to the OSHA document for detailed guidelines for
the analytical procedure8.
Table 4: Diffusive samplers validated by OSHA Method 1007
Assay Technology
Specifications

ChemDisk 571
Aldehyde Monitor

SKC UMEx 100

Passive Sampler

Supelco DSD-DNPH
Diffusive Sampling
Device

High Efficiency (HE)

model

Reagent

Tape (material

Spherical silica gel

unknown)

(105 210 m)

100 ppm-hrs

29 g

150 g for HE model

15 min

330 ppb

200 ppb (0.24 mg/m3)

8 hr

10 ppb

5 ppb (6 g/m3)

24 hr

N.A.

2 ppb (2 g/m3)

7 days

N.A.

0.2 ppb (0.2 g/m3)

Collection medium

Fiberglass

Capacity
Lower
Detection
Limits

2,4-dinitrophenyl hydrazine (DNPH)

Unknown; HE model
not recommended for
STEL

OSHA, Method 1007: Formaldehyde (Diffusive Samplers), T-1007-FV-01-0505-M, May 2005

15 of 26

Limitations
This method is not suitable for sampling formaldehyde exposure at workplaces where
formalin solutions, formaldehyde/water solution stabilized with methyl alcohol, is used;
OSHA recommends the active sampling method (OSHA Method 52) to be used when
monitoring exposures resulting from the use of formalin solutions.
This method is not suitable for atmospheres with more than 0.5 ppm ozone concentration due
to interference of DNPH reaction with formaldehyde. DNPH was found to be resistant to
interference from other aldehydes such as, acetaldehyde, butyraldehyde, benzaldehyde and
glutaraldehyde. The samplers also requires at least 10% humidity for best performance and
should be stored at 4 C before and after sampling.

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2.3

NIOSH 5700

In the wood and textile industries, there is potential for airborne formaldehyde to be bound to
inhalable dust. NIOSH Method 5700 is an active sampling method using a sampler
developed by the Institute of Occupational Medicine (IOM). The sample and filter is
designed to collect inhalable dust and comes with a PVC filter with pore size of 5 m.
An example of the sampler is shown in Figure 6. The sampler is fully evaluated for
concentration range of between 0.007 and 0.16 mg/m3.
The recommended analytical method is HPLC using UV detector at 365 nm wavelength.
However, the VAS analytical method used in NIOSH Method 3500 is applicable provided
that there are no substances in the sample which can interfere with the chromotropic acid
analysis. These substances include phenol, oxidizable organic material, other aldehydes and
alcohols.
As the results collected by this method are not required for compliance, the NIOSH manual
cautioned against combining the results from this method together with results collected by
methods which measures the vapour-phase concentration.

Figure 6. SKC IOM Sampler

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2.4

Other Methods

2.4.1 Direct Reading Instruments

Direct reading instruments provide fast access to results at the field and is more useful than
the standardized methods in cases where qualitative measurements are desired in real-time to
pinpoint hot spots. Current direct reading instruments for airborne formaldehyde makes use
of electrochemical sensing, photoelectric photometry, colorimetric or photo-ionization
technologies to detect the target molecules.
These equipment are primarily used as a screening tool to establish the orders of magnitude
of the airborne concentration levels of formaldehyde, where higher than desired levels will
warrant the more costly and time-consuming standardized laboratory methods to be carried
out. The instruments have many limitations affecting the accuracies of the readings. These
limitations include: sensitivity to temperature, pressure and humidity; non-selective to
formaldehyde; and prone to contamination and adsorption effects. A recent research
compares two direct reading instruments to NIOSH Method 2016 and found that one of the
instrument significantly underestimated formaldehyde concentration as compare to the
laboratory method whereas the other instrument produced results that are not statistically
significantly different9.

2.4.2 Emission testing standards

Apart from indoor and ambient air concentrations, formaldehyde emissions from
manufactured products are also regulated in countries in North America, Europe and Asia.
Different standards are employed in various countries. In the US, the California Air
Resources Board (CARB) approved the use of ASTM E 1333 and ASTM D 6007 as the
standards for emission testing in large and small chambers respectively. A smaller chamber,
known as the Dynamic Micro Chamber (DMC), although not included in the standards, has
shown good comparability with large chambers for measuring formaldehyde emissions. In
Europe, EN 717-1 (large chamber method) and EN 717-2 (gas analysis method) are two
common standards used in emission testing 10 . Other methods includes the EN 120
(perforator method), EN 717-3 (flask method) and JIS A 1460 (desiccator method).
A highly portable and widely tested device, called the field and laboratory emission cell
(FLEC), has been in use since 1991 to carry out emission testing and quality assurance on
location. The major advantages are its portability and that the test procedure is nondestructive

Hirst, D.V.L; Gressel, M.G.; Flanders, W.D., Short-Term Monitoring of Formaldehyde: Comparison of Two
Direct-Reading Instruments to a Laboratory-Based Method, Journal of Occupational and Environmental
Hygiene, Vol. 8, pg 357-363
10
Bhm, M.; Salem, M.Z.M; Srba, J., Formaldehyde emission monitoring from a variety of solid wood,
plywood, blockboard and flooring products manufactured for building and furnishing materials, Journal of
Hazardous Materials, 2012, pg 68-79

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in nature11. The design and properties of this type of emission cell is covered by the ISO
16000-10 standard.
Figure 7, 8 and 9 illustrates the various test methods

Figure 7: European chamber method EN 717-1

Figure 8: Other emission testing methods

11

Salthammer, T.; Mentese, S.; Marutzky, R., Formaldehyde in the Indoor Environment, Chemical Reviews,
2010, Vol. 110, pg 2536-2572

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Figure 9: Field and laboratory emission cell (FLEC)

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2.5

Novel Methods

Since 2012, the WHO International Agency for Research on Cancer (IARC) has expanded its
classification of formaldehyde as a known carcinogen (Group 1), with positive links to
nasopharyngeal cancer, leukaemia, as well as sinonasal cancer12 . As such, with the hazards
of formaldehyde attracting increasing attention, the need for a reliable yet cost effective
method for measuring accurately formaldehyde levels in the environment is apparent.
As discussed in the previous chapters, while NIOSH approved methods are the gold standard
for sampling and analyzing formaldehyde concentration in ambient air for compliance
monitoring, these are primarily chromatography based methods which are ex-situ, requiring
analysis in a lab following collection in the field. These methods are hence not suited for
rapid, real time monitoring of formaldehyde concentration in the environment.
As such, some research have explored novel methods of on-site quantification of
formaldehyde in air, which does not use the traditional methods of liquid or gas
chromatography, but instead uses other methods which fulfil the requirements of being both
simple and portable, as well as being sufficiently specific and sensitive enough for large scale
deployment for environment monitoring in-situ.
While these requirements are partly fulfilled by some currently available direct measurement
methods which uses electrochemical gas sensors and colorimetric detection tabs 13 , these
direct measurements methods suffer from several limitations, which affects the accuracies of
the reading. Hence although portable, and able to give fast access to results on the field in
real time, the equipment are not cost-effective, and in some cases of insufficient sensitivity
and selectivity to provide reliable measurements.
Thus, one of the new novel method which stands out is biosensors, specifically an enzyme
based detection method, which can give provide readings in-situ, with greater selectivity and
reliability than current commercially available direct measurement methods.

2.5.1 Biosensors
Biosensor is a general term that describe devices which can be used to detect a specific
substances, using a combination of biological components and physiochemical detector. The
biological component of a biosensor, such as enzymes or cell receptors, are usually highly
specific, reacting or binding only with the specific desired substance. The reaction between
the biological component and the target substance then generate specific physiochemical
signals, such as color or florescence, which can then be detect and quantified by the
physiochemical detector.

12

International Agency for Research on Cancer (IARC), Formaldehyde, IARC Monographs on the Evaluation
of Carcinogenic Risks to Humans, 2012, vol. 100F
13
Hirst, D. V., Gressel, M. G., & Flanders, W. D. (2011). Short-Term Monitoring of Formaldehyde:
Comparison of Two Direct-Reading Instruments to a Laboratory-Based Method. Journal of occupational and
environmental hygiene, 8(6), 357-363.

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The novel methods of formaldehyde measurement in the environment using biosensors hence
could potentially provides several advantages over both the approved NIOSH methods and
commercially available direct measurement methods, These advantages are:

On-situ measurements and reading

High specificity of detection
Cost effective

Two of such novel formaldehyde detection methods using biosensors will be further
discussed below. These two methods make use of DNAzymes and formaldehyde
dehydrogenase respectively, with both having their own which uses and advantages.

2.5.2 DNAzymes
DNAzymes, or catalytic DNA are a kind of artificial enzymes which are capable of specific
catalytic activities. They are widely used for a variety of biochemical reaction, such as DNA
glycosidic bond cleavage and DNA self-modification. They have also been used as the
biological component of biosensors, being used to detect nucleic acid, proteins and metal ions.
As such, research has been made to apply the use of DNAzymes into the detection of
formaldehyde, to develop a low cost, sensitive and selective biosensor.
In a research paper by Yang and et al14, they discussed the procedure used for optimizing the
colorimetric property of 2,2-azino-bis(3-ethylben-zothiazoline-6-sulfonic acid)(ABTS) for
the detection of formaldehyde.
ABTS+ is a blue-green-colored free-radical cation, and the reaction of ABTS with H2O2 to
form ABTS+ is catalyzed by the hermin-G-quadruples complex (DNAzymes). Formaldehyde
participates in a competing reduction-oxidation reaction with H2O2, which thus prevents the
formation of the ABTS+. As such, the concentration of formaldehyde present can be deduced,
through the indirect measurement of ABTS+ using a colorimetric assay.
One possible advantage of this method of formaldehyde analysis is the selectivity of the
process compared to available direct reading instruments, as various other possible
contaminants tested, such as various alcohols (known interferent for the htV formaldehyde
meter) do not have any significant effect on the measured results.
Through the use of a smartphone application and a portable set up consisting of a dark room
with a LED light, the colorimetric assay can be performed in the field, for rapid assessment of
the results:

14

Yang, X., Wang, Y., Liu, W., Zhang, Y., Zheng, F., Wang, S., & Wang, J. (2016). A portable system for onsite quantification of formaldehyde in air based on G-quadruplex halves coupled with A smartphone reader.
Biosensors and Bioelectronics, 75, 48-54.

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Figure 9: Schematic of the portable smartphone-based optical reader

This detector setup was found to be able to detect formaldehyde in a linear range of 0.02 to
14 ppm, and is thus suitable for practical usage, based on the maximum threshold level of 0.1
ppm recommended by NEA.

2.5.3 Formaldehyde dehydrogenase

Similarly, in another research paper by Kudo and et al15, the use of another novel biosensor
for formaldehyde monitoring was demonstrated. Their technique is also enzyme-based,
similar to the previous one discussed, but for this the fluorescence property of nicotinamide
adenine dinucleotide (NADH) was used as an indirect measurement of formaldehyde
concentration.
Formaldehyde dehydrogenase (FALDH), an enzyme which catalyzes the chemical reaction
between formaldehyde and NAD+ (oxidized form) to formate and NADH (reduced form),
was prepared and immobilized on a membrane, which act as the biological component of the
biosensor. Hence, the amount of NADH measured on the membrane after exposure can be
correlated with the amount of formaldehyde originally present.
The membrane was mounted in a flow cell set up, together with a custom fiber-optic NADH
measurement system which can measure the fluorescent intensity of the membrane, to create
a formaldehyde-sensitive optode.
By connecting the optode to a pump system for circulation of a phosphate buffer solution
containing NAD+, the membrane can be rinsed, enabling continuous monitoring of
formaldehyde levels, as compared to the previous biosensor setup:

15

Kudo, H., Suzuki, Y., Gessei, T., Takahashi, D., Arakawa, T., & Mitsubayashi, K. (2010). Biochemical gas
sensor (bio-sniffer) for ultrahigh-sensitive gaseous formaldehyde monitoring. Biosensors and Bioelectronics,
26(2), 854-858.

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Figure 10: Structure of flow-cell and formaldehyde-sensitive optode

The setup was found to be highly sensitive and selective in comparison to conventional
formaldehyde gas sensor. The selectivity was to be expected, due to the specificity of the
FALDH enzyme reaction, and the optode was able to monitor formaldehyde levels
continuously at very low concentrations from 2.5 ppb to 10 ppm.

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3.0 Conclusion
Formaldehyde can be an invisible killer, if not for regulations put in place to limit its
concentration at the workplace. Standardized methods provide a way for enforcing the
regulation at the workplace where formaldehyde is used. However, it can still creep into our
lives unsuspectingly through the use of shoddy building material emitting high concentration
of the chemical. Direct reading instruments utilizing the novel technologies provide a quick
and reliable measurement of airborne formaldehyde concentration. They should be widely
used to provide assurances for indoor air quality in high risk locations such as newly
constructed homes, newly opened underground retail spaces, etc.
The usage of either the direct-reading instruments or the standardized laboratory methods
depend on the objective of the experiment, the condition of the sample, the equipment
available and the requirements of the regulations. All the limitations and the advantages of
the method must be considered before choosing it.
At the cutting edge, there are several novel methods of formaldehyde detection which are
being researched and tested in the lab. These methods use differing principles and concepts,
which have several advantages over the convention and traditional methods, particularly in
for on-site monitoring in the field, and could be of great utility and benefit if realized in the
future.
This literature review exercise has given the group members a more thorough understanding
about the hazards of formaldehyde and the methods of monitoring exposure to this chemical.

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4.0 References
[1]
[2]
[3]
[4]
[5]

[6]

[7]

[8]
[9]

[10]

[11]
[12]
[13]

[14]

[15]

Formaldehyde, World health Organization, 2002

IAQ, Indoor Air quality website url: http://www.iaqsg.com/chemicalparameters/formaldehyde , accessed on 04/04/2016
NIOSH, NOISH Manual of Analytical Methods, Fourth Ed., 1994
NEA, National Environment Agency website, url: www.nea.gov.sg, date retrieved:
29th March 2016
Kennedy, E. R. (1994). FORMALDEHYDE: METHOD 3500, Issue 2. NIOSH
Manual of Analytical Methods (NMAM), Fourth Edition, 8/15/94. Retrieved April 12,
2016, from http://www.cdc.gov/niosh/docs/2003-154/pdfs/3500.pdf
Kennedy, E. R., Fischbach, T. J., Song, R., Eller, P. M., & Shulman, S. A. (1996).
Summary of the NIOSH Guidelines for Air Sampling and Analytical Method
Development and Evaluation. Analyst, 121. Retrieved April 4, 2016, from
http://www.ncbi.nlm.nih.gov/pubmed/8831274
Khanzadeh, F. A., & Park, C. K. (1997). Field Precision of Formaldehyde Sampling
and Analysis Using NIOSH Method 3500. American Industrial Hygiene Association
Journal, 58(9), 657-660. doi:10.1080/15428119791012450
OSHA, Method 1007: Formaldehyde (Diffusive Samplers), T-1007-FV-01-0505-M,
May 2005
Hirst, D.V.L; Gressel, M.G.; Flanders, W.D., Short-Term Monitoring of
Formaldehyde: Comparison of Two Direct-Reading Instruments to a LaboratoryBased Method, Journal of Occupational and Environmental Hygiene, Vol. 8, pg 357363
Bhm, M.; Salem, M.Z.M; Srba, J., Formaldehyde emission monitoring from a
variety of solid wood, plywood, blockboard and flooring products manufactured for
building and furnishing materials, Journal of Hazardous Materials, 2012, pg 68-79
Salthammer, T.; Mentese, S.; Marutzky, R., Formaldehyde in the Indoor
Environment, Chemical Reviews, 2010, Vol. 110, pg 2536-2572
International Agency for Research on Cancer (IARC), Formaldehyde, IARC
Monographs on the Evaluation of Carcinogenic Risks to Humans, 2012, vol. 100F
Hirst, D. V., Gressel, M. G., & Flanders, W. D. (2011). Short-Term Monitoring of
Formaldehyde: Comparison of Two Direct-Reading Instruments to a LaboratoryBased Method. Journal of occupational and environmental hygiene, 8(6), 357-363.
Yang, X., Wang, Y., Liu, W., Zhang, Y., Zheng, F., Wang, S., & Wang, J. (2016). A
portable system for on-site quantification of formaldehyde in air based on Gquadruplex halves coupled with A smartphone reader. Biosensors and Bioelectronics,
75, 48-54.
Kudo, H., Suzuki, Y., Gessei, T., Takahashi, D., Arakawa, T., & Mitsubayashi, K.
(2010). Biochemical gas sensor (bio-sniffer) for ultrahigh-sensitive gaseous
formaldehyde monitoring. Biosensors and Bioelectronics, 26(2), 854-858.

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