ELSEVIER Journal of Chromatography A, 763 (1997) 179-185
JOURNAL OF
CHROMATOGRAPHYA
Analysis of foods for heterocyclic aromatic amine carcinogens by
solid-phase extraction and high-performance liquid chromatography
Mark G. Knize*, Cynthia P. Salmon, Ellen C. Hopmans, James S. Felton
Biology and Biotechnology Research Program, L-452, Lawrence Livermore National Laboratory,,, Livermore, CA 94550, USA
Abstract
Carcinogenic and mutagenic heterocyclic aromatic amines (HAA) are natural products often present at ng/g levels in
muscle meats when they are cooked at temperatures over 150°C. Using solid-phase extraction and high performance liquid
chromatography (HPLC) with photodiode array UV detection, samples were analyzed for the following heterocyclic amines:
DiMeIQx (2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline); IQ (2-amino-3-methylimidazo[4,5-f]quinoline); MeIQx (2-
amino-3,8-dimethylimidazo[4,5-f]quinoxaline); and PhIP (2-amino-l-methyl-6-phenylimidazo[4,5-b]pyridine). Quality con-
trol samples, analyzed periodically over two years in a blind study, show relative standard deviations ranging from 22 to
38% for the compounds found, variations typical for analysis at ng/g levels. Amounts range from undetectable levels (less
than 0.1 ng/g) to hundreds of ng/g of PhIP for frying or grilling at high meat surface temperatures. Beef, chicken, pork and
lamb can all have greater than 10 ng/g of PhIE Ground chicken breast meat has lower amounts of heterocyclic amines than
intact muscle pieces of the same size cooked identically. Restaurant prepared samples that we analyzed contained
undetectable levels up to 14 ng/g total heterocyclic amines for a beef steak sample. Not extracted with the above method are
related mutagenic heterocyclic amines, which have been reported in cooked foods in our laboratory and others. Method
development using ion exchange on an SCX solid-phase extraction cartridge shows promise in providing a method for the
quantitation of these mutagenic dimethyl-, trimethyl- and furo-imidazopyridines where a practical analysis method is needed.
Keywords: Food analysis; Aromatic amines, heterocyclic; Amines
1. Introduction
The search for carcinogenic agents in foods is
directed towards explaining differences in cancer
occurrence in humans. Analysis of the health risks of
dietary chemicals has focused either on exogenous
chemicals added to foods, such as pesticides and
artificial sweeteners, or endogenous substances natu-
rally present or formed within foods, such as fats and
fungal metabolites.
The finding that extracts of cooked muscle meats
produce a potent response in the Ames~Salmonella
mutation test led to studies using analytical chemis-
*Corresponding author.
try methods to isolate and identify the chemicals
responsible for the mutagenic activity. These potent
mutagens in bacterial test systems have been shown
to be carcinogenic in animal test systems and have
been the subject of hundreds of research articles in
the last 17 years [1-5].
The formation of mutagenic chemicals in meats
has been explained by the condensation of creatine
or creatinine with amino acids and sugars or their
thermal decomposition products in model systems
and meats [6,7].
Many heterocyclic aromatic amines have been
isolated and identified from cooked meats or model
systems, but four compounds are frequently reported
in food surveys [8-12]. These are: DiMeIQx (2-
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