PROCESSING CONTAMINANTS

Furan
C Crews, The Food and Environment Research Agency, York, UK
r 2014 Elsevier Inc. All rights reserved.

Furan
Furan (Figure 1) is a five-membered unsaturated cyclic ether
(C4H4O). It is a very volatile colorless liquid with a boiling
point of 31.4 1C. It is only poorly soluble in water, but
dissolves in organic solvents. Furan is produced commercially
for use as a chemical intermediate and as a solvent. It has long
been known a component of cigarette smoke. The name is
also applied as an abbreviation of polychlorinated dibenzofurans, which are associated with the environmental contaminants known as polychlorinated dioxins, these should not
be confused with the monocyclic compound.

Occurrence
Furan in Food
Furan was reported as present in a wide range of foods
during the 1960s. The foods included canned cooked meat,
hydrolyzed proteins, bread, and coffee. These findings were
not followed up to a significant degree partly because furan
was not expected to be a widespread food contaminant and
partly because its volatility was so high that many analytical
methods aimed at screening foods for volatile components
simply missed its presence. Interest in furan as a food contaminant was revitalized in 1996 when it was found during
tests of the effects of ionizing irradiation used for preservation
of apple juice.
The first major survey of the levels of furan in food
was conducted by the US Food and Drug Administration
(FDA) in 2004. The FDA published an analytical method
that was used to measure furan in a range of particular foods.
The survey targeted foods that were sold in cans and
jars as furan formed during manufacture would not have escaped through evaporation, and included baby foods, infant
formulae, canned vegetables, packaged fruits, and sauce mixtures. The highest levels were found in roasted coffee and in
starchy foods such as beans that had been heated in jars
or cans.

H
Figure 1 Structure of furan.

Encyclopedia of Food Safety, Volume 2

H
H

Furan levels of over 100 mg kg 1 have been found in three

major food groups sampled in the US and Europe: coffee,
baby food, and sauces and soups. Furan was detected in 262 of
the 273 baby food samples reported by FDA (11) and European Food Safety Authority (EFSA) (10) with an average level
of 28 mg kg 1, and in 70 of 71 infant foods at similar levels.

Food Safety Issues

Toxicity
Furan is readily absorbed from the lung or intestine. After
ingestion it primarily affects the liver where it is metabolized
by the P-450 enzyme system with the formation of cis-2butene-1,4-dial. This highly reactive compound is considered
to be the genotoxic principle (causing damage to deoxyribonucleic acid, DNA) as it can bind to cellular nucleophiles including proteins and nucleosides. In the liver furan depletes
adenosine triphosphate (ATP) irreversibly and causes doublestrand breaks in DNA, leading ultimately to cell death.
Some studies of the toxicity and carcinogenicity of furan
have been conducted by the US National Toxicology Program
(NTP) using rats and mice, but only limited data are available,
and there are no human studies. In NTP studies furan administrated by gavage in corn oil induced liver tumors in mice
and cholangiocarcinomas, hepatocellular tumors, and mononuclear cell leukemia in rats. The mechanism of this carcinogenicity in rodents has not been fully clarified yet, but both
genotoxic and nongenotoxic mechanisms have been proposed.

Carcinogenicity
Furan administered to rats and mice daily at between 2 and
8 mg kg 1 body weight per day (rats), and 815 mg kg 1 body
weight per day to mice caused lesions of the liver and increased hepatocellular adenomas and carcinomas.
In a 2-year carcinogenicity study in rats and mice given
repeated doses over 16 days or 13 weeks by gavage in corn oil
increased mortality was seen with doses at or over 80 mg per
kg body weight per day. Dose-related liver lesions were seen
at high dose rats (60 mg kg 1) with mice being slightly less
affected. Hepatocyte proliferation and apoptosis were seen in
a 3-week exposure of female animals at levels of up to 15 mg
kg 1 body weight per day.
With lower doses of furan (up to 8 mg kg 1 body weight
per day over 3 weeks) mice exposed to 1 mg kg 1 body weight
per day or more had increased liver weight and incidence of

doi:10.1016/B978-0-12-378612-8.00208-0

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Processing Contaminants: Furan

hepatic cytotoxicity. Mice exposed to 8 mg kg 1 body weight

per day had hepatocyte proliferation.
Detailed studies of the mechanisms of tumor induction by
furan compared the range of gene mutations with those of
controls and concluded that the hepatocarcinogenicity might
be partially attributable to genotoxicity, but the evidence is so
far inconclusive. Epidemiological comparisons of coffee consumption with human cancers do not show a correlation.

Genotoxicity
Three in vitro studies into the genotoxicity of furan had inconclusive results. Furan has been shown not to be mutagenic
but its metabolite cis-2-butene-1,4-dial is directly mutagenic at
nontoxic concentrations in sensitive strains of Salmonella
typhimurium. The metabolite forms adducts with DNA and
proteins.
Accordingly, the International Agency for Research on
Cancer has concluded that furan is reasonably anticipated to
be a human carcinogen based on sufficient evidence of malignant tumor formation at multiple tissue sites in multiple
species of experimental animals.
Furan is carcinogenic to rats and mice, with a dosedependent increase in liver adenomas and carcinomas. EFSA
have concluded that the weight of evidence indicates that
furan is a carcinogen and is probably genotoxic.

Exposure
Previous to the discovery of the widespread presence of furan
in food the major source of human intake was thought to be
commercial use in the workplace. Furan has also been detected in the exhaled breath of smokers, and in the indoor air
of homes. Another possible important source is in the air of
kitchens and other places where food is heated.
Some typical ranges of furan levels determined in a number of foods are provided in Table 1. The data are taken
mainly from surveys reported by the FDA and EFSA. It is of
concern that possible human exposure is close to the
equivalent doses that produce carcinogenic effects in

Table 1
Mean and maximum levels of furan (mg kg 1) typically
found in foods

experimental animals. The two food items that are the cause of
most concern regarding exposure to furan are canned and
jarred baby foods and coffee.

Coffee
Furanic compounds are important contributors to the flavor of
coffee. The unroasted (green) beans are virtually free of furan
but very high levels (B4 mg kg 1) are formed when the beans
are roasted. Handling processes including grinding lead to a
reduction of furan levels but coffee powder still contains
approximately 2 mg kg 1 furan. Other processes, such as the
manufacture of instant coffee, cause a further reduction to
1 mg kg 1 or less.
Brewing coffee for consumption decreases the furan level
much more significantly depending on the process. Espresso
coffees have a high concentration on account of their small
volume, and the doses from these and percolator machines are
higher than that from cafetiere and instant coffee powder
(Table 2).

Baby Food
A very high proportion of baby foods sold in can and jars
contain significant levels of furan, typical 520 mg kg 1, this
being due to the industrial cooking, sterilization, and pasteurization processes and the presence of precursors in many of the
food formulations. The highest concentrations (1535 mg
kg 1) are found in canned or jarred baby foods based on pasta,
meat, or vegetables, with lower levels (10 mg kg 1 or less) in
canned or jarred infant beverages, cereals, and fruits.

Other Foods
Of the widely consumed canned and jarred foods surveyed by
the FDA and EFSA canned starchy foods such as beans and
soups contained the most furan, typically 100 mg kg 1. Some
other foods (malted products, gravies, and caramels) contained higher levels. Limited surveys have shown that many
foods that are not cooked in closed containers also contain
relatively high levels of furan. These are mainly crispbreads
and toasted cereal products such as toasted bread.

Product

Mean

Maximum

Effects of Domestic Cooking

Coffee, instant
Coffee, roast bean
Coffee, roast ground
Baby food
Infant formula
Baked beans
Beer
Fruit juice
Meat products
Milk products
Sauces
Soups
Soy sauce
Vegetable juice
Vegetables

500
2000
1000
25
20
25
5
5
20
15
10
25
25
5
10

2000
5000
6000
200
50
120
30
420
120
80
120
220
80
20
75

Although the topic has received little study it appears that

domestic cooking procedures invariably reduce the furan
content of foods. Although some furan is almost certainly
formed during, for example, the reheating of canned soup, the
Table 2
Furan (mg kg 1) typically found in coffee powders and
brewed coffee

Regular
Decaffeinated
Espresso
Instant

Powder

Brew

1800
2000
1700
400

24
16
44
8

Processing Contaminants: Furan

procedure leads to an overall loss of furan, presumably to the

atmosphere. Actions such as stirring and dispensing food on
to plates, and leaving food and beverages to stand causes loss
of furan. Mild domestic cooking methods such as reheating
prepacked ready meals or soups in a microwave oven do not
increase the furan content. There is some evidence that furan
driven out of food during domestic cooking can be inhaled
from the kitchen air during preparation.

foods may form a high proportion of their diet as well as the

larger amounts (relative to body weight) of certain foods.
From the FDA data a mean intake for infants of approximately 0.4 mg furan per kg body weight was calculated for
infant foods, and again, similar results were calculated by the
BfR for Germany and for the EU by EFSA, which estimated the
exposure of babies to furan at o0.226 mg furan per day or
o0.033.5 mg kg 1 body weight (bw) per day for a 6-monthold baby weighing 7.5 kg consuming food exclusively from
glass jars.
Estimates of exposure indicate a small margin (a factor of
approximately 2000) between human exposure doses and
those causing liver tumors in experimental animals.

Dietary Exposure
Dietary exposure to furan can be estimated from knowledge of
the furan content and intake of foods. These estimates are
necessarily based on the food types tested, which have tended
to be those likely to contain relatively high furan levels. For
adults the most important source is brewed coffee beverages.
The intake from this source will obviously vary with the choice
of brewing procedure and level of consumption, with cultural
differences being significant. The intake for an infrequent
consumer of instant coffee, for example, will be much lower
than that of the typical Mediterranean heavy consumer of
espresso coffees. EFSA has estimated the daily adult intake
from coffee to be 2.4116 mg per person, compared to
1.123 mg per person from canned or jarred vegetables and
1.350 mg per person from beer.
From the FDA data the adult intake mainly from brewed
coffee, was approximately 0.15 mg kg 1 body weight per day.
Exposure calculations for Germany made by the Federal Institute for Risk Assessment (BfR) were similar to the FDA.
From EFSA data collected within the EU the furan intake estimates based on coffee were higher at approximately
0.50.7 mg kg 1 body weight per day, probably on account of
different coffee consumption data.
There is concern regarding the exposure of babies to furan
not only because its levels are relatively high in canned and
jarred baby foods but also because canned and jarred baby
HO

Formation
Several chemical routes of furan formation in foods have been
identified. The principal ones being the thermal oxidative
degradation of ascorbic acid and unsaturated fatty acids, with
degradation of sugars and carotenoids also being important.
These reactions are complex but have been studied in some
detail through experiments on model food systems comprising only a few reactants. It has become clear; however, that
they fall short of representing what happens in whole foods.
The furan formation routes shown in Figures 24 have been
simplified considerably.
When food is heated, sugar and amino acids undergo a
series of reactions known as the Maillard reactions, to form
products having the distinctive brown color. Large numbers of
compounds having a furan ring are formed along with furan
itself. Many of these compounds are important flavor constituents and are nontoxic.
In many mechanisms furan is ultimately formed by the
decarboxylation of 2-furoic acid or the breakdown of
2-furfural.

OH
O

HO

HO
O

OH

HO

HO
Ascorbic acid

OH

Deoxy aldotetrose

Furan

Figure 2 Simplified furan formation route from ascorbic acid.

O
OH
HO

O
HO
OH

OH

HO

COOH

OH

HO
Sugar

Aldotetrose

Figure 3 Simplified furan formation route from sugars.

401

Furoic acid

Furan

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Processing Contaminants: Furan

PUFA

HO
O

4-Hydroxy-2-butenal

OH

Furfural

O
Furan

Figure 4 Simplified furan formation route from polyunsaturated fats.

Formation from Ascorbic Acid

Heat treatment of ascorbic acid readily forms furan but the
degree of formation is reduced significantly in the presence of
other compounds, even some that are also known to be furan
precursors. It is strongly affected by the pH and the presence of
sugars.
On heating ascorbic acid behaves in similar manner to
reducing sugars. In the presence of air it is oxidized to dehydroascorbic acid which is then hydrolyzed to 2,3-diketogulonic acid, decarboxylated, and ultimately dehydrated to
2-furoic acid, 3-deoxypentosulose, and furfural.
In anaerobic conditions ascorbic acid is not oxidized but
undergoes hydrolysis, elimination, and decarboxylation to
form 2-deoxyaldotetrose and then furan.
Ascorbic acid can act as an oxidizing agent suspected of
promoting oxidative degradation of lipids to form furan in
some foods that are high in polyunsaturated fatty acids.

Formation from Carbohydrates

Several amino acids and carbohydrates react on heating to
form aldotetrose derivatives that undergo cyclization to form
furan. Glucose can be dehydrated and subjected to retro-aldol
cleavage forming 2-deoxy-3-ketoaldotetrose and ultimately
3-furanone and furan. The final stages of furan formation
from sugars is probably the reduction of 3-furanone by
formic acid.
In amino acids heating produces acetaldehyde and a glycolaldehyde that undergo aldol condensation to form furan.
Not all amino acids form glycolaldehyde and need another
source such as reducing sugars for furan formation.

Formation from Fatty Acids

Furan is formed from mono- and diunsaturated fatty acids on
heating, whether they are free or esterified in triacylglycerols.
The mechanism is one of the free radical autoxidation, which
is enhanced by lipid oxidation catalysts such as metal ions,
and probably followed by cyclization and dehydration of
4-hydroxy-2-butenal.

Analysis
Early methods for the determination of volatile compounds in
food were based on types of distillation with trapping using
cold traps or solvent. These methods were not really appropriate for compounds as volatile as furan because evaporation
of solvents used to elute analytes from traps also caused loss of
furan. Modern methods are virtually all based on headspace

gas chromatography with mass spectrometric detection. In this

the food sample is placed in a vial sealed with a septum and
warmed to partition the furan between the food and the air
above it, known as the headspace.
Furan in the air of headspace vial is transferred to a gas
chromatograph (GC) with a heated syringe (Figure 5), with a
transfer tube or with a solid phase microextraction (SPME)
device, which is an absorbent phase on a retractable needle
held in the headspace. Detection is invariably by mass spectrometry operated in the selected ion monitoring mode.
The analysis requires considerable care at various stages.
The food sample must be homogenized in order to obtain a
representative sample. This necessitates stirring, with the
concomitant potential for loss of furan, therefore a brief stirring procedure at low temperature is required. The sample is
heated for approximately 20 min to equilibrate the furan between the sample and the headspace. At this stage the temperature must be low enough to avoid furan formation,
typically 50 1C. A sample of the headspace (approximately
1 ml) is transferred to the GC by means of a heated syringe or
a transfer line. Alternatively, SPME may be used in which furan
is absorbed on to a coated needle and carried to the GC. All of
these methods are easily automated.
GC separation of volatiles including furan can often best
be achieved using a porous layer open tube column. This is a
bonded porous-polymer phase based on polystyrene and
divinylbenzene that is relatively inert and stable to water.
Mass spectrometry is used universally as the furan detector
for GC. The mass spectrum of furan has a relatively intense
molecular ion at m/z 68 and a fragment ion at m/z 39. Furan
can be quantified by using a calibration graph prepared by
standards or by adding a range of known levels of furan to
samples (standard addition procedure).
Correction for the loss of furan in the later stages of the
analysis can be made by adding deuterium labeled furan to
the vial. The deuterated furan has all four hydrogen atoms
replaced by deuterium. It mimics the behavior of the native
furan through the analysis but can be measured independently
by the mass spectrometer as it has a molecular ion at m/z 72.
The labeled furan is unfortunately too expensive to be added
to the food before homogenization unless only a small sample
is taken, but this then runs the risk of getting an unrepresentative sample if the food is not homogeneous.
Recoveries from foods are generally better than 90% with
limits of detection usually better than 0.3 mg kg 1.

Control
There is so far only a limited and incomplete picture of the
levels of furan in foods. There is no evidence so far to suggest

Processing Contaminants: Furan

403

In terms of industrial processing there is limited scope for

action. Particular heating regimes are necessary to reduce
or prevent the microbiological growth. It must also be considered that changes to the heating regime might make the
product unacceptable in terms of taste and appearance and/or
promote the formation of other food processing contaminants
such as acrylamide and chloropropanols.
As many of the formation mechanisms involve oxidation
steps, a promising approach to mitigation is to reduce oxygen
by the use of modified atmospheres during heating. Certain
additives might also reduce oxidation, for example, by scavenging free radicals. Sulfite added to many foods reduces furan
formation significantly.
Furan formation cannot viably be reduced by altering the
formulation of some foods because some precursors and
catalysts such as ascorbic acid, polyunsaturated fatty acid, and
iron are beneficial to health and therefore are desirable food
components.

See also: Foodborne Diseases: Overview of Chemical, Physical,

and Other Significant Hazards. Risk Analysis: Risk Assessment:
Chemical Hazards

Further Reading

Figure 5 Headspace sampling.

that consumers should alter an infant or childs diet or eating

habits to avoid exposure to furan. Also, on account of their
complexity, information is lacking with regard to the formation mechanisms.
However, as furan is believed to be carcinogenic some efforts will undoubtedly be made to reduce consumer exposure,
and various approaches are available.
Reduction of furan formation in food is challenging due to
the large number of precursors in many foods, the requirement to heat process foods to give microbiological safety, and
the necessity to heat food in sealed containers to maintain that
safety during storage before consumption.

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