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Fact sheet:

Polycyclic Aromatic Hydrocarbons


(PAH4)

Version: 09/01/2015

GMP+ International B.V.

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Content

General Summary

Summary of GMP+ products standards for the animal feed sector

More Facts
1. Nature, history and prevalence of polycyclic aromatic hydrocarbons (pah4)
2. Transmission to the environment, plants, animals and humans
3. Diagnose of poisoning
4. Potential hazards and adverse effects
5. Severity of the hazard
6. Standards
7. Analysis methods
8. Control measures
9. References
10. Websites

APPENDIX / APPENDICES

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General Summary

Name: Polycyclic Aromatic Hydrocarbons (PAH4)

code: C35a

Description:

Type: chemical

Severity: high

Control measures: - Air filtration


- Analyse intermediate product(s)
- Analysis of received soya meal
- Calculation model drying
- Drying/Heating (indirect)
- Establish purchasing requirements
- Establish purchasing requirements for fertilizers
- Feed/Food grade lubricants
- Finished product analysis
- History of the mine/source
- Limiting cyclone dust
- Maintenance of machines and safe fuels
- Monitor complete combustion
- Monitor cultivation area (certified)
- No burning of leafs
- No using of burned products
- Plot history
- Product analysis (in oil)
- Production in agricultural areas (in ponds)
- Proper drying conditions
- Received product/raw material analysis
- Safe fuels for the drying process
- Soil history
- Water management

The control measures specified in this fact sheet are all control measures which can be used depending on the
product and/or process step.

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SUMMARY OF GMP+ SPECIFIC FEED SAFETY LIMITS FOR THE ANIMAL FEED SECTOR
Contaminant Product Action limit(1) Rejection limit(1) Source Supplementary requirements Analysis method
Chemical: Toxic substances

C35a Polycyclic Aromatic Oils and fats (excluding palm(kernel)-, 160 g/kg 200 g/kg GMP+ (PAH4=sum of benzo(a)pyrene,
Hydrocarbons (PAH4) coconutoil and products derived thereof) (on fat basis) (on fat basis) benzo(a)anthracene,
benzo(b)fluoranthene and chrysene
Palm(kernel)-, coconutoil and and products 320 g/kg 400 g/kg See the GMP+ D documents: See the GMP+ D
derived thereof) (on fat basis) (on fat basis) - GMP+ D4.14 documents:
- GMP+ D415 - GMP+ D4.14
- GMP+ D415
http://www.gmpplus.org/nl/gmp+_fsa/D-
documenten.php

[1 ] Action limit: A feasible limit agreed in consultation with the sector, supplier or customer. If this limit is exceeded then an investigation into the cause should be undertaken and corrective measures should be
taken to remove or control that cause.

Rejection limit: A feasible limit agreed in consultation with the sector, supplier or customer. If this limit is exceeded then the product is not suitable for use as feed material or animal feed.

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More facts
Chemical name
Polycyclic Aromatic Hydrocarbons (PAHs).
PAHs represent a group of polycyclic aromatic hydrocarbons. For chemical names of
individual PAHs within this group, see Appendix I.

CAS-number
The CAS-numbers of the individual PAHs are shown in Appendix I.

Synonyms
PAHs, for individual PAH synonyms, see Appendix I

In this fact sheet polycyclic aromatic hydrocarbons will be referred to as PAHs. For
individual PAHs abbreviations will be used as indicated in Appendix III.

1. Nature, history and prevalence of polycyclic aromatic hydrocarbons


Polycyclic aromatic hydrocarbons (PAHs) are organic compounds that are composed
of two or more fused aromatic rings. PAHs generally occur in complex mixtures
which may consist of hundreds PAHs. So far about 500 PAHs have been detected in
air (EFSA1, 2008). In figure 1 the chemical structure of the PAH benzo(a)pyrene
(BaP), considered to be the most toxic PAH, is shown.

Figure 1. Chemical structure of benzo(a)pyrene.

The natural and man-made sources in the environment are numerous and the
composition of the PAH mixtures varies with the generating process. PAHs are
primarily formed by incomplete combustion or pyrolysis of organic matter at
high temperatures and during various industrial processes (EFSA1, 2008).

There are two main routes of entry of PAHs in the feed/food chain:
a. Contamination by environmental PAHs that are present in air, soil and water
(WHO1, 2005);
b. Formation during processing (e.g. drying, grilling, smoking, roasting, frying etc.)
(WHO1, 2005). Related to drying, several authors report the presence of PAHs in
fly ash, so deposition of fly ash on food or feed materials, these products are
also of risk (Liu et al., 2000; GMP+3, 2004). However no quantitative data were
found concerning the contribution of fly ash compared to other sources (e.g. fuel
source, direct drying etc.). For more information concerning the hazards of drying
is referred to the Study into drying processes for animal feed materials and
HACCP (GMP+3, 2004).
Another route is contact with petrol, diesel fuels, heating oils, lubricating oils and
engine exhaust.

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As pure chemicals, PAHs generally exist as colourless, white, or pale yellow-green
solids. They have a faint, pleasant odour (ATSDR, 1995). PAHs are chemically
rather inert. Generally they have high melting and boiling points, low vapour
pressure, very low water solubility (Bulder1 et al., 2006), but are readily soluble in
organic solvents and organic acids (EFSA1, 2008) and very soluble in fat. A
classification used is classifying on number of fused aromatic rings: light and
heavy PAHs. PAHs containing up to four fused benzene rings are known as light
PAHs and those containing more than four benzene rings are called heavy PAHs
(Mafra et al., 2010).

Most of the PAHs have no known use except for research purposes. A few PAHs are
used in medicines and to make dyes, plastics, and pesticides. Others are contained
in asphalt used for road construction (ATSDR, 1995).

PAHs toxicity
Concerning the toxicity of PAHs; not every individual PAH is toxic and the toxicity
varies per individual PAH. The CONTAM panel of the EFSA1 (2008) explored
whether a Toxic Equivalent Factor (TEF) approach in the risk characterisation, as
being used in dioxin compounds, of the PAHs could be applied. The conclusion was
that the TEF approach is not scientifically valid because of the lack of data from oral
carcinogenicity studies on individual PAHs, their different modes of action and the
evidence of poor predictability of the carcinogenic potency of PAH mixtures based on
the currently proposed TEF values. Also the use of BaP as the only indicator for the
occurrence of PAHs in feed and food was studied, but it was concluded that BaP is
not a suitable indicator. However, based on the in 2008 available data, the CONTAM
Panel concluded that the use of PAH4 (the PAHs benzo[a]pyrene, chrysene,
benz[a]anthracene and benzo[b]fluroanthene) and PAH8 (the PAH4 and
benzo[k]fluoranthene, benzo[ghi]perylene, dibenz[a,h]anthracene en indeno[1,2,3-
cd]yrene) are the most suitable indicators, with PAH8 not providing much added
value compared to PAH4 (EFSA1, 2008). In 2011 the EU food legislation adopted the
PAH4 method. In 2012 GMP+ International also adopted the PAH4 standard and
new feed limits were formulated, repealing the PAH12 standard using the BaPEQ -
method (GMP+1, 2012).

2. Transmission and likelihood of occurrence

Environment
PAHs are released to the environment through natural and man-made sources.
Natural sources include emissions from volcanoes and forest fires. Man-made
sources provide a greater release volume than natural sources (ATSDR, 1995). Man-
made PAHs are emitted from the processing of coal, crude oil, petroleum and natural
gas, from production of aluminium, iron and steel, from heating in power plants and
homes (oil, gas, charcoal-fired stoves), burning of refuse, wood fires, and from motor
vehicle exhaust (EFSA1, 2008). The composition of PAH emissions vary with the
combustion source (ATSDR, 1995). Hazardous waste sites can be concentrated
sources of PAHs on a local scale as are discharges from industrial plants and
improper disposal of used motor oil (ATSDR, 1995).

PAHs emissions are largely to the atmosphere. The releases are primarily the result
of inefficient combustion. In air they are found bound to particulates and as gases.
Particle-bound PAHs are transported long distances and are removed from the
atmosphere through wet and dry deposition on to soil, water and vegetation (EFSA1,
2008). In the air PAHs can undergo chemical reactions. The most important are
reactions between PAHs adsorbed on the particle surfaces and gases like NO2, O3

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and SO3, and photo oxidation of PAHs irradiated under solar radiation (ATSDR,
1995). Photolysis is the most important factor in the decay of PAHs adsorbed to
particles in the atmosphere. Many PAHs such as BaP are, however, rapidly
destroyed by UV-light (EFSA1, 2008).
In water, PAHs can be volatilised, photolysed, biodegraded and bind to suspended
particles or sediments, or accumulate in aquatic organisms (EFSA1, 2008). The
contribution of the individual processes will depend on the temperature, depth,
pollution status, flow rate and oxygen content of the water. As a result, a process that
is a major degradation process for a particular PAH in a certain surface water may
not be so in another surface water with different water quality. In the United Stated
PAHs have been found in drinking water (ATSDR, 1995) and the WHO reports that
drinking water can be contaminated with PAHs. Fluoranthene being the most comely
detected PAH in drinking water and is associated with coal-tar linings of water
distribution pipes (WHO4, 2003).
PAHs are adsorbed strongly to the organic fraction of soils (WHO2, 1998). They can
be volatilised or biodegraded by, mainly, photolysis and oxidation (EFSA1, 2008).
The ATSDR (1995) states that photolysis and oxidation generally are not considered
to be important processes for the degradation of PAHs in soils but that microbial
metabolism is the major process for degradation. The rate and extent of
biodegradation of PAHs in soil are affected by environmental factors; the organic
content; structure and particle size of the soil; characteristics of the microbial
population; the presence of contaminants such as metals and cyanides that are toxic
to micro-organisms; and the physical and chemical properties of the PAHs (ATSDR,
1995).

Mo1,2 et al. (2005; 2008) studied organic pollutants among which PAHs in fertilizers
used in China. BaP was detected in two fertilizers. No other PAHs data in fertilizers
were found so the extent to which PAHs are present in fertilizers globally is not clear.

Any product of mineral origin that is dried incorrectly: directly dried with
unsuitable fuel, is of risk. Also products of mineral origin originating in a PAHs
contaminated area are of risk due to the PAHs binding capacity of certain minerals.
Besides these products, products of volcanic origin are of risk (e.g. clinoptilolite).
Products of mineral origin can be used as processing aids. During the refining of
crude oils activated coal or bleaching earth can be used to purify the crude oil. In
case the activated coal or bleaching earth is contaminated with PAHs transfer to oil
may be possible. On the other hand activated coal and bleaching earth absorb PAHs
present in the crude oil (FEDIOL, 2010). Adding spent activated coal and
bleaching earth to feed materials may be a PAHs source (see below in section
plants).

Mineral oils, e.g. used as lubricants, can have a significant PAH content (ATSDR,
1995). The International Agency for Research on Cancer (IARC1, 1989) reports that
some marine diesel fuels may contain more than 10% PAHs. Leakage of these
mineral oil / lubricants into feed and food materials during processing is of concern.

Plants
Plants can take up PAHs from soil via the roots or from air via the foliage (e.g.
leaves, fruit); uptake rates are dependent on the concentration, solubility, and
molecular weight of the PAH and on the plant species. The uptake of PAHs from soil
to plants and the subsequent concentration of PAHs in plants is generally quite low
(ATSDR, 1995; WHO2, 1998). Certain plant species may promote PAH degradation
in soils because plant root exudates, rich in organic acids and mineral nitrogen, may
increase the indigenous soil microbial population including PAH-degrading
microorganisms (Wetzel et al., 1997; Binet et al., 2000;Fu et al., 2012).

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Studies show that leaves and to a certain extent other above-ground organs such as
bark, fruits and stems are the main sinks of airborne PAH compounds in plants
(Vaughan 1984; Slaski et al., 2000). The process of interception depends on several
biotic and abiotic factors, including phase state of PAH, leaf surface area, lipid
concentration in plant tissue and ambient temperature (Slaski et al., 2000). Edwards
et al. (1982) studied the uptake and metabolism of anthracene (AN) by soybeans.
Soybeans grown in solution culture and in soil containing AN, assimilated AN and
trans-located it to stems and leaves. Soybeans grown in solution culture and
exposed to an atmosphere containing AN, assimilated the AN through the leaves and
trans-located it to stems and roots.
Species that metabolize PAHs to little or no extent, like algae, accumulate high
concentrations of PAH (WHO2, 1998).

There are two main routes of entry of PAHs in the feed/food chain of vegetal origin:
a. Contamination by environmental PAHs that are present in air, soil and water
(WHO1, 2005). The waxy surface of vegetables and fruits can concentrate low
molecular mass PAH mainly through surface adsorption. The concentrations of
PAH are generally greater on plant surface (peel, outer leaves) than on internal
tissue (EC1, 2002), e.g. on grass, spinach and kale (GMP+2, 2002).
b. Formation during processing (e.g. drying, grilling, smoking, roasting, frying etc.).
High values are reported in grilled and barbecued foods. Direct smoking,
especially using traditional methods, results in contamination with PAHs (WHO1,
2005). Concerning feed, dried feed materials are of risk in case inadequate
drying methods are used especially in high fat products (due to the high
solubility of PAHs in fat and solvents). PAHs contamination is relevant for soy,
sunflower seed, rape seed, citrus and coconut products (GMP+2, 2002).
Products of specific concern are also vegetable oils and fats. The occurrence of
PAH in vegetable oils is mostly related to the drying processes of the seeds and
pulp (e.g. coconut) where combustion gases may come into contact with the
seeds (Halim et al. 2007; EC2, 2001) combined with the high PAHs solubility in
fat and organic solvents. Larsson et al. (1987) found high PAH levels in crude
coconut oil. The levels of PAHs in crude edible oils vary widely and refining
(based on the deodorization step) reduces the concentration of a number of the
lower molecular weight compounds such as FA, while no corresponding effect is
observed for the higher molecular weight PAHs. The level of the latter may be
reduced by treatment with activated coal (Larsson et al., 1987); this refining
method is widely used. Keep in mind that refining of crude oils may lead to the
concentration of PAHs in by-products of the oil refining industry used in feed
materials (e.g. fatty acid distillates originating form physical refining). In fatty
acids originating from chemical refining the PAHs content is believed to be similar
to that of the content in crude oil. Adding of spent activated coal or bleaching
earth, possibly contaminated with PAHs, either by nature or via PAHs
contaminated crude oil, to feed is also of risk. This may be added to oils seed
expeller or meal.
The presence of PAHs in coffee and cocoa beans has also been reported, the
most critical step being the drying of the beans in the respective country of origin
(Houessou et al., 2005). More specifically Misnawi (2012) reports that the
contamination of cocoa beans can occur by drying cocoa on asphalt, on bitumen
in the sun, or by using direct firing drying model. Furthermore, cocoa beans can
be contaminated with PAH during storage and transport in jute or sisal bags
that had been treated with batching oil (Grob et al., 1993).

Bulder1 et al. (2006) reported maximum levels of individual PAHs in feed as shown in
table 1.

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Table 1. Maximum PAH concentration(g/kg) in feed as measured in the Control program animal feed
from 2000-2004.
Feed ACE ACY BAA BAP BBF BKF CHR DBA PHE FLU IDP PYR
Coconut 34.7 2.00 3.17 2.00 1.74 0.38 4.79 0.14 76.1 15.8 1.10 31.8
expeller 8 6 3 7
Citrus 5.30 2.50 7.60 9.60 6.50 2.40 9.20 0.10 0.10 0.10 6.90 0.10

Roughage 13.3 12.9 14.3 9.80 10.1 8.80 15.0 8.40 80.8 157. 8.50 98.2
(dried) 6 4 0 8 7 0 40 0
Roughage 1.20 1.80 8.20 7.90 9.10 4.30 0.72 1.20 3.90 2.70 5.40 1.90
(silage)
Fresh 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 34.5 18.2 0.50 31.6
*
grass 4 2 2
*
= not measured in Control program data gathered from literature

Washing or peeling may remove a significant proportion of the total PAH. Particle
bound high molecular mass PAH which remain on the surface are easily washed off
whereas low molecular mass compounds which are in the vapour phase can
penetrate the waxy layer of fruits and vegetables and are less efficiently removed by
washing (EC1, 2002). Zohair et al. (2006) studied residues several contaminants,
among which PAHs, in vegetables and concluded that peeling carrots and potatoes
was found to remove 52-100% of the contaminant residues depending on crop
variety and the properties of the contaminants. Mind that, when cultivated in
contaminated soil, the peelings might contain PAHs.

In the GMP+ Monitoring database data can be found concerning PAHs in feed
materials of vegetal origin.

Animals
Exposure:
Data concerning oral PAHs exposure of food producing animals are scarce.
Bulder1 et al. (2006) state that the calculated intake of PAHs by cows is 65 to 1000
times higher than the calculated intake by humans. Which PAHs level are included
and the level of exposure level is not known.
Grazing cattle and poultry, which may ingest particulate matter from soil, are
susceptible to contamination by PAH (EC1, 2002). This may also go for other free
range animals. However no data was found concerning PAHs burden in soil and the
exposure of free range animals (e.g. via soil, worms). Sinha et al. (2008) report that
earthworms have been found to remove PAHs from soil however no data were found
the subsequent biodegradation or accumulation in earthworms.

Absorption:
The absorption of PAHs from the diet is determined by the size and the lipophilicity of
the molecule, the presence of bile in the digestive tract, the dose ingested and the
lipid content of the diet (EFSA1, 2008). Increasing lipophilicity tends to increase
absorption, whereas increasing molecular weight tends to decrease it (Baars et al.,
2001). This is confirmed in an experiment of Laurent et al. (2001), studying the
absorption of radiolabelled BaP and PHE following oral administration to pigs in a
lipophilic milieu (via milk). The results in this experiment suggested that PAH
absorption was most likely related to fat absorption. Hoogenboom et al. (2005), cited
in Bulder1 et al. (2006), concluded from his study that the heavier PAHs are
apparently not absorbed from the gastro-intestinal tract. Absorption of PAHs from the
gastro-intestinal tract also appears to vary per animal species.
Generally, absorption after oral exposure appears to be 50% (Baars et al., 2001).
Cavret et al. (2003) fed pigs milk containing radiolabelled BaP or PHE and found
absorption rates of 30.5% and 86.1%, respectively. Following a single oral
administration in lactating goats, absorption of PHE and PY was about 75%, whereas

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absorption was 12% for BaP (Grova1 et al., 2002; Lapole et al., 2007 as cited by
EFSA1, 2008).

Distribution:
PAH are widely distributed and are found in almost all internal organs, but particularly
those rich in lipids (WHO2, 1998). The rate of distribution of PAHs can be influenced
by the presence of other (fatty) compounds that may enter the body at the same time
with PAHs. They tend to be stored mostly in the kidneys, liver, and fat (ATSDR,
1995). The gastrointestinal tract also contains high levels of hydrocarbon and
metabolites (WHO2, 1998). Smaller amounts are stored in the spleen, adrenal
glands, and ovaries (ATSDR, 1995). The organs rich in adipose tissue act as depots
from which material is slowly released (EC1, 2002).
Studies in pregnant mice and rats have shown that certain PAHs, including BaP,
were widely distributed in maternal tissues and were detected in foetuses showing
that they crossed the placenta (EC1, 2002). The ATSDR (1995) states that placental
transfer of PAHs appears to be limited, and therefore, foetal levels are not as high as
maternal levels.

Metabolism:
A major part of the PAHs ingested, are metabolised (EFSA1, 2008). The metabolism
of PAH is complex. Most metabolism results in detoxification, but some PAH are
activated to DNA-binding species, which can initiate tumours (WHO2, 1998). Grova2
et al. (2006) studied the effect of oral exposure to PAHs on goat's milk contamination
and found PAH metabolites in goat milk.

Excretion:
A major part of the PAHs ingested, are metabolised and excreted. Most of the
metabolites are excreted into the bile and then subsequently eliminated in the
faeces. A smaller proportion is excreted in urine (EFSA1, 2008).
PAHs are excreted in milk as parent compounds or as metabolites (Grova1 et al.,
2002; Bulder2 et al., 2008). Grova1 et al. (2002) found a low milk transfer (1.6% PHE
and 1.9% PY) and BaP was not significantly detected in milk.
Fournier et al. (2010) studied the transfer kinetics of PAHs in laying hens to egg yolk.
Of the three administered PAHs (PHE, PY and BaP) all three PAHs were recovered
in yolks, mainly as metabolites, indicating an active biotransformation of these
compounds in hens. The amounts assayed demonstrated that a small proportion
(less than 1%) of the PAHs ingested was excreted via egg yolk.

Humans via animal products


Meat, milk, poultry and eggs will normally not contain high levels of PAHs due to
rapid metabolism of these compounds in the species of origin (EC1, 2002). Grova2 et
al. (2006) state that in spite of the absence of a significant transfer of parent PAHs to
milk, PAH metabolites appeared in milk raises questions of their impact on human
health.

Some marine organisms, such as mussels and lobsters are known to adsorb and
accumulate PAHs from water, which may be contaminated, for example by oil spills
(EC1, 2002). Muscle meat of fish (other than smoked) may also contain high PAH
levels (EFSA1, 2008), however the WHO2 (1998) reports that fish are known to
metabolise PAHs and accumulate little to no PAHs. The presence of PAHs in fish
meal and fish oil is demonstrated in GMP+ Monitoring database.
No PAHs transfer data in animal fat were found. However based on the lipophilic
characteristics PAHs may be present although extensive PAHs metabolism in
animals is reported.

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Besides the presence of transfer levels of PAHs in products of animal origin,
processing techniques can influence the levels of PAHs. Since these do not origin
from animal feed, the processing technique will only be addressed briefly.
a. Traditional commercial smoking techniques, in which smoke from incomplete
wood burning comes into direct contact with the product, can lead to its
considerable contamination with various PAHs if the process is not adequately
controlled (EFSA1, 2008).
b. Considerable differences in the PAH levels can be found in grilled products.
Depending on the heat source as well as the type and geometry of the grill. The
fat content also influences the PAHs levels. Higher levels of fat can result in
higher PAHs levels. This is especially important for home cooking practices
(EFSA1, 2008).
c. Also by inadequate drying, roasting, frying or heating techniques, products of
animal origin are contaminated with PAHs (EFSA1, 2008).
So products of animal origin which are inadequately smoked, grilled, dried,
roasted, fried or heated are of risk. These may be used in animal feed.

In the GMP+ Monitoring database data can be found concerning PAHs in feed
materials of animal origin.

Humans
Exposure:
The EFSA1 (2008) calculated the median dietary BaP and PAH4 exposure across
European countries both for mean and high dietary consumers and varied between:
235 ng/day (3.9 ng/kg bodyweight per day) and 389 ng/day (6.5 ng/kg
bodyweight per day) respectively for BaP alone;
1168 ng/day (19.5 ng/kg bodyweight per day) and 2068 ng/day (34.5 ng/kg
bodyweight per day) respectively for PAH4 (being BaP, CHR, BaA and BbFA);
The EFSA states that food can be contaminated from environmental sources,
industrial food processing and from home food processing (e.g. drying / barbecuing).
High consumption of certain home barbecued foods may lead to an exposure to
PAHs that considerably exceeds the above estimated background dietary exposure
to these compounds (EFSA1, 2008).
The contribution of products of animal origin contaminated via PAH feed transfer is
not mentioned in this report. No data were found concerning the PAH transfer via
feed to products of animal origin and the consequent contribution to human dietary
PAH exposure.

Absorption:
Absorption of BaP following ingestion is low in humans (ATSDR, 1995). However in
an experiment of Hecht et al. (1979), analysing faeces for BaP after consumption of
charcoal-broiled beef by humans, BaP was not detected in the faeces, suggesting
that most of the ingested BaP was absorbed. No other data were found concerning
the absorption of PAHs by humans.

Distribution:
The WHO2 (1998) reports that it can be inferred from the available information on the
total human body burden that PAHs do not persist in the body and that turnover is
rapid. Madhavan and Naidu (1995) studied the presence PAHs in placenta, maternal
blood and umbilical cord blood of Indian women. The umbilical cord blood showed
the relatively highest levels of BaP, CHR and dibenzo[a,c]anthracene. The authors
concluded that developing foetuses and new-born infants were exposed to these
PAHs, probably from the maternal diet. In addition the EC1 (2002) also states that it
is reasonable to assume that because of their lipid solubility, most PAH are likely to
pass into the embryo and foetus.

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Metabolism:
The lipophilicity of PAHs enables them to readily penetrate cellular membranes and
remain in the body indefinitely. However, the metabolism of PAHs renders them
more water-soluble and more extractable. Metabolism of PAHs occurs in all tissues.
The metabolic process involves several possible pathways with varying degrees of
enzyme activities (ATSDR, 1995; WHO1, 2005).

Excretion:
PAHs and PAHs metabolites are excreted via the urine and faeces. Conjugates are
excreted in the bile can be hydrolysed by enzymes of the gut flora and reabsorbed
(WHO2, 1998). In a study by Madhaven and Naidu (1995) PAHs (BaP, CHR and
dibenzo[a,c]anthracene) were found in breast milk.

3. Diagnose of poisoning

Animals
Most of the metabolised are excreted into the bile as metabolites and then
subsequently eliminated in the faeces. A smaller proportion is excreted in urine
(EFSA1, 2008). PAHs form DNA adducts that can be measured in body tissues or
blood (ATSDR, 1995). 1-Hydroxypyrene could be considered as a marker of
ruminant exposure to polycyclic aromatic hydrocarbons (Lapole et al., 2007).
In addition feed can be analysed for PAHs.

Humans
The most prominent biomarker of exposure to PAHs in humans is the level of one or
more PAH metabolites is urine. The EFSA1 (2008) refer to studies stating that 1-
hydroxypyrene, hydroxynaphtalenes and hydroxyphenanthrenes are the PAH
metabolites most widely accepted as reliable biomarkers for internal PAH exposure
because they are excreted in urine at substantial extent, making possible then
monitoring by analytical methods currently available. However these studies are
related to inhalation or dermal exposure.
PAHs form DNA adducts which can be measured in body tissues or blood in humans
(ATSDR, 1995).
In addition food can be analysed for PAHs.

4. Potential adverse effects

Environment
No data were studied

Animals
Grazing cattle and poultry, which may ingest particulate matter from soil are
susceptible to contamination by PAH (EC1, 2002). This may also go for other free
range animals, however no scientific data were found to confirm this.

No data was found concerning adverse effects in food producing animals. Data
below concerns laboratory animals (rodents).

There is limited or no evidence on the reproductive toxicity of individual PAHs, other


than BaP, in animals (WHO1, 2005). Reproductive and developmental effects
(reduced number of pregnancies, embryo-lethality, reduced foetal weight and
malformations) are reported in response to BaA, BaP, DBahA (WHO3, 2006).

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The WHO3 (2006) also reports several other adverse effects, being increased organ
weight, decreased body weight, damage to kidney and liver, haematological
changes, immunotoxicity and death as end effect.

The carcinogenicity of PAHs administered by oral routes has been assessed in


studies. In most studies, the site of tumour development was related to the route of
administration, e.g. gastric tumours after oral administration. Tumours at other sites
have also been observed (WHO3, 2006; EFSA1, 2008; IARC2, 2010). The IARC3
(2012) has concluded that there is sufficient evidence for the carcinogenicity of BaP
in experimental animals.

In Appendix II the potential adverse effects of PAHs in animals are shown. For
toxicity data, see Appendix III.

Humans
In 2002 the Scientific Committee on Food (EC1, 2002) stated that there were almost
no published studies on health effects in humans following oral exposure to PAHs. In
the majority of studies humans had been occupationally exposed to PAHs via
inhalation and in a few studies the exposure had been dermal. Recently the EFSA1
(2008), as did the WHO2 (2005) and IARC3 (2012), again concluded that the
available evidence regarding human oral exposure to PAHs was indirect and did not
include data on quantitative exposure, and thus is not suitable for use in the risk
assessment for PAHs. The IARC3 (2012) however did conclude that BaP is
carcinogenic to humans despite the lack of epidemiological data. The strong and
extensive experimental evidence for the carcinogenicity of BaP in many animal
species, supported by the consistent and coherent mechanistic evidence from
experimental and human studies provide biological plausibility to support the overall
classification of BaP as a human carcinogen (IARC2, 2012).

In Appendix II the potential adverse effects of PAHs in animals are shown. For
toxicity data, see Appendix III.

5. Severity of the potential adverse effects


The severity of contamination of feed materials with PAHs is based on the worst
case scenario, as shown in table 2, and is based upon the potential adverse effects
stated in chapter 4 and Appendix II.

The severity of PAH toxicosis in animals is classified as high because:


Reproductive and developmental effects (reduced number of pregnancies,
embryo-lethality, reduced foetal weight and malformations) are reported in
response to BaA, BaP, DBahA (WHO3, 2006);
The WHO3 (2006) reports death as end effect;
The IARC3 (2012) has concluded that there is sufficient evidence for the
carcinogenicity of BaP in experimental animals

The severity of PAH toxicosis in humans is classified as high because:


BaP is carcinogenic to humans (IARC3, 2012).

Table 2. Severity of certain PAHs.


Severity
Low Medium High
Animals x

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Humans x

6. Legislation and standards


No feed data were found.

7. Methods of analysis
Sample preparation and analytical procedures play an important role for a reliable
determination of PAHs in foodstuffs (EFSA1, 2008) and consequently also in feed.
Containers shall be rinsed with high purity acetone or hexane before use to minimise
the risk of contamination. Wherever possible, apparatus and equipment coming into
contact with the sample shall be made of inert materials such as aluminium, glass or
polished stainless steel. Plastics such as polypropylene or polytetrafluoroethylene
(PTFE) shall be avoided because the PAHs can adsorb onto these materials (EFSA1,
2008). Losses of PAHs may also occur if the sample is exposed to light and high
temperatures during the sample collection and storing, or PAHs react with other
matrix substances during a long-term storage. Exposure to tobacco smoke may
increase the PAH levels in the sample (WHO3, 2006).

The extraction method used for extracting PAHs from food or feed samples greatly
depends on the nature of the matrix. Nowadays the two main analytical techniques
for determining PAHs in food or feed materials are high performance liquid
chromatography (HPLC) coupled to a fluorescence detector (FLD) and gas
chromatography-mass spectrometry (GC-MS) (GMP+1, 2012; EFSA2, 2008).
Analysis should include the PAH4 set of markers. Both of these methods are
sufficiently sensitive for determining PAH concentrations usually found in foods.
Earlier HPLC with an ultraviolet (UV) or a photo-diode array (PDA) detector and GC
with a flame ionisation detector (FID) were also methods often applied but today they
are not state of the art anymore due to their poorer selectivity and sensitivity.
Levels of detection (LODs) and recoveries for PAHs are compound, matrix and
method dependent. The LODs for PAHs typically range from 0.1 to 1 g/kg.
However, for some PAHs lower and higher LODs, even up to 20 g/kg, are
determined (EFSA2, 2008).

8. Possible control measures


The HACCP system should be used to assess the risk of radionuclides in feed and
consequently the control measures needed to control this risk. All parts in the feed
and food chain should be included, starting from cultivation or husbandry. These
specific control measures are included in the appendices:
Cultivation, harvesting, processing, transport and storage on farm, see Appendix
IV;
Husbandry, see Appendix V;
Transport, see Appendix VI;
Storage and transhipment, see Appendix VII;
Processing of feed, see Appendix VIII.

The possible control measures should focus on products with a higher risk to contain
PAHs are summarised in table 3. Products derived from the products in table 3
should also be considered as risk products.

Table 3. Products with a higher risk to contain PAHs.

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Products exposed to incomplete combustion or pyrolysis of organic matter at high
temperatures (e.g. during drying, grilling, smoking, roasting, frying);
Products that are dried incorrectly: e.g. directly dried with unsuitable fuel;
Products in general
Smoked products;
Products originating in a PAHs contaminated area;
Products contaminated with PAHs containing mineral oils, e.g. used as lubricants and
diesel fuels, petrol, heating oils;
Products in direct contact with PAHs contaminated engine exhaust;
Products in direct contact with jute or sisal bags that has been treated with PAHs
contaminated batching oil;
Products containing PAHs contaminated fly ash;
Drinking water;

Products of volcanic origin (e.g. clinoptilolite);


of mineral
Products

Activated coal or bleaching earth;


origin

Spent activated coal and bleaching earth

Algae;
Products of vegetal origin, in general, originating in a PAHs contaminated area, via
atmospheric deposition or soil contamination, outer leaves and peel;
Specific products of vegetal origin

Specific products of vegetal origin originating in a PAHs contaminated area, via


atmospheric deposition or soil contamination, e.g. grass, kale, spinach;
Products of vegetal origin containing adherent soil contaminated with PAHs;
Inadequately dried products of vegetal origin, e.g. cereal grains, forage and roughage,
oilseeds (e.g. sunflower seed, rape seed, soy bean), coconut products, coffee and cocoa
beans;
High-fat products of vegetal origin, e.g. crude vegetal oils and fats, specifically crude
coconut oil;
Refined vegetal oils and fats processed with PAHs contaminated activated coal or
bleaching earth;
By-products of the vegetable oil and fats refinery, specifically fatty acid distillates;
Products of vegetal origin containing spent activated coal or bleaching earth, e.g. oilseed
expeller or meal;
Products of vegetal origin containing spent activated coal or bleaching earth, e.g. oilseed
expeller or meal;

Marine organisms, e.g. mussels and lobsters;


products of

Inadequately dried products of animal origin, e.g. fish meal;


Specific

animal
origin

High-fat products of animal origin, e.g. crude fish oil.

Grazing cattle and poultry, which may ingest particulate matter from soil are
susceptible to contamination by PAH (EC1, 2002). This may also go for other free
range animals, however no scientific data were found to confirm this.

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9. References
1. ATSDR (Agency for Toxic Substances & Disease Registry), Toxicological profile
for polycyclic aromatic hydrocarbons (PAHs), 1995
2. Baars et al. (RIVM), Re-evaluation of human-toxicological maximum permissible
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4. Bulder1 et al. (RIKILT), Initial risk assessment of polycyclic aromatic
hydrocarbons (PAHs) in feed (materials), Addendum to Report: 03/0027745,
Report 2006.001, 2006
5. Bulder2 et al. (RIKILT), Risk assessment of Nickel, Mineral Oils, Polycyclic
Aromatic Hydrocarbons and Volatile Organic Compounds in animal feed
materials, Report 2007.020, 2008
6. Cravet et al., Intestinal absorption of 14C from 14C-phenanthrene, 14C-
benzo[a]pyrene and 14C-tetrachlorodibenzo-para-dioxin: approaches with the
Caco-2cell line and with portal absorption measurements in growing pigs,
Reproduction, Nutrition Development, Volume 43(2), 2003, pages 145-154
7. EC1 (European Commission), Opinion of the Scientific Committee on Food on the
risks to human health of polycyclic aromatic hydrocarbons in food, 2002
8. EC2 (European Commission), Outcome of the expert group meeting on 3 October
on ways to prevent contamination of olive residue oil and other oils with polycyclic
aromatic hydrocarbons (PAH), Summary record of the 85th meeting of the
Standing Committee on Foodstuffs, Agenda item 9, 25th October 2001
9. Edwards et al., Uptake and metabolism of 14C anthracene by soybean (Glycine
max), Environmental and Experimental Botany, Volume 22(13), 1982, pages 349-
357
10. EFSA1, Polycyclic aromatic hydrocarbons in food: Scientific opinion of the Panel
on Contaminants in the Food Chain, The EFSA Journal 724, 2008
11. EFSA2, Findings of the EFSA Data Collection on Polycyclic Aromatic
Hydrocarbons in Food, A Report from the Unit of Data Collection and Exposure
on a Request from the European Commission, Revision 1, 2008
12. FEDIOL (The European vegetable oil and proteinmeal industry), Chain risk
assessment coconut oil products for feed application in the EU, December 2010
13. Fournier et al., Transfer kinetics to egg yolk and modelling residue recovered in
yolk of readily metabolized molecules: Polycyclic aromatic hydrocarbons orally
administered to laying hens, Chemosphere, Volume 78(8), 2010, pages 1004-
1010
14. Fu et al., Effects of alfalfa and organic fertilizer on benzo[a]pyrene dissipation in
an aged contaminated soil, Environmental Science and Pollution Research
International, Volume 19(5), 2012, pages 1605-1611
15. GMP+1 International, Elaboration of limit values for polycyclic aromatic
hydrocarbons in oil for feed based on the PAH4 methodology, GMP+ D4.12,
2012
16. GMP+2 International, Minimum specifications for feed fats, Supporting document
of GMP+ FSA Scheme, GMP+ D4.12, 2002
17. GMP+3 International, Study into drying processes for animal feed materials and
HACCP, GMP+ D4.4, 2004
18. GMP+4 International, GMP+ B6, Feed materials cultivation, GMP+ Feed Safety
Assurance scheme, 2013
19. GMP+2 International, GMP+ B1, Production, trade and services, GMP+ Feed
Safety Assurance scheme, 2013
20. GMP+3 International, GMP+ B4, Transport, GMP+ Feed Safety Assurance
scheme, 2013

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Version: 09/01/2015 GMP+ International B.V.
21. GMP+4 International, GMP+ B4.1, Road transport, GMP+ Feed Safety Assurance
scheme, 2013
22. GMP+5 International, GMP+ B4.2, Affreightment of short sea shipping and inland
waterway transport, GMP+ Feed Safety Assurance scheme, 2013
23. GMP+6 International, GMP+ B4.3, Short sea shipping and inland waterways
transport, GMP+ Feed Safety Assurance scheme, 2013
24. GMP+7 International, GMP+ B4.4, Sea transport and affreightment, GMP+ Feed
Safety Assurance scheme, 2013
25. GMP+8 International, GMP+ B4.5, Rail transport and affreightment, GMP+ Feed
Safety Assurance scheme, 2013
26. GMP+9 International, GMP+ B3, Trade, collections and storage & transhipment,
GMP+ Feed Safety Assurance scheme, 2013
27. GMP+10 International, GMP+ B2, Quality control of feed materials, GMP+ Feed
Safety Assurance scheme, 2013
28. Grob et al., Contamination of hazelnuts and chocolate by mineral-oil from jute
and sisal bags. Zeitschrift Lebensmittel-Untersuchung und -Forschung 197(4),
1993, pages 370-374.
29. Grova1 et al., 14C-milk, urine and faces excretion kinetics in lactating goats after
an oral administration of 14C-polycyclic aromatic hydrocarbons, International
Dairy Journal, Volume 12(12), 2002, pages 1025-1031
30. Grova2 et al., Effect of oral exposure to polycyclic aromatic hydrocarbons on
goat's milk contamination, Agronomy for Sustainable Development, Volume
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31. Halim et al., Determination of benzo[a]pyrene in vegetable oils, Journal of Oil
Palm Research, Volume 19, 2007, pages 428-434
32. Hecht et al., Analysis of faeces for benzo[a]pyrene after consumption of charcoal-
broiled beef by rats and humans, Food and Cosmetics Toxicology, Volume 17(3),
1979, pages 223-227
33. Hoogenboom (cited in Bulder1 et al., 2006), Behaviour of polyhalogenated and
polycyclic aromatic hydrocarbons in food- producing animals, In: Reviews in Food
and Nutition Toxicity, Preedy and Watson (ed.), Volume 2, 2005, pages 269-299
34. Houessou et al., Determination of polycyclic aromatic hydrocarbons in coffee
brew using solid-phase extraction, Journal of Agricultural and Food Chemistry,
Volume 53(4), 2005, pages 871-879
35. IARC1 (International Agency for Research on Cancer), Occupational exposures in
petroleum refining; crude oil and major petroleum fuels, Volume 45, 1989
36. IARC2 (International Agency for Research on Cancer), Some non-heterocyclic
Polycyclic Aromatic Hydrocarbons and Some Related Exposures, Volume 92,
2010
37. IARC3 (International Agency for Research on Cancer), Chemical agents and
related occupations, IARC Monographs, Volume 100F, 2012
38. JECFA, Benzo[a]pyrene, Summary of Evaluations Performed by the Joint
FAO/WHO Expert Committee on Food Additives, 2001
39. Lapole et al. (cited in EFSA1, 2008), Milk and urine excretion of polycyclic
aromatic hydrocarbons and their hydroxylated metabolites after a single oral
administration in ruminants, Journal of Dairy Science, Volume 90(6), 2007, pages
2624-2629
40. Larsson et al., Polycyclic aromatic hydrocarbons in crude and deodorized
vegetable oils, Journal of the American Oil Chemists Society, Volume 64(3),
1987, pages 365-370
41. Laurent et al., Milk-blood transfer of 14C-tagged polycyclic aromatic hydrocarbons
(PAHs) in pigs, Journal of Agricultural and Food Chemistry, Volume 49(5), 2001,
pages 2493-2496

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Version: 09/01/2015 GMP+ International B.V.
42. Liu et al. Investigation of polycyclic aromatic hydrocarbons in fly ash from
fluidized bed combustion systems, Environmental Science and Technology,
Volume 23, 2000, pages 2273-2279
43. Madhaven and Naidu, Polycyclic aromatic hydrocarbons in placenta, maternal
blood, umbilical cord blood and milk of Indian women, Human and Experimental
Toxicology, Volume 14(6), 1995, pages 503-506
44. Mafra et al., Polycyclic aromatic hydrocarbons (PAH) in olive oils and other
vegetable oils; potential for carcinogenesis, In: Olives and olive oil in health and
disease prevention, Reedy and Watson (ed.), 2010
45. Misnawi, Effect of cocoa bean drying methods on polycyclic aromatic
hydrocarbons contamination in cocoa butter, International Food Research
Journal, Volume 19(4) 2012, pages 1589-1594
46. Mo1 et al., Preliminary determination of organic pollutants in agricultural
fertilizers, Huan Jing Ke Xue, Volume 26(3), 2005, pages 198-202
47. Mo2 et al., Occurrence of priority organic pollutants in the fertilizers, China,
Journal of Hazardous Materials, Volume 152(3), 2008, pages 1208-1213
48. Sinha et al., Converting wasteland into wonderland by earthworms a low-cost
natures technology for soil remediations: a case study of vermiremediation of
PAHs contaminated soil, Environmentalist, Volume 28, 2008, pages 466-475
49. Slaski et al., Evaluation of polycyclic aromatic hydrocarbon (PAH) accumulation
in plants, Report prepared for the Air Research Users Group, Alberta
Environment, 2000
50. US EPA1 (Environmental Protection Agency), Acenaphthene, Integrated Risk
Information System, 1990
51. US EPA2 (Environmental Protection Agency), Fluorene, Integrated Risk
Information System, 1990
52. US EPA3 (Environmental Protection Agency), Fluoranthene, Integrated Risk
Information System, 1990
53. US EPA4 (Environmental Protection Agency), Pyrene, Integrated Risk Information
System, 1990
54. Vaughan, State of Research: Environmental pathways and food chain transfer,
Environmental Health Perspectives, Volume 54, 1984, pages 353-371
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in soil, In: Phytoremediation of soil and water Contaminants, 1997, pages 254-
262
56. WHO1, Evaluation of certain food contaminants: the sixty-fourth meeting of the
Joint FAO/WHO Expert Committee on Food Additives (JECFA), Technical Report
Series 930, 2005
57. WHO2, Selected and non-heterocyclic polycyclic aromatic hydrocarbons,
Environmental Health Criteria 202, 1998
58. WHO3, Safety evaluation of certain contaminants in food: polycyclic aromatic
hydrocarbons, WHO Food Additives Series 55, 2006, pages 563-743
59. WHO4, Polynuclear aromatic hydrocarbons in drinking-water, Background
document for development of WHO Guidelines for Drinking-water Quality, 2003
60. Zohair et al., Residues of polycyclic aromatic hydrocarbons (PAHs),
polychlorinated biphenyls (PCBs) and organochlorine pesticides in organically-
farmed vegetables, Chemosphere, Volume 63(4), 2006, pages 541-553

10. Websites
1. http://www2.gmpplus.org/lmbinaries/gmp_d4.15_-
_uk_transfer_of_polycyclic_aromatic_hydrocarbons_in_oil_for_feed_to_edible_fo
od_commodities_10117.pdf
2. http://www.efsa.europa.eu/en/efsajournal/doc/724.pdf
3. http://www.efsa.europa.eu/en/efsajournal/doc/33r.pdf

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4. http://www.atsdr.cdc.gov/toxprofiles/tp69.pdf
5. http://whqlibdoc.who.int/publications/2006/9241660554_PAH_eng.pdf

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Appendix I Some Polycyclic Aromatic Hydrocarbons.
Common name IUPAC name Abbreviation CAS nr. Molecular formula
Acenaphthene Acenaphthene AC; ACP 83-32-9 C12H10
Acenaphthylene Acenaphthylene ACL; ACY 208-96-8 C12H8
Acepyrene 3,4-Dihydrocyclopenta[cd]pyrene 25732-74-5 C18H12
Anthanthrene Dibenzo[def,mno]chrysene ATR 191-26-4 C22H12
Anthracene Anthracene AN; ANT 120-12-7 C14H10
11H-Benz[b,c]aceanthrylene 11H-Benz[b,c]aceanthrylene 202-94-8 C19H12
Benz[j]aceanthrylene Benz[j]aceanthrylene 202-33-5 C20H12
Benz[l]aceanthrylene Benz[l]aceanthrylene 211-91-6 C12H10
Benz[a]anthracene Benz[a]anthracene BaA 56-55-3 C12H10
Benzo[b]chrysene Benzo[b]chrysene 214-17-5 C22H14
Benzo[g]chrysene Benzo[g]chrysene 196-78-1 C22H14
Benzo[a]fluoranthene Benzo[a]aceathrylene 203-33-8 C20H12
Benzo[b]fluoranthene Benz[e]acephenanthrylene BbFA; BbF 205-99-2 C20H12
Benzo[ghi]fluoranthene Benzo[ghi]fluoranthene BghiF 203-12-3 C18H10
Benzo[j]fluoranthene Benzo[j]fluoranthene BjFA; BjF 205-82-3 C20H12
Benzo[k]fluoranthene Benzo[k]fluoranthene BkFA; BkF 207-08-9 C20H12
Benzo[a]fluorene 11H-Benzo[a]fluorene BaFL 238-84-6 C17H12
Benzo[b]fluorene 11H-Benzo[b]fluorene BbFL 243-17-4 C17H12
Benzo[c]fluorene 7H-Benzo[c]fluorene BcFLBcL 205-12-9 C17H12
Benzo[ghi]perylene Benzo[ghi]perylene BghiP; BgP 191-24-2 C22H12
Benzo[c]phenanthrene Benzo[c]phenanthrene BcPH 195-19-7 C18H12
Benzo[a]pyrene Benzo[a]pyrene BaP 50-32-8 C20H12
Benzo[e]pyrene Benzo[e]pyrene BeP 192-97-2 C20H12
Chrysene Chrysene CHR 218-01-9 C18H12
Coronene Coronene COR 191-07-1 C24H12
4H-Cyclopenta[def]chrysene 4H-Cyclopenta[def]chrysene 202-98-2 C19H12
Cyclopenta[cd]pyrene Cyclopenta[cd]pyrene CPP 27208-37-3 C18H10
5,6-Cyclopenteno-1,2-benzanthracene 2,3-Dihydro-1H-benzo[a]cyclopent[h]anthracene 7099-43-6 C21H16
Dibenz[a,c]anthracene Bezno[b]triphenylene 215-58-7 C22H14
Dibenz[a,h]anthracene Dibenz[a,h]anthracene DBahA; DhA 53-70-3 C22H14
Dibenz[a,j]anthracene Dibenz[a,j]anthracene 224-41-9 C22H14
Dibenzo[a,e]fluroanthene Dibenz[a,e]aceanthrylene 5385-75-1 C24H14
13H-Dibenzo[a,g]fluorene 13H-Dibenzo[a,g]fluorene 207-83-0 C21H14
Dibenzo[h,rst]pentaphene Dibenzo[h,rst]pentaphene 192-47-2 C28H16
Dibenzo[a,e]pyrene Naphtho[1,2,3,4-def]chrysene DBaeP; DeP 192-65-4 C24H14
Dibenzo[a,h]pyrene Dibenzo[b,def]chrysene DBahP; DhP 189-64-0 C24H14

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Common name IUPAC name Abbreviation CAS nr. Molecular formula
Dibenzo[a,i]pyrene Benzo[rst]pentaphene DBaiP; DiP 189-55-9 C24H14
Dibenzo[a,l]pyrene Dibenzo[def,p]chrysene DlP 191-30-0 C24H14
Dibenzo[e,l]pyrene Dibenzo[fg,op]naphthacene DBalP 192-51-8 C24H14
1,2-Dihydroaceanthrylene 1,2-Dihydroaceanthrylene 641-48-5 C16H12
1,4Dimethylphenanthrene 1,4Dimethylphenanthrene 22349-59-3 C16H14
Fluoranthene Fluoranthene FA; FLT 206-44-0 C16H10
Fluorene 9H-Fluorene FL; FLR 86-73-7 C13H10
Indeno[1,2,3-cd]pyrene Indeno[1,2,3-cd]pyrene IP; IcP 193-39-5 C22H12
1-Methylchrysene 1-Methylchrysene 3351-28-8 C19H14
2-Methylchrysene 2-Methylchrysene 3351-32-4 C19H14
3-Methylchrysene 3-Methylchrysene 3351-31-3 C19H14
4-Methylchrysene 4-Methylchrysene 3351-30-2 C19H14
5-Methylchrysene 5-Methylchrysene 5-MCH; 5MC 3697-24-3 C19H14
6-Methylchrysene 6-Methylchrysene 1705-85-7 C19H14
2-Methylfluoranthene 2-Methylfluoranthene 33543-31-6 C17H12
3-Methylfluoranthene 3-Methylfluoranthene 1706-01-0 C15H12
1-Methylphenanthrene 1-Methylphenanthrene 832-69-9 C24H14
Naphtho[1,2-b]fluoranthene Indeno[1,2,3,-hi]chrysene 1-MPH 111189-32-3 C24H14
Naphtho[2,1-a]fluoranthene Dibenz[a,j]aceanthrylene 203-20-3 C24H14
Naphtho[2,3-e]pyrene Dibenzo[de,qr]naphthacene 193-09-9 C24H14
Perylene Perylene PE 198-55-0 C20H12
Phenanthrene Phenanthrene PHE 85-01-8 C14H10
Picene Picene 213-46-7 C22H14
Pyrene Pyrene PY; PYR 129-00-0 C16H10
Triphenylene Triphenylene TRI 217-59-4 C18H12

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APPENDIX II Potential adverse effect of certain PAHs

1,2 1,2 1,2 1,2 2 2


PAHs Death Carcinogen Mutagen Reproductive Internal injury Neurological Immunological Organs
2
(physical effect
contamination)
1,2

Animals x x x x x

Humans x (BaP)

2 2 2 2
PAHs Dermal and Respiratory Musculo- Cardiovascular Gastrointestinal Hematological Endocrine Body weight
2 2
ocular skeletal
Animals x x

Humans

1
This potential adverse effect is classified as high severity for animals
2
This potential adverse effect is classified as high severity for humans

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APPENDIX III Toxicity data of certain PAHs

NOAEL (mg/kg BW) ADI (mg/kg BW) LD50 (mg/kg BW)


Naphthalene 100-500 (mice) (WHO2,
1998)
2700 (rats) (WHO2, 1998)
Anthracene 18000 (mice) (WHO2, 1998)
Benzo(a)pyrene 3 (rat) (EC1, 2002)1 PTWI* not established >1600 (mice) (WHO2, 1998)
(JECFA, 2001)
Fluoranthene 125 (mice) (US EPA3)4 2000 (rat) (WHO2, 1998)
Phenanthrene 700 (mice) (WHO2, 1998)
Acenaphthene 175 (mice) (US EPA1)2
Fluorene 125 (mice) (US EPA2)3
Pyrene 75 (mice) (US EPA4)5
*
PTWI = provisional tolerable weekly intake
1
during 90 days, NOAEL for effect on the liver and immunotoxicity
2
during 90 days, NOAEL for hepatotoxicity
3
during 13 weeks, NOAEL for haematological effects
4
during 13 weeks, NOAEL for nephropathy, increased liver weights, haematological alterations, and
clinical effects
5
during 13 weeks, NOAEL for renal effects

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APPENDIX IV PAHs control measures: cultivation, harvesting, processing,
transport and storage of feed on farm.
Specific requirements and control measures related to feed ingredient cultivation are
stated in the GMP+ B6 standard (GMP+4, 2013). This standard should be complied
with. Additional recommendations for general control measures are stated below in
this appendix.

Cultivation, harvesting, processing, transport and storage on farm

Use the HACCP system to assess the risk of PAHs in feed. Besides others, the
following items should be addressed:
Determine the history and the present situation in the cultivation area and focus
on PAHs emitting activities. E.g. industrial power generation, production of
aluminium, iron and steel, petroleum catalytic cracking and production of asphalt,
coal tar and coke, manufacture of pesticides, rubber or dyes, sewage treatment
plant, hazardous waste sites, forest fires etc.;
In case of drying of harvested crop: use the HACCP drying processes calculation
model of GMP+ International to assess the risk of PAHs contamination. This
HACCP calculation model is solely meant to make a quick and systematic first
risk analysis of a drying process that is applied. This is based on essential
information that is available (or should be) concerning the applied drying process.
Based on the analysis control measures can be presented that follow directly
from the risks that are identified by the calculation model;
Apply the control measures as mentioned in the GMP+3 D4.4 International
publication (2004) Study into drying processes for animal feed materials and
HACCP;
Prevent formation and deposition of fly ash and cyclone dust (GMP+3, 2004);
Prevent contact of harvested crop with engine exhaust;
Prevent contact of harvested crop with mineral oils, e.g. lubricating oil, engine oil,
hydraulic oil, petrol or diesel fuels. Storage of these oils and fuels should be
physical segregated from crop and a machinery maintenance program is in place.
Leakage should be prevented.

PAHs monitoring program:


Cultivation, harvesting, processing, transport and storage on farm

Products to be monitored, as is determined using the HACCP system, may be


sowing seeds, soil, fertilizer, manure, compost materials, residues and spills in
specific areas, silage, other roughage and harvested crop;
In the event of PAHs contamination corrective measures will be taken
immediately (e.g. detect source, determine if other crops are contaminated).

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APPENDIX IV PAHs control measures: husbandry.

Husbandry

Use the HACCP system to assess the risk of PAHs in feed during husbandry.
Besides others, the following items should be addressed:
Determine the history and the present situation in the cultivation area and focus
on PAHs emitting activities. E.g. industrial power generation, production of
aluminium, iron and steel, petroleum catalytic cracking and production of asphalt,
coal tar and coke, manufacture of pesticides, rubber or dyes, sewage treatment
plant, hazardous waste sites, forest fires etc.;
Prevent contact of animals, feed and drinking water with mineral oils, e.g.
lubricating oil, engine oil, hydraulic oil, petrol or diesel fuels. Storage of these oils
and fuels should be physical segregated from animals, feed and drinking water
and a machinery maintenance program is in place. Leakage should be
prevented.

PAHs monitoring program: husbandry

Products to be monitored, as is determined using the HACCP system, may be


feed, drinking water products of animal origin (e.g. eggs, milk and other diary
products);
In the event of PAHs contamination corrective measures will be taken
immediately (e.g. detect source, determine if products of animal origin are
contaminated).

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APPENDIX V PAHs control measures: transport of feed.
In GMP+ B1 standard general control measures and requirements are stated which
should be complied with (GMP+2, 2013). Specific requirements and control measures
related to transport are stated in various GMP+ standards (GMP+3,4,5,6,7,8, 2013). The
applicable GMP+ standard depends on the means of transport. The applicable
standard should be complied with.

Transport

Use the HACCP system to assess the risk of PAHs in the feed during transport.
Besides others, the following items should be addressed:
Prevent contact of feed with mineral oils, e.g. lubricating oil, engine oil, hydraulic
oil, petrol or diesel fuels. Storage of these oils and fuels should be physical
segregated from animals, feed and drinking water and a machinery maintenance
program is in place. Leakage should be prevented;
Prevent contact of feed with engine exhaust;
Covering of feed during transport.

PAHs monitoring program: transport

The HACCP system should be used to determine the products to be included in


the PAHs monitoring program;
In the event of PAHs contamination corrective measures will be taken
immediately (e.g. detect source, determine if other feed is contaminated).

Fact sheet: Polycyclic Aromatic Hydrocarbons (PAH4) 26 / 29


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APPENDIX VI PAHs control measures: storage and transhipment of feed.
In GMP+ B1 standard general control measures and requirements are stated which
should be complied with (GMP+2, 2013). Specific requirements and control measures
related to transport are stated in the GMP+ B3 standard (GMP+9, 2013). Additional
recommendations for general control measures are stated below in this appendix.

Storage and transhipment

Use the HACCP system to assess the risk of PAHs in feed during storage. Besides
others, the following items should be addressed:
Determine the history and the present situation in the storage and transhipment
area and focus on PAHs emitting activities. E.g. industrial power generation,
production of aluminium, iron and steel, petroleum catalytic cracking and
production of asphalt, coal tar and coke, manufacture of pesticides, rubber or
dyes, sewage treatment plant, hazardous waste sites, forest fires etc.;
Prevent contact of feed with mineral oils, e.g. lubricating oil, heating oil (in case of
heated storage of liquids in tanks), engine oil, hydraulic oil, petrol or diesel fuels.
Storage of these oils and fuels should be physical segregated from animals, feed
and drinking water and a machinery maintenance program is in place. Leakage
should be prevented.

PAHs monitoring program: storage and transhipment

The HACCP system should be used to determine the products to be included in


the PAHs monitoring program, e.g. heat-stored liquid feed heated via heating oils;
In the event of PAHs contamination corrective measures will be taken
immediately (e.g. detect source, determine if other feed is contaminated).

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APPENDIX VII PAHs control measures: processing of feed.
In GMP+ B1 and B2 standard general control measures and requirements are stated
which should be complied with (GMP+2,10, 2013). Additional recommendations for
general control measures are stated below in this appendix.

Processing
Use the HACCP system to assess the risk of PAHs contamination in feed during feed
processing. Besides others, the following items should be addressed:
Determine the history and the present situation in the feed processing area and
focus on PAHs emitting activities. E.g. industrial power generation, production of
aluminium, iron and steel, petroleum catalytic cracking and production of asphalt,
coal tar and coke, manufacture of pesticides, rubber or dyes, sewage treatment
plant, hazardous waste sites, forest fires etc.;
In case of mined products: determine the history and the present situation in the
mining area and focus on the possible PAHs contamination by volcanoes;
Verify yourself if PAHs risk products are used in the processing of feed. Include
all products that are included in the feed and products that may come in direct
contact with the feed (e.g. processing agents, water, steam, lubricating oil);
Verify if the supplier/producer of feed (also include premixes, additives) has
assessed the hazard and risk of PAHs;
Verify if the supplier/producer of products other than feed, but that come in direct
contact with feed has assessed the hazard and risk of PAHs;
Selecting of the supplier/producer based on their implementation of programs for
the control of PAHs;
Feed or other products that are included in the feed or may come in direct contact
with the feed arriving at the production site should be subjected to arrival
inspections and include the following:
o Inspection of visible oil leakage in feed.
o Assessment of transport entities with respect to maintenance and defects.
Pay special attention to possible contact of exhaust of the transport entity
(e.g. truck, train, boat) with feed or food
In case of drying of feed: use the HACCP drying processes calculation model of
GMP+ International to assess the risk of PAHs contamination. This HACCP
calculation model is solely meant to make a quick and systematic first risk
analysis of a drying process that is applied. This is based on essential information
that is available (or should be) concerning the applied drying process. Based on
the analysis control measures can be presented that follow directly from the risks
that are identified by the calculation model;
Apply the control measures as mentioned in the GMP+3 D4.4 International
publication (2004) Study into drying processes for animal feed materials and
HACCP;
Prevent formation and deposition of fly ash and cyclone dust (GMP+3, 2004);
Prevent contact of feed with mineral oils, e.g. lubricating oil, engine oil, hydraulic
oil, petrol or diesel fuels. Storage of these oils and fuels should be physical
segregated from crop and a machinery maintenance program is in place.
Leakage should be prevented.
Determination if concentration of PAHs might occur in certain (by) products
during processing and if these are used in feed or (by) products added to feed
(e.g. in fatty acid distillates);
Use of possible PAHs contaminated additives / processing aids and its possible
contamination of feed (e.g. bleaching earth, activated carbon);

PAHs monitoring program: processing

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PAHs monitoring program: processing

The HACCP system should be used to determine the products to be included in


the PAHs monitoring program, e.g. feed ingredients, by products, processing
agents, water, additives, premixes, end product (e.g. compound feed);
In the event of PAHs contamination corrective measures will be taken
immediately (e.g. detect source, determine if other feed is contaminated).

Fact sheet: Polycyclic Aromatic Hydrocarbons (PAH4) 29 / 29


Version: 09/01/2015 GMP+ International B.V.

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