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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.
H
H
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
399
400
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
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
Regular
Decaffeinated
Espresso
Instant
Powder
Brew
1800
2000
1700
400
24
16
44
8
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
O
OH
HO
O
HO
OH
OH
HO
COOH
OH
HO
Sugar
Aldotetrose
401
Furoic acid
Furan
402
PUFA
HO
O
4-Hydroxy-2-butenal
OH
Furfural
O
Furan
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
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
403
Further Reading
Blank I (2008) Furan in processed foods. In: Gilbert J and Senyuva HZ (eds.)
Bioactive Compounds in Foods, pp. 291322. Bognor Regis: Wiley.
Bolger PM, Tao SS-H, and Dinovi M (2009) Hazards of dietary furan. In: Stadler R
and Lineback DR (eds.) Process-Induced Food Toxicants: Occurrence,
Formation, Mitigation, and Health Risks, pp. 117133. Bognor Regis: Wiley.
Crews C and Castle L (2007) A review of the occurrence, formation, and analysis
of furan in heat-processed foods. Trends in Food Science and Technology 18:
365372.
EFSA (2009) Technical report of EFSA prepared by Data Collection and Exposure
Unit (DATEX) on Monitoring of furan levels in food. The EFSA Scientific
Report 304: 123. http://www.efsa.europa.eu/
Nyman PJ (2009) Furan in thermally processed foods. In: Al-Taher F, Jackson L,
and DeVries JW (eds.) American Chemical Society Symposium Series, Volume
1020. Intentional and Unintentional Contaminants in Food and Feed, pp.
115128. Washington: American Chemical Society.
Vranova J and Ciesarova Z (2009) Furan in food A review. Czech Journal of
Food Science 27: 110.