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PROCESSING
CONTAMINANTS IN
EDIBLE OILS
This page intentionally left blank
PROCESSING
CONTAMINANTS IN
EDIBLE OILS
MCPD and Glycidyl Esters
SECOND EDITION

Edited by

SHAUN MACMAHON
U.S. Food and Drug Administration,
Center for Food Safety and Applied Nutrition (CFSAN),
MD, United States

JESSICA K. BEEKMAN
U.S. Food and Drug Administration,
Center for Food Safety and Applied Nutrition (CFSAN),
MD, United States
Academic Press and AOCS Press
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in cooperation with American Oil Chemists Society.
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Contents

Contributors ix

1. Introduction 1
Shaun MacMahon
Formation 1
Mitigation 1
Analysis 2
Toxicology 3
Regulations 4
References 5

2. Formation mechanisms 7
Brian D. Craft and Frédéric Destaillats
Introduction 7
MCPD esters 8
Glycidyl esters 12
Conclusions and perspectives 20
References 20

3. Mitigation of MCPD and glycidyl esters in edible oils 23

Bertrand Matthäus and Frank Pudel
Introduction 23
Influence of precursors on ester formation 26
Mitigation in field 37
Mitigation of the raw material 39
Mitigation in refining 42
Additives 52
Removal from fully refined oils (post-refining) 56
References 59

4. Indirect detection techniques 65

Karel Hrncirík
Introduction 65
Main steps in the analysis of 2- and 3-MCPD esters 66
Main approaches toward the analysis of glycidyl esters 75

v
vi Contents

Officially adopted methods 83

Method comparison 89
Method automation 96
Analysis of oil-based foodstuffs 97
Challenges in foodstuff analysis 98
Conclusions 103
References 104

5. Direct analytical detection methods for the food-borne

toxicants glycidyl esters 109
Alice Ewert and Michael Granvogl
Introduction 109
Direct methods 111
References 142

6. Direct detection techniques for MCPD esters 145

Shaun MacMahon
Background 145
Direct methods 146
The Institute of Chemical Technology 162
Conclusion 191
References 191

7. Methods to detect MCPD and glycidyl esters in complex food

matrices 195
Shaun MacMahon, Jessica Beekman and Michael Granvogl
Background 195
Discussion 196
Conclusions 217
References 217

8. Toxicological properties of glycidyl esters 221

Gabriele Scholz and Benoît Schilter
Introduction 221
Biological properties of glycidyl esters 222
Biological properties of free glycidol 225
Conclusions 231
References 232
 Contents vii

9. Toxicological properties of MCPD fatty acid esters 235

Alfonso Lampen
Abbreviations 235
Introduction 235
Toxicology of 3-MCPD 236
Hazard potential of 3-MCPD fatty acid esters 242
Toxicology of 2-MCPD esters 247
Risk characterization 248
Conclusions 249
References 250

Index 253
This page intentionally left blank
Contributors

Jessica Beekman
FDA Center for Food Safety and Applied Nutrition, College Park, MD, United States
Brian D. Craft
Nestlé Research Center, Food Science and Technology Department, Lausanne,
Switzerland
Frédéric Destaillats
Nestlé Research Center, Food Science and Technology Department, Lausanne,
Switzerland
Alice Ewert
German Research Center for Food Chemistry, Freising, Germany
Michael Granvogl
University of Hohenheim, Institute of Food Chemistry, Department of Food Chemistry
and Analytical Chemistry (170a), Stuttgart, Germany; Technical University of Munich,
Department of Chemistry, Chair for Food Chemistry, Freising, Germany
Karel Hrncirík
Upfield, Rotterdam, the Netherlands
Alfonso Lampen
Federal Institute for Risk Assessment (BfR), Berlin, Germany
Shaun MacMahon
FDA Center for Food Safety and Applied Nutrition, College Park, MD, United States
Bertrand Matthäus
Max Rubner-Institut, Department for Safety and Quality of Cereals, Working Group for
Lipid Research, Detmold, Germany
Frank Pudel
Pilot Pflanzenöltechnologie Magdeburg e.V., Magdeburg, Germany
Benoît Schilter
Société des Produits Nestlé S.A., Nestlé Research, Lausanne, Switzerland
Gabriele Scholz
Société des Produits Nestlé S.A., Nestlé Research, Lausanne, Switzerland

ix
This page intentionally left blank
CHAPTER 1

Introduction
Shaun MacMahon
FDA Center for Food Safety and Applied Nutrition, College Park, MD, United States

Formation
To improve consumer acceptance, edible oils are industrially processed to
remove or modify components that can negatively impact appearance, taste,
and shelf stability. However, undesirable chemical changes can take place
during the refining process. Fatty acid esters of 3-chloro-1,2-propanediol
(3-MCPD), 2-chloro-1,3-propanediol (2-MCPD), and glycidol are heat-
induced contaminants that are not present in virgin unrefined oils, but
they can be produced by the high temperatures applied during deodorization
[1e3]. There is evidence that 3-MCPD esters are formed from iron chloride
and/or natural organochlorines present in native oils [4e7]. The predomi-
nant precursors and formation pathways for MCPD and glycidyl esters will
be thoroughly reviewed in Chapter 2 of this text.

Mitigation
The fact that MCPD esters begin forming at 200 C makes mitigation
difficult, as deodorizations are generally run at temperatures greater than
200 C [4]. Many factors contribute to the formation of MCPD and glycidyl
esters. The growing conditions and harvesting of the palm fruit can have
profound effects on an oil’s capacity to form contaminants. The extraction,
washing, and processing steps that take place prior to deodorization can
influence the formation of these toxicants during deodorization, as can the
specifics of the deodorization scheme. It is also possible to remove MCPD
and glycidyl esters using appropriate adsorbents or enzymes. There have
been a number of recent advances in mitigation of MCPD and glycidyl
esters, including industrial scale production of mitigated palm oil for use in
infant formula in the United States [8]. Chapter 3 of this text discusses the
optimization of all of these steps to reduce and eliminate the presence of
these contaminants in refined edible oils.

Copyright © 2022 AOCS Press.

Processing Contaminants in Edible Oils Published by Elsevier Inc. All rights reserved.
ISBN 978-0-12-820067-4 Published in cooperation with
https://doi.org/10.1016/B978-0-12-820067-4.00007-3 American Oil Chemists Society. 1
2 Processing Contaminants in Edible Oils

Analysis
Processed edible oils are commonly consumed worldwide and used in the
production of many foods including infant formula, highlighting the need
for accurate analytical methodology for their detection. Indirect approaches
requiring ester hydrolysis followed by derivatization and analysis by GCe
MS were the first methods developed to detect MCPD and glycidyl esters
[9e11]. While these early methods played a crucial role in bringing
attention from industry and regulators to the presence of these contami-
nants in refined oils, the early conditions for base-catalyzed hydrolyzes were
shown to be potentially unreliable, raising questions about the trustwor-
thiness of indirect methodology [12,13]. More recently, however, these
issues have been addressed and the quality and reliability of these indirect
methods has improved greatly. Several indirect approaches (including those
involving automation) have recently completed successful collaborative
studies, reaching official compendial method status with organizations such
as the American Oil Chemists’ Society (AOCS) and the International
Organization for Standardization (ISO). The application of these indirect
methods to the analysis of MCPD and glycidyl esters in oils and high fat
matrices like dressings/spreads will be covered in Chapter 4.
Partly in response to the lack of dependability of early indirect meth-
odology, direct methods were developed for glycidyl esters (GEs) and
3-MCPD esters, with contaminants analyzed intact as they occur in pro-
cessed oils. Although direct techniques require a large number of standards
(some of which are not commercially available) for quantitative analysis, this
methodology can provide information about the individual MCPD and
glycidyl esters present in a refined oil e indirect methods, on the other
hand, provide quantitative information regarding the total ester content in
an oil expressed as bound MCPD and glycidol. Detailed information about
the structure of the individual esters can be useful in a number of appli-
cations. Some studies have indicated potential toxicological differences
between different 3-MCPD esters; this information is lost when applying
indirect methodology. In addition, as methods have begun to be extended
to complex foods, the use of a direct approach can ensure acceptable
extraction recoveries of all the different esters, which do have distinct
polarity differences in some cases. Information about individual esters can
also be useful in evaluating the effectiveness of mitigation approaches. The
use of direct methods for the analysis of intact esters of glycidol (Chapter 5)
and 3-MCPD (Chapter 6) in edible oils will be discussed.
 Introduction 3

Since refined oils are the primary fat source in commercial infant
formulas, the presence of MCPD and glycidyl esters is a source of potential
concern due to infants’ low body weight and consumption of infant
formula as the sole source of nutrition in some children. As a result, research
efforts have focused on the development of analytical methods for the
analysis of MCPD and glycidyl esters in infant formula, as well as in other
complex foods commonly consumed by children. Chapter 7 will review
the analysis of MCPD esters and glycidyl esters in infant formula as well as
in other complex foods.

Toxicology
Free glycidol, 3-MCPD, and 2-MCPD all pose concerns from a food safety
perspective. Glycidol is a genotoxic carcinogen that is probably carcino-
genic to humans [14]. According to the Federal Institute for Risk Assess-
ment in Berlin, Germany (BfR), concentrations should be kept as low as are
reasonably achievable in food [15]. Due to its genotoxicity, the Food Safety
Commission of Japan has suggested glycidol intake should be based on the
ALARA principle (As Low As Reasonably Achievable) [16]. Negative
effects on kidneys and reproductive systems have been seen from 3-MCPD
in toxicological studies [17], and it was classified by the European Scientific
Committee on Food as a nongenotoxic threshold carcinogen [18]. Free
3-MCPD has been labeled as a group 2B carcinogen (possibly carcinogenic
to humans) by the International Agency for Research on Cancer (IARC)
[19]. There are toxicological concerns shown in limited studies related to
2-MCPD; one unpublished report showed that high doses affected striated
muscles and the heart, as well as the kidneys and the liver in rats [20].
Relative to the free forms of these contaminants, research on the fatty
acid esters that are formed in deodorized oils has only been initiated more
recently [15,20,21]. In vivo toxicological work has demonstrated that free
3-MCPD is liberated from the diester form in rats [22] as is glycidol from
glycidyl esters [23] in relatively high yields. Initial risk assessments
conducted by the BfR have concluded that using a worst-case scenario,
infants who are fed only commercial infant formulas could potentially
ingest amounts of glycidol and 3-MCPD exceeding the Joint Food and
Agriculture Organization/World Heath Organization Expert Committee
on Food Additives (JECFA) recommended maximum tolerable daily intake
levels [21]. Exposures to 3-MCPD esters in the United States from
consumption of infant formulas, estimated using data on 3-MCPD ester
4 Processing Contaminants in Edible Oils

concentrations in formula samples collected between 2013 and 2015, are

higher than those estimated for European infants. However, estimated
glycidyl ester exposures were comparable for US and European infants in
that time range [8]. The full results of all toxicological studies on these
contaminants will be discussed in Chapter 8 (glycidyl esters) and Chapter 9
(MCPD esters).

Regulations
In response to the detection of free 3-MCPD in hydrolyzed vegetable
protein, soy sauce, and baked goods, many international organizations
addressed the issue in those matrices. The JECFA recommended a
maximum tolerable daily intake for 3-MCPD of 2 m[mu]g/kg body weight
per day [24]. The European Commission established a maximum level of
20 m[mu]g/kg (ppb) for 3-MCPD in hydrolyzed vegetable protein and soy
sauce [25], which was also adopted by Food Standards Australia New
Zealand (FSANZ) [26]. The Codex Alimentarius adopted a maximum level
of 400 m[mu]g/kg (ppb) in liquid condiments containing acid-hydrolyzed
vegetable protein (excluding naturally fermented soy sauce) in 2008 [27].
The US Food and Drug Administration Compliance Policy Guide states
that hydrolyzed vegetable protein that contains 3-MCPD at levels greater
than 1 m[mu]g/g (ppm) is not generally recognized as safe (GRAS), and
therefore is an unsafe food additive [28]. Health Canada also set a maximum
contaminant concentration of 1 m[mu]g/g (ppm) in Asian-style sauces [29].
Regulations regarding MCPD or glycidyl ester concentrations in
processed oils have begun to appear in recent years. The European
Commission (EC) published an initial maximum level for glycidyl esters
(expressed as glycidol) in powdered infant formula of 75 mg/kg that was
reduced to 50 mg/kg in July 2019; and a maximum level in liquid formula
of 10 mg/kg that was reduced to 6 mg/kg in July 2019 [30]. In addition, the
maximum level for bound glycidol in vegetable oils and fats is 1000 mg/kg
except for those used to produce baby food and processed cereal-based food
for infants and young children, where the limit is 500 mg/kg [30]. The EC
has proposed levels for the sum of free 3-MCPD and bound 3-MCPD for
several products, although these have not been finalized. The proposed
limits for the sum of bound and free 3-MCPD are 1250 mg/kg for oils/fats
from individual or oil mixes from coconut, corn, canola, sunflower,
soybean, and palm kernel; 2500 mg/kg for oils/fats from individual or mixes
from other vegetable oils and fish oil, and 2500 mg/kg for mixtures of oils
from both categories. Vegetable oils and fats destined for the production of
 Introduction 5

baby food and processed cereal-based food for infants and young children
have a proposed limit of 750 mg/kg. Infant formula, follow-on formula, and
foods for special medical purposes intended for infants and young children
have proposed limits of 125 mg/kg for powders and 15 mg/kg for liquids.
The EC has also discussed bringing fish/marine oils into the existing
published limits for bound glycidol, although no final decisions have been
made at press time.

References
[1] Hrncirik K, van Duijn G. An initial study on the formation of 3-MCPD esters during
oil refining. Eur J Lipid Sci Technol 2011;113:374e9.
[2] Matthäus B, Pudel F, Fehling P, Vosmann KL, Freudenstein A. Strategies for the
reduction of 3-MCPD esters and related compounds in vegetable oils. Eur J Lipid Sci
Technol 2011;113:380e6.
[3] Pudel F, Benecke P, Fehling P, Freudenstein A, Matthäus B, Schwaf A. On the
necessity of edible oil refining and possible sources of 3-MCPD and glycidyl esters. Eur
J Lipid Sci Technol 2011;113:368e73.
[4] Destaillats F, Craft BD, Sandoz L, Nagy K. Formation mechanisms of mono-
chloropropanediol (MCPD) fatty acid diesters in refined palm (Elaeis guineensis) oil and
related fractions. Food Addit Contam A 2012;29:29e37.
[5] Destaillats F, Craft BD, Dubois ML, Nagy K. Glycidyl esters in refined palm (Elaeis
guineensis) oil and related fractions. Part I: formation mechanism. Food Chem
2012;131:1391e8.
[6] Nagy K, Sandoz L, Craft B, Destaillats F. Mass-defect filtering of isotope signatures to
reveal the source of chlorinated palm oil contaminants. Food Addit Contam
2011;28:1492e500.
[7] Smidrkal J, Tesarová M, Hrádková I, Bercíková M, Adamcíková A, Filip V. Mecha-
nism of formation of 3-chloropropan-1,2-diol (3-MCPD) esters under conditions of
the vegetable oil refining. Food Chem 2016:124e9.
[8] Spungen JH, MacMahon S, Leigh J, Flannery B, Kim G, Chirtel S, Smegal D.
Estimated US infant exposures to 3-MCPD and glycidyl esters from consumption of
infant formula. Food Addit Contam A 2018:1085e92.
[9] Divinová V, Svejkovská B, Dolezal M, Velísek J. Determination of free and bound 3-
chloropropane-1,2-diol by gas chromatography with mass spectrometric detection
using deuterated 3-chloropropane-1,2-diol as internal standard. Czech J Food Sci
2004;22:182e9.
[10] Weibhaar R. Determination of total 3-chloropropane-1,2-diol (3-MCPD) in edible
oils by cleavage of MCPD esters with sodium methoxide. Eur J Lipid Sci Technol
2008;110:183e6.
[11] Zelinková V, Svejkovská B, Dolezal M, Velísek J. Fatty acid esters of 3-chloropropane-
1,2-diol in edible oils. Food Addit Contam 2006;23:1290e8.
[12] Haines TD, Adlaf KJ, Pierceall RM, Lee I, Venkitasubramanian P, Collison M. Direct
determination of MCPD fatty acid esters and glycidyl fatty acid esters in vegetable oils
by LC-TOFMS. J Am Chem Soc 2011;88:1e14.
[13] Kaze N, Sato H, Yamamoto H, Watanabe Y. Bidirectional conversion between 3-
monochloro-1,2-propanediol and glycidol in course of the procedure of DGF stan-
dard methods. J Am Oil Chem Soc 2011;88:1143e51.
6 Processing Contaminants in Edible Oils

[14] IARC (International Agency for Research on Cancer). Some industrial chemicals. In:
IARC monographs on the evaluation of carcinogenic risk of chemicals to humans, vol.
77. Lyon, France: International Agency for Research on Cancer; 2000. p. 469e86.
[15] Bakhiya N, Abraham K, Gürtler R, Appel KE, Lampen A. Toxicological assessment of
3-chloropropane-1,2-diol and glycidol fatty acid esters in food. Mol Nutr Food Res
2011;55:509e21.
[16] Food Safety Commission of Japan (FSCJ). Considerations on glycidol and its fatty acid
esters in foods. Risk Assess Rep - Novel Foods & Food Addit 2015. FS/185/2015, Japan.
[URL: http://www.fsc.go.jp/english/evaluationreports/others/annex_glycidol_26-52.pdf.
[17] Cho WS, Han BS, Nam KT, Park K, Choi M, Kim SH, Jeong J, Jang DD. Carci-
nogenicity study of 3-monochloropropane-1,2-diol in sprague-dawley rats. Food
Chem Toxicol 2008;46:3172e7.
[18] European Commission Health and Consumer Protection Directorate. Opinion of the
scientific committee on food on 3-monochloro-propane-1,2-diol (3-MCPD). 2001.
[19] IARC (International Agency for Research on Cancer). IARC monographs on some
chemicals present in industrial and consumer products. Food & Drink Wkly: 3-
Monochloro-1,2-Propanediol 2016:349e74.
[20] Schilter B, Scholz G, Seefelder W. Fatty acid esters of chloropropanols and related
compounds: toxicological aspects. Eur J Lipid Sci Technol 2011;113:309e13.
[21] Buhrke T, Weißhaar R, Lampen A. Absorption and metabolism of the food
contaminant 3-chloro-1,2-propanediol (3-MCPD) and its fatty acid esters by human
intestinal caco-2 cells. Arch Toxicol 2011;85:1201e8.
[22] Abraham K, Appel KE, Berger-Preiss E, Apel E, Gerling S, Mielke H,
Creutzenberg O, Lampen A. Relative oral bioavailability of 3-MCPD from 3-MCPD
fatty acid esters in rats. Arch Toxicol 2013;87:649e59.
[23] Appel KE, Abraham K, Berger-Preiss E, Hansen T, Apel E, Schuchardt S, Vogt C,
Bakhiya N, Creutzenberg O, Lampen A. Relative oral bioavailability of glycidol from
glycidyl fatty acid esters in rats. Arch Toxicol 2013;87:1649e59.
[24] WHO. Safety evaluation of certain food additives and contaminants, 3-chloro-1,2-
propanediol. WHO Food Addit Ser 2002;48. http://www.inchem.org/documents/
jecfa/jecmono/v48je18.htm.
[25] European Commission Health and Consumer Protection Directorate. Commission
regulation (EC) No 1881/2006 of 19 December 2006: setting maximum levels for
certain contaminants in foodstuffs. 2006.
[26] FSANZ. Chloropropanols in food, an analysis of the public health risk; technical report
series No. 15; food standards, Australia/New Zealand. 2003. http://www.foodstandards.
gov.au/publications/Documents/Technical Report Chloropropanol Report 11 Sep 03.
doc.
[27] Codex Alimentarius. Codex general standard for contaminants and toxins in food and
feed, codex stan 193e1995; amended. 2012. www.codexalimentarius.org/download/
standards/17/CXS_193e_2012.pdf.
[28] U.S. Food and Drug Administration. Guidance levels for 3-MCPD (3-chloro-1,2-
propanediol) in acid-hydrolyzed protein and asian-style sauces. Compliance Policy
Guide Section 500.500. March 14, 2008. http://www.fda.gov/ICECI/Compliance
Manuals/CompliancePolicyGuidanceManual/ucm074419.htm.
[29] Health Canada. Canadian standards (maximum levels) for various chemical contami-
nants in foods. Modified. June 28, 2012. http://www.hc-sc.gc.ca/fn-an/securit/chem-
chim/contaminants-guidelines-directives-eng.php.
[30] European Commission. Commission regulation (EU) 2018/290 of 26 February 2018
amending regulation (EC) No 1881/2006 as regards maximum levels of glycidyl fatty
acid esters in vegetable oils and fats, infant formula, follow-on formula and foods for
special medical purposes intended for infants and young children. 2018.
CHAPTER 2

Formation mechanisms
Brian D. Craft and Frédéric Destaillats
Nestlé Research Center, Food Science and Technology Department, Lausanne, Switzerland

Introduction
Since the publication of [1] and the heightened awareness of fatty esters of
monochloropropanediol (MCPD-FE) in refined edible oils, the circum-
stances surrounding their formation have been subject to large amounts of
speculation. For instance, some researchers speculated that precursors for
MCPD-FE formation (e.g., chlorine and diacylglycerols) are present in
partially refined oils [2]. Other researchers suspected that the refining
process results in the uncontrolled introduction of certain compounds to
the oils (e.g., inorganic chlorides in the stripping stream), so it should be the
first place to explore mitigation strategies [3]. Further, amid analytical
developments in MCPD-FE quantification, another family of compounds
was discovered in refined edible oils, namely the fatty esters of glycidol
(G-FE). G-FE were found to be partially responsible for inflation of the
results of MCPD-FE quantifications due to the generation of artifacts
during sample preparation before analysis using indirect methods [4].
Despite these early hurdles, some recent breakthroughs were made by
Refs. [5e7] on the formation mechanisms of both MCPD-FE and G-FE
during palm oil refining. Within this chapter we will take a focused look
at the status of the literature to date as it pertains to the formation pathways
of MCPD-FE and G-FE in refined edible oils. Critical topics will be
covered, including the most prevalent precursor compounds and detailed
formation mechanisms responsible for the generation of these process
contaminants during oil production and refining. Because both MCPD-FE
and G-FE have been found in the highest average abundance in palm oil,
the majority of the research reviewed herein involves crude palm oil
production and refining.

Copyright © 2022 AOCS Press.

Processing Contaminants in Edible Oils Published by Elsevier Inc. All rights reserved.
ISBN 978-0-12-820067-4 Published in cooperation with
https://doi.org/10.1016/B978-0-12-820067-4.00004-8 American Oil Chemists Society. 7
8 Processing Contaminants in Edible Oils

MCPD esters
Precursors
Chlorine is ubiquitous in nature. Thus, one can speculate about a wide
variety of chlorine sources, whether organic or inorganic, as potential
precursor compounds to MCPD-FE formation during edible oil produc-
tion. Further, a host of lipid types and compositions (e.g., acylglycerols,
phospholipids, glycolipids) are available in the raw materials used to pro-
duce edible oils. Many of these lipids could theoretically interact with
chlorine sources and result in the formation of MCPD-FE during oil
refining. The critical precursors responsible, however, are mostly dependent
on the oil type, quality, and, to a lesser degree, the circumstances
of manufacture, as will be described below. Given that refined palm oil
specifically has been shown to contain significant levels of MCPD-FE
(2.7 mg/kg) [8], it has been exclusively used as a model matrix in the
literature.
The first question often raised regarding MCPD-FE precursors is the
origin of chlorine involved in the MCPD-FE reaction during oil refining
and why it is potentially more abundant in crude palm oil (CPO) in
comparison to other crude vegetable oils [9]. Recently [5], demonstrated
that many sources of covalently bound inorganic chlorine exist at ppm
(mg/kg) levels in crude palm oil, including FeCl3, FeCl2, MgCl2, and
CaCl2. Further, a “pool” (n ¼ 300) of organic monochlorinated com-
pounds was also found and it appears to undergo a transformation
throughout the stages of oil refining with certain compounds being formed
while others decompose over time. In order to elucidate the composition of
the more predominant chlorine “donor” compounds [5], used LC-MSn in
the framework of model experiments. Therein the authors identified a
specific family of chlorinated compounds present in both the lipids
extracted from hand-picked Malaysian palm fruits and commercially pro-
cured CPO samples. Fig. 2.1, taken from Ref. [5]; shows the proposed
structure and chemical formulas of this monochlorinated family of com-
pounds. The authors suggest that given their structural similarities to
phytosphingosines, it is perhaps more likely that the chlorine donors
identified are endogenous plant metabolites as opposed to chlorinated
contaminants introduced to the oil palm’s direct environment during
growth and maturation. Extrapolating from this hypothesis, one might tend
to the logic that the raw materials intended for production of each edible
vegetable oil have their own reactive-chlorine pool capable of donating
chlorine during oil refining and ultimately resulting in MCPD-FE
generation.
 Formation mechanisms 9

OH
O
HN
OH Cl
HO
OH

Elemental composition Exact m/z

C42H83O4NCl 700.60280
C42H85O4NCl 702.61807
C42H83O5NCl 716.59723
C42H85O5NCl 718.61357
C42H85O6NCl 734.60809

Figure 2.1 Proposed structure and chemical formulas of an organochlorine family of

compounds found in crude palm oil. (Reprinted with permission from Nagy K, Sandoz L,
Craft BD, Destaillats F. Mass-defect filtering of isotope signatures to reveal the source of
chlorinated palm oil contaminants. Food Addit Contam 2011;28:1492e1500).

In terms of the most predominant lipid precursors of MCPD-FE in

edible oils [1], proposed that there may be a link between the content of
diacylglycerols (DAGs) in refined edible oils and their MCPD-FE levels.
This assertion was likely due to the fact that the highest MCPD-FE levels
were observed within the fruit pulp oils analyzed. Fruit pulp oils, such as
olive and palm, are known for having high DAG contents compared to
seed oils, due to the greater prevalence of lipolytic reactions during harvest
[10]. This correlation, however, has been disproved in recent literature
[11,12]. Although DAGs could potentially react with chlorine donors
during oil refining and result in the formation of MCPD-FE, they are not
the most critical lipid precursors of these process contaminants. Further,
lipids such as monoacylglycerols (MAGs), phospholipids, and glycolipids are
largely removed during oil degumming and are not present during the later
stages of oil refining [10].
Because the bulk of MCPD-FE have been shown to be generated
during oil deodorization [2,13], the entirety of the aforementioned lipid
classes is not expected to be greatly involved in MCPD-FE formation
reactions. This of course leaves the triacylglycerols (TAGs) up for consid-
eration. TAGs can represent more than 90%e95% (v/v) of refined vege-
table oils, whether pressed from nuts, seeds, or fruit pulps. TAGs are,
therefore, the most logical critical lipid precursor available for MCPD-FE
formation during oil deodorization. The results of in vitro thermal reac-
tion experiments carried out by Ref. [7] appear to confirm this hypothesis
[7]. demonstrated in controlled conditions that TAGs, not DAGs, are
preferentially reacting with chlorine donors to form MCPD-FE.
Another random document with
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double action which pours it into Water, and volatilizes it into Air, and sifts
it to ashes which are Earth. For man can fashion effigies, but the spark of
Life he can neither infuse nor control.

As a sharp sun this man passed across his century, and of the cenotaphs
of his burning, some remain as a shadow of splendour in the streets of his
city, but others have returned whence he gathered them, for the years of
these are many and the touch of kings upon them is as the dropping of
particles of dust.

VENICE AGAIN

Sunday evening, May 23, 1915. A beautiful Sunday evening with the
Lagoon just going purple, and the angel on the tip of the new Campanile
dissolved to a spurt of crocus-coloured flame. Up into the plum-green sky
mount the angels of the Basilica of Saint Mark, their wings, curved up and
feathered to the fragility of a blowing leaf, making incisive stabs of
whiteness against the sky.

An organ moans in the great nave, and the high voices of choristers float
out through the open door and surge down the long Piazza. The chugging of
a motor-boat breaks into the chant, swirls it, churns upon it, and fades to a
distant pulsing down the Grand Canal. The Campanile angel goes suddenly
crimson, pales to rose, dies out in lilac, and remains dark, almost invisible,
until the starting of stars behind it gives it a new solidity in hiding them.

In the warm twilight, the little white tables of the Café Florian are like
petals dropped from the rose of the moon. For a moment they are weird and
magical, but the abrupt glare of electric lights touches them back into mere
tables: mere tables, flecked with coffee-cups and liqueur-glasses; mere
tables, crumpling the lower halves of newspapers with their hard edges;
mere tables, where gesticulating arms rest their elbows, and ice-cream
plates nearly meet disaster in the excitement of a heated discussion. Venice
discusses. What will the Government do? Austria has asked that her troops
might cross over Italian territory, South of Switzerland, in order to attack
the French frontier. Austria! "I tell you, Luigi, that alliance the Government
made with the Central Powers was a ghastly blunder. You could never have
got Italians to fight on the side of Austrians. Blood is thicker than ink,
fortunately. But we are ready, thanks to Commandante Cadorna. It was a
foregone conclusion, ever since we refused passage to their troops." "I saw
Signor Colsanto, yesterday. He told me that the order had come from the
General Board of Antiquities and Fine Arts to remove everything possible
to Rome, and protect what can't be moved. He begins the work to-morrow."
"He does! Well, that tells us. Here, Boy, Boy, give me a paper. Listen to that
roar! There you are, cinque centesimi. Well, we're off, Luigi. It's declared.
Italy at war with Austria again. Thank God, we've wiped off the stain of
that abominable treaty." With heads bared, the crowd stands, and shouts,
and cheers, and the pigeons fleer away in frightened circles to the
sculptured porticoes of the Basilica. The crowd bursts into a sweeping song.
A great patriotic chorus. It echoes from side to side of the Piazza, it runs
down the colonnades of the Procuratie like a splashing tide, it dashes upon
the arched portals of Saint Mark's and flicks upward in jets of broken
music. Wild, shooting, rolling music; vibrant, solemn, dedicated music;
throbbing music flung out of loud-pounding hearts. The Piazza holds the
sound of it and lifts it up as one raises an offering before an altar. Higher—
higher—the song is lifted, it engulfs the four golden horses over the centre
door of the church. The horses are as brazen cymbals crashing back the
great song in a cadence of struck metal, the carven capitals are fluted reeds
to this mighty anthem, the architraves bandy it to and fro in revolving
canons of harmony. Up, up, spires the song, and the mounting angels call it
to one another in an ascending scale even to the star of fire on the topmost
pinnacle which is the Christ, even into the distant sky where it curves up
and over falling down to the four horizons, to the highest point of the
aconite-blue sky, the sky of the Kingdom of Italy.

Garibaldi's Hymn! For war is declared and Italy has joined the Allies!

Soft night falling upon Venice. Summer night over the moon-city, the
flower-city. Fiore di Mare! Garden of lights in the midst of dark waters,
your star-blossoms will be quenched, the strings of your guitars will snap
and slacken. Nights, you will gird on strange armour, and grow loud and
strident. But now— The gilded horses shimmer above the portico of Saint
Mark's! How still they are, and powerful. Pride, motion, activity set in a
frozen patience.

Suddenly—Boom! A signal gun. Then immediately the shrill shriek of a

steam whistle, and another, and whistles and whistles, from factories and
boats, yawling, snarling, mewling, screeching, a cracked cacophony of
horror.

Minutes—one—two—three—and the batteries of the Aerial-Guard

Station begin to fire. Shells—red and black, white and grey—bellow, snap,
and crash into the blue-black sky. A whirr—the Italian planes are rising.
Their white centre lights throw a halo about them, and, tip and tip, a red
light and a green, spark out to a great spread, closing together as the planes
gain in altitude. Up they go, the red, white, and green circles underneath
their wings and on either side of the fan-tails bright in the glow of the white
centre light. Up, up, slanting in mounting circles. "Holy Mother of God!
What is it?" Taubes over the city, flying at a great height, flying in a wedge
like a flight of wild geese. Boom! The anti-aircraft guns are flinging up
strings of luminous balls. Range 10,000 feet, try 10,500. Loud detonations,
echoing far over the Lagoon. The navigation lights of the Italian planes are
a faint triangle of bright dots. They climb in deliberate spirals, up and up,
up and up. They seem to hang. They hover without direction. Ah, there are
the Taubes, specks dotting the beam of a search-light. One of them is
banking. Two Italian machines dart up over him. He spins, round—round—
top-whirling, sleeping in speed, to us below he seems stationary. Pup-pup-
pup-pup-pup—machine-guns, clicking like distant typewriters, firing with
indescribable rapidity. The Italian planes drop signal balloons, they hang in
the air like suspended sky-rockets, they float down, amber balls, steadily
burning. The ground guns answer, and white buds of smoke appear in the
sky. They seem to blossom out of darkness, silver roses beyond the silver
shaft of the search-light. The air is broken with noise: thunder-drumming of
cannon, sharp pocking of machine-guns, snap and crack of rifles. Above,
the specks loop, and glide, and zig-zag. The spinning Taube nose-dives,
recovers, and zums upward, topping its adversary. Another Taube swoops in
over a Nieuport and wags its tail, spraying lead bullets into the Italian in a
wide, wing-and-wing arc. The sky is bitten red with stinging shrapnel. Two
machines charge head on, the Taube swerves and rams the right wing of the
Nieuport. Flame! Flame leaping and dropping. A smear from zenith to—
following it, the eye hits the shadow of a roof. Blackness. One poor devil
gone, and the attacking plane is still airworthy though damaged. It wobbles
out of the search-light and disappears, rocking. Two Taubes shake
themselves free of the tangle, they glide down—down—all round them are
ribbons of "flaming onions," they avoid them and pass on down, close over
the city, unscathed, so close you can see the black crosses on their wings
with a glass. Rifles crack at them from roofs. Pooh! You might as well try to
stop them with pea-shooters. They curve, turn, and hang up-wind. Small
shells beat about them with a report like twanged harp-strings. "Klar sum
Werfen?" "Jawohl." "Gut dock, werfen." Words cannot carry down
thousands of feet, but the ominous hovering is a sort of speech. People
wring their hands and clutch their throats, some cover their ears. Z-z-z-z-z!
That whine would pierce any covering. The bomb has passed below the
roofs. Nothing. A pause. Then a report, breaking the hearing, leaving only
the apprehension of a great light and no sound. They have hit us!
Misericordia! They have hit Venice! One—two—four—ten bombs. People
sob and pray, the water lashes the Rivas as though there were a storm.
Another machine falls, shooting down in silence. It is not on fire, it merely
falls. Then slowly the Taubes draw off. The search-light shifts, seeking
them. The gun-fire is spaced more widely. Field-glasses fail to show even a
speck. There is silence. The silence of a pulse which has stopped. But the
people walk in the brightness of fire. Fire from the Rio della Tanna, from
the Rio del Carmine, from the quarter of Santa Lucia. Bells peal in a fury,
fire-boats hurry with forced engines along the canals. Water streams jet
upon the fire; and, in the golden light, the glittering horses of Saint Mark's
pace forward, silent, calm, determined in their advance, above the portal of
the untouched church.

The night turns grey, and silver, and opens into a blue morning. Diamond
roses sparkle on the Lagoon, but the people passing quickly through the
Piazza are grim, and workmen sniff the smoky air as they fix ladders and
arrange tools. Venice has tasted war. "Evviva Italia!"
 City of soft colours, of amber and violet, you are turning grey-green, and
grey-green are the uniforms of the troops who defend you. The Bersaglieri
still wear their cocks' feathers, but they are green too, and black. Black as
the guns mounted on pontoons among the Lagoons before Venice, green as
the bundles of reeds camouflaging them from Austrian observation
balloons. Drag up metre after metre of grey-green cloth, stretch it over the
five golden domes of Saint Mark's Basilica. Hood their splendour in
umbrella bags of cloth, so that not one glint shall answer the mocking
shimmer of the moon. Barrows and barrows of nails for the wooden bastion
of the Basilica, hods and hods of mortar and narrow bricks to cover the old
mosaics of the lunettes. Cart-loads of tar and planking, and heaps, heaps,
hills and mountains of sand—the Lido protecting Venice, as it has done for
hundreds of years. They shovel sand, scoop sand, pour sand, into bags and
bags and bags. Thousands of bags piled against the bases of columns, rising
in front of carved corners, blotting out altars, throttling the open points of
arches. Porphyries, malachites, and jades are squarely boarded, pulpits and
fonts disappear in swaddling bands. Why? The battle front is forty miles
away in Friuli, and Venice is not a fortified town. Why? Answer, Reims!
Bear witness, Ypres! Do they cover Venice without reason? Nietzsche was a
German, still I believe they read him in Vienna. Blood and Iron! And is
there not also Blood and Stone, Blood and Bronze, Blood and Canvas?
"Kultur," Venetians, in the Rio del Carmine; there is no time to lose. Take
down the great ceiling pictures in the Ducal Palace and wrap them on
cylinders. Build a high trestle, and fashion little go-carts which draw with
string.

Hush! They are coming—the four beautiful horses. They rise in a whirl
of disturbed pigeons. They float and descend. The people watch in silence
as, one after another, they reach the ground. Across the tiles they step at
last, each pulled in a go-cart; merry-go-round horses, detached and solitary,
one foot raised, tramp over chequered stones, over chequered centuries. The
merry-go-round of years has brought them full circle, for are they not
returning to Rome?

For how long? Ask the guns embedded in the snow of glaciers; ask the
rivers pierced from their beds, overflowing marshes and meadows, forming
a new sea. Seek the answer in the faces of the Grenatieri Brigade, dying to a
man, but halting the invaders. Demand it of the women and children fleeing
the approach of a bitter army. Provoke the reply in the dryness of those eyes
which gaze upon the wreck of Tiepolo's ceiling in the Church of the Scalzi.
Yet not in Italy alone shall you find it. The ring of searching must be
widened, and France, England, Japan, and America, caught within its edge.
Moons and moons, and seas seamed with vessels. Needles stitching the
cloth of peace to choke the cannon of war.

The boat draws away from the Riva. The great bronze horses mingle
their outlines with the distant mountains. Dim gold, subdued green-gold,
flashing faintly to the faint, bright peaks above them. Granite and metal,
earth over water. Down the canal, old, beautiful horses, pride of Venice, of
Constantinople, of Rome. Wars bite you with their little flames and pass
away, but roses and oleanders strew their petals before your going, and you
move like a constellation in a space of crimson stars.

So the horses float along the canal, between barred and shuttered
palaces, splendid against marble walls in the fire of the sun.

Printed in the United States of America.

Books by AMY LOWELL

PUBLISHED BY
HOUGHTON MIFFLIN COMPANY

Poetry

WHAT'S O'CLOCK
LEGENDS
PICTURES OF THE FLOATING WORLD
CAN GRANDE'S CASTLE
MEN, WOMEN AND GHOSTS
SWORD BLADES AND POPPY SEED
A DOME OF MANY-COLOURED GLASS
A CRITICAL FABLE

(IN COLLABORATION WITH FLORENCE ATSCOUGH)

FIR-FLOWER TABLETS: POEMS TRANSLATED FROM THE
CHINESE

Prose

TENDENCIES IN MODERN AMERICAN POETRY

SIX FRENCH POETS: STUDIES IN CONTEMPORARY LITERATURE
JOHN KEATS
 *** END OF THE PROJECT GUTENBERG EBOOK CAN
GRANDE'S CASTLE ***

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