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Evaluation of chocolate as a source of dietary copper

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Chocolate has frequently been proposed to be a valuable source of dietary copper, but data on the copper content of major contemporary chocolate brands are scarce. The copper content of 22 brands of chocolate, many of which are sold worldwide, is thus presented here. A reliable hot ashing procedure to determine the copper content of chocolate by inductively coupled plasma atomic emission spectroscopy is also described. It was found that the copper contents of the chocolates analyzed here varied in the range of 1.85 ± 0.10 to 16.50 ± 1.29 μg/g. There was a linear correlation of the copper content of chocolate to its cocoa content with a correlation coefficient R 2 of 0.89, showing that the copper was largely contributed to the chocolate by the cocoa. The value of chocolate as a source of dietary copper is discussed.
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Eur Food Res Technol (2014) 238:1063–1066
DOI 10.1007/s00217-014-2240-x
SHORT COMMUNICATION
Evaluation of chocolate as a source of dietary copper
Thomas Weber · Marc Solioz
Received: 4 February 2014 / Revised: 14 April 2014 / Accepted: 28 April 2014 / Published online: 10 May 2014
© Springer-Verlag Berlin Heidelberg 2014
day recommended for grown-up, healthy adults [1]. Copper
intake beyond the DRI should probably be of no concern
for healthy adults. According to a recent study, a copper
intake of up to 8 mg/day for 6 months did not appear to
have any adverse effects in healthy individuals [2]. There
are, however, conditions in which excessive copper intake
may pose a risk, such as for individuals with Wilson dis-
ease, a genetic defect in copper secretion [24].
There is considerable debate of whether the DRI levels
are sufficient and in fact, recommendations for adults in the
United Kingdom, the European Community, and Australia/
New Zealand are higher and range from 1.1 to 1.2 mg/day.
The required copper intake may vary a great deal depend-
ing on the source of the copper and the nutritional context,
both of which can affect the bioavailability (bioaccessibil-
ity) of the copper [3]. The focus in establishing nutritional
guidelines for copper and maximal tolerable copper levels
in drinking water has traditionally been placed on toxic-
ity rather than essentiality. Currently, there is concern that
some populations may be copper deficient and this prob-
lem may be exacerbated in special circumstances, such as
in disease or following bariatric surgery, which is dramati-
cally on the rise [48].
The copper content of food varies over a wide range. It
is lowest in fats and oils, dairy products, sugar, tuna, and
lettuce (<0.4 μg/g). Higher copper levels are present in leg-
umes, mushrooms, chocolate, nuts, and seeds (>2.4 μg/g).
The best sources of copper are beef liver and oysters, which
typically contain 70–200 μg/g of copper [9, 10]. With the
increasing awareness in nutrition, particularly in the West-
ern world, people frequently turn to Internet sites for infor-
mation on nutritional aspects. As a good nutritional source
of copper, chocolate is often being recommended (e.g.,
http://www.healthaliciousness.com/articles/high-copper-
foods.php). On the other hand, liver and oysters are absent
Abstract Chocolate has frequently been proposed to be
a valuable source of dietary copper, but data on the copper
content of major contemporary chocolate brands are scarce.
The copper content of 22 brands of chocolate, many of
which are sold worldwide, is thus presented here. A reliable
hot ashing procedure to determine the copper content of
chocolate by inductively coupled plasma atomic emission
spectroscopy is also described. It was found that the copper
contents of the chocolates analyzed here varied in the range
of 1.85 ± 0.10 to 16.50 ± 1.29 μg/g. There was a linear
correlation of the copper content of chocolate to its cocoa
content with a correlation coefficient R2 of 0.89, showing
that the copper was largely contributed to the chocolate by
the cocoa. The value of chocolate as a source of dietary
copper is discussed.
Keywords Chocolate · Copper content · Nutrition ·
Deficiency
Introduction
Copper is an essential micronutrient and functions as a
cofactor in over 30 enzymes in humans. The latest dietary
reference intakes (DRI) for copper range form 0.5 g/day for
infants to 1.3 mg/day for lactating women, with 0.9 mg/
T. Weber · M. Solioz (*)
Department Clinical Research, University of Bern, Murtenstrasse 35,
3010 Berne, Switzerland
e-mail: marc@solioz-scientific.ch
M. Solioz
Department of Plant Physiology and Biotechnology, Tomsk
State University, Prospect Lenina 36, 634050 Tomsk, Russian
Federation
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1064 Eur Food Res Technol (2014) 238:1063–1066
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in many recommendations for copper-rich foods, probably
due to the lack of tradition of eating these foods in some
countries.
Due to a lack of data on the copper content of contem-
porary chocolates, we here determined the copper content
of 22 major brands of chocolate by dry ashing and induc-
tively coupled plasma atomic emission spectroscopy (ICP–
AES). It was found that the copper content linearly corre-
lated with the cocoa content. Thus, cocoa-rich chocolates
should be recommended if chocolate is to serve as a source
of dietary copper.
Materials and methods
Different brands of chocolate were bought in local shops
and supermarkets in Berne, Switzerland, and stored at
room temperature. The cocoa content was taken either from
the product label or was inquired at the manufacturer. For
copper measurements, samples of 1–1.5 g of chocolate
were ashed in a kiln at 400 °C for 3 h and at 600 °C for
14 h. Fused silica crucibles (99.7 % Al2O3, Alsint, Faust
Laborbedarf AG, Schaffhausen, Switzerland) rather than
ceramic crucibles had to be used. Extensive experiments in
our laboratory had shown that standard ceramic crucibles
were unsuitable as they absorbed variable amounts of cop-
per, depending on the history of the crucibles. After cooling
of the ashed samples, the residues were dissolved in 1 ml
of 67 % HNO3 for 1 h under agitation. After addition of
1 ml of 30 % H2O2 and further incubation for 1 h at room
temperature, the sample was brought to a final volume of
6 ml with water. This resulted in a clear solution without
insoluble residues. Copper concentrations were meas-
ured by ICP–AES, using a Jobin–Yvon JY 24 instrument
(HORIBA Jobin–Yvon GmbH, Munich, Germany) at a
wavelength of 324.754 nm and using Gauss integration for
0.5 min. The lower limit of detection for copper was five
parts per billion.
Results
A number of published methods were assessed in their
reliability to measure copper in chocolate. It was found
that published wet ashing procedures in mixtures of con-
centrated HNO3 and H2O2, or dry ashing at 500 °C gave
poor reproducibility across chocolates with widely dif-
fering cocoa and fat contents [11, 12]. These published
methods had been evaluated with standard reference mate-
rials, which were based on bovine liver or rice flour sam-
ple matrices. However, these matrices are a poor reference
material for chocolate, which is rich in fats highly resistant
to wet oxidation. So, these published methods necessitate
filtration or centrifugation of the samples. The dry ashing
procedure described here resulted in clear, residue-free
samples, which gave reproducible copper values across all
samples.
Table 1 shows the copper contents of 22 brands of choc-
olate. Many of the brands are marketed worldwide, while
a few are products specific to the Swiss market. The low-
est copper contents were found in two brands of white
chocolate, which are not chocolates in the strict sense of
the word, since they do not contain cocoa. They had cop-
per contents of 0.11 ± 0.05 and 1.02 ± 0.13 μg/g. For
the cocoa-containing chocolate brands, the copper values
ranged from 1.85 ± 0.10 to 16.50 ± 1.29 μg/g. Interest-
ingly, there was a very good, linear correlation between the
cocoa content and the copper content of chocolate brands
(R2 = 0.89), without any dramatic outliers (Fig. 1). This
suggests that the copper content of chocolate originates
largely from the cocoa. This is also supported by the two
white “chocolates”, which did not contain cocoa and exhib-
ited the lowest copper contents. Thus, the value of choco-
late as a source of dietary copper directly depends on the
cocoa content: Chocolates with a high cocoa content are
a better source of dietary copper than those with a low
content.
Discussion
The copper content of chocolate has not systematically
been addressed in the scientific literature. Although a num-
ber of reports deal with the copper content of chocolate and
other cocoa products such as chocolate drinks, cakes, etc.,
chocolate brands and cocoa contents were not given [8, 9,
1216]. We thus saw a need to assess the copper content
of specific chocolate brands and relate them to the cocoa
content.
We here determined the copper content of 22 differ-
ent chocolates, many of which find worldwide distribu-
tion today. There was a linear correlation between the
cocoa content of these chocolates and the copper content,
which ranged from 1.85 ± 0.10 μg/g of a chocolate con-
taining 31 % cocoa to 16.50 ± 1.29 μg/g of a chocolate
with 85 % cocoa. This clearly suggests that the copper is
contributed by the cocoa. Indeed, cocoa beans are high in
copper. The copper content of fermented cocoa beans from
Ghana was reported to range from 88 to 173 μg/g, depend-
ing on the length of pod storage [17]. How storage could
affect the copper content is hard to perceive and may reflect
a methodological problem. The copper content of cocoa
powder from local markets in Greece, Pakistan, and Brazil
ranged from 27 to 52 μg/g [12, 18, 19]. Hernandez et al.
[20] analyzed the copper, zinc, manganese, iron, and mag-
nesium content of primary chocolate mass from different
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manufacturers and found copper to vary between 11 and
27 μg/g. They concluded that the metal contents depended
on both, the origin of the cocoa beans and the grinding
and milling process, necessary to obtain a smooth choco-
late texture. Grinding and milling involves heavy equip-
ment and extended contact times of the cocoa mass with
various metal alloys. This can of course lead to enrich-
ment of the cocoa with metal ions. Raw cocoa beans from
plantations in Nigeria had a copper contents ranging from
104 to 642 μg/g [21]. According to the authors, the higher
copper contents were due to the use of copper sulfate for
disease prevention on these plantations. Clearly, cocoa in
various forms has an intrinsically high copper content. It
would be interesting to know how this relates to cocoa spe-
cies, origin, and growth conditions. However, in today’s
global markets, it has become impossible to track the origin
and species of the cocoa beans and chocolate producers are
unwilling or probably even unable to provide correspond-
ing information.
A majority of chocolates on the market have a cocoa
content in the range of 30–60 % and thus an average copper
content of around 4 μg/g. A typical 100 g bar of choco-
late thus contains 400 μg of copper and would contribute
44 % of the daily DRI for adults. On the other hand, 50 g of
chocolate high in cocoa would contribute 100 % of the DRI
for copper. In contrast to the copper content, the caloric
value of chocolate does not differ much between brands
and is around 5 kcal/g (21 kJ/g). If chocolate is considered
as a copper source, preference should clearly be given to
brands with a high cocoa and thus a high copper content to
minimize fat and energy intake.
According to an analysis of the eating habits of the
elderly in the USA in 2000, chocolate contributed only
12 % to the individual copper consumption [22]. This
implies the consumption of 5–40 g/day of chocolate,
Table 1 Copper and cocoa
content of different chocolate
brands
a STD, standard deviation
based on at least three
measurements
Nr. Chocolate brand Cocoa (%) Cu (μg/g) STDa (μg/g)
1 Lindt Excellence 70 12.14 1.04
2 Cailler Frigor Black 46 5.78 0.36
3 Cailler Frigor Milk 36 4.20 0.08
4 Lindt Excellence Prodigieux 90 15.28 1.17
5 Lindt Cresta Classic 30 2.64 0.13
6 Cailler Crémant Intense 64 10.80 0.47
7 Toblerone, legendary triangular chocolate 28 2.47 0.03
8 Lindt Excellence Puissant 85 16.50 1.29
9 Coop Prix Garantie chocolate with milk 30 2.42 0.10
10 Frey Giandor Noir 44 5.05 0.09
11 Coop Qualité & Prix Milk 31 1.85 0.10
12 Frey Milk Extra 31 2.37 0.10
13 Coop Qualité & Prix Les Classiques Crémant 60 7.51 0.39
14 Frey Noir Special 72 9.84 0.29
15 Criollo 1er Cru Orinoco 72 9.67 0.60
16 MBudget chocolate white 0 0.11 0.05
17 Wander Ovomaltine noir (Ovaltine) 60 6.91 0.47
18 MBudget milk chocolate 30 2.23 0.13
19 Suchard Marzipan 18 2.50 0.07
20 Frey Giandor milk chocolate with almond cream 37 3.58 0.30
21 Camille Bloch Torino 34 3.19 0.44
22 Frey Giandor White 0 1.02 0.13
R² = 0.8929
0
5
10
15
20
0 20406080100
Copper content [μg/g]
Cocoa content [%]
Fig. 1 Relationship of copper content and cocoa content of choco-
late. The copper content of 22 brands of chocolate was plotted against
the cocoa content. The error bars show the standard deviations of at
least three independent measurements. The linear regression exhib-
ited a correlation of R2 = 0.89
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1066 Eur Food Res Technol (2014) 238:1063–1066
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depending on the cocoa content. Chocolate is clearly a
good source of copper, and cocoa powder has successfully
been used to combat copper deficiency associated with tube
feeding in Japan [23]. Nevertheless, better sources for extra
copper would be beef liver or oysters, of which 5–15 g
would suffice to provide the DRI and would be accompa-
nied by a lower fat and energy intake.
Chocolate contains several biologically active con-
stituents such as methylxanthines, biogenic amines, and
cannabinoid-like fatty acids, all of which are potentially
addictive substances. Indeed, excessive craving for choco-
late is a well-known phenomenon [25]. In addition, choco-
late has also been advocated as an antioxidant nutrient for
cardiovascular health [26]. These aspects are beyond the
realm of this discussion, but it should be noted that, aside
of its value as a copper source, chocolate remains a highly
interesting and enigmatic component of the human diet and
clearly deserves further research.
Acknowledgments This work was supported by Grant
CR32I3E-136073 from the Swiss National Science Foundation and a
Russian Federation Government Grant to leading scientists.
Conflict of interest None.
Compliance with Ethics Requirements This article does not con-
tain any studies with human or animal subjects.
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... The concentration of Cu in the dark chocolate varied between 6.70 mg/kg (S3) and 17.14 (S12), which was in line with the literature [25][26][27][28][29][30]32], whilst substantially higher concentrations of Cu were reported by Karas , et al. [31]. In addition, some authors reported a linear correlation between cocoa and Cu content [26], but no such correlation was observed in this study. ...
... The concentration of Cu in the dark chocolate varied between 6.70 mg/kg (S3) and 17.14 (S12), which was in line with the literature [25][26][27][28][29][30]32], whilst substantially higher concentrations of Cu were reported by Karas , et al. [31]. In addition, some authors reported a linear correlation between cocoa and Cu content [26], but no such correlation was observed in this study. ...
... respectively. Indeed, 100 g of chocolate may contribute to 50% of Cu daily recommended intake, and those with higher cocoa percentage even more [26]. Substantially lower dietary intake was observed for Zn, 12.2−34.6% ...
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Cocoa beans are part of the cocoa plant fruit (Theobroma cacao L.) used to prepare various products such as chocolate, cocoa butter, jelly, liqueurs, cosmetics, etc. Dark chocolate is consumed worldwide by different populations and is known for its good taste, making it one of the most favoured food products. This work aimed to determine the content of total polyphenols (TPC), total flavonoids (TFC), and the antioxidant potential measured through the ability to scavenge DPPH free radicals (DPPH), ferric reducing power (FRAP), and total antioxidant capacity (TAC), as well as major and trace elements contained in twelve commercially available dark chocolate samples, with cocoa content ranging from 40% to 99%. The total polyphenols content ranged between 10.55 and 39.82 mg/g GAE, while the total flavonoid content was from 10.04 to 37.85 mg/g CE. All applied antioxidant assays indicate that the sample with the highest cocoa percentage shows the greatest antioxidant activity (DPPH: 48.34% of inhibition; FRAP: 89.00 mg/g GAE; TAC: 83.86 mg/g AAE). Statistical methods were applied to establish the differences between the samples concerning TPC, TFC, DPPH, FRAP and TAC, as well as to differentiate the samples according to the mineral content. The results indicated that the differences in TPC and TFC between different samples depended on the cocoa content and the addition of dried fruit pieces. A good correlation between antioxidant potency composite index (ACI) and declared cocoa content was noticed (R2 = 0.8034), indicating that the declared percentage of cocoa is a reliable indicator for antioxidant activity of analysed dark chocolate samples. The nutritional evaluation proved that the studied chocolate samples were an excellent source of Mg, Fe, Mn and Cu.
... Similarly, and most importantly in the clinical context of Wilson disease, products containing high amounts of copper like dark chocolate and cocoa should not be consumed by patients with Wilson disease [66]. This is in line with early observations that chocolate contains copper in amounts up to 16.50 ± 1.29 μg/g of a chocolate with 85% cocoa, and is associated with a linear correlation between the copper content of the chocolate and its cocoa content and a correlation coefficient of 0.89, showing that the cocoa largely contributed to the copper in the chocolate [67]. Raw cocoa beans from plantations in Nigeria had copper contents ranging from 104 μg/g to 642 μg/g, attributed to the use of copper sulfate as a fungicide for disease prevention on these plantations and detected in soil and vegetation components [68]. ...
... Most of the commonly consumed foods contain trace amounts of copper [66,136], which makes dietary copper restriction less feasible, although foods with high copper content should be avoided to support therapy with chelators [66]. Foods with a high copper content include cocoa derived from Owena cocoa (Theobroma cacao L.) and contaminated with copper from copper-containing fungicides, dark chocolate from contaminated cocoa, nuts, raisins, shellfish, oysters, and butchery foodstuff from liver and kidneys derived from cattle grazing, possibly, on grounds with plants contaminated by copper [67,68,128,136]. ...
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Humans are continuously exposed to various heavy metals including copper, iron, cadmium, and arsenic, which were specifically selected for the current analysis because they are among the most frequently encountered environmental mankind and industrial pollutants potentially causing human health hazards and liver injury. So far, these issues were poorly assessed and remained a matter of debate, also due to inconsistent results. The aim of the actual report is to thoroughly analyze the positive as well as negative effects of these four heavy metals on human health. Copper and iron are correctly viewed as pollutant elements essential for maintaining human health because they are part of important enzymes and metabolic pathways. Healthy individuals are prepared through various genetically based mechanisms to maintain cellular copper and iron homeostasis, thereby circumventing or reducing hazardous liver and organ injury due to excessive amounts of these metals continuously entering the human body. In a few humans with gene aberration, however, liver and organ injury may develop because excessively accumulated copper can lead to Wilson disease and substantial iron deposition to hemochromatosis. At the molecular level, toxicities of some heavy metals are traced back to the Haber Weiss and Fenton reactions involving reactive oxygen species formed in the course of oxidative stress. On the other hand, cellular homeostasis for cadmium and arsenic cannot be provided, causing their life-long excessive deposition in the liver and other organs. Consequently, cadmium and arsenic represent health hazards leading to higher disability-adjusted life years and increased mortality rates due to cancer and non-cancer diseases. For unknown reasons, however, liver injury in humans exposed to cadmium and arsenic is rarely observed. In sum, copper and iron are good for the human health of most individuals except for those with Wilson disease or hemochromatosis at risk of liver injury through radical formation, while cadmium and arsenic lack any beneficial effects but rather are potentially hazardous to human health with a focus on increased disability potential and risk for cancer. Primary efforts should focus on reducing the industrial emission of hazardous heavy metals.
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Wilson disease is a genetic disorder of the liver characterized by excess accumulation of copper, which is found ubiquitously on earth and normally enters the human body in small amounts via the food chain. Many interesting disease details were published on the mechanistic steps, such as the generation of reactive oxygen species (ROS) and cuproptosis causing a copper dependent cell death. In the liver of patients with Wilson disease, also, increased iron deposits were found that may lead to iron-related ferroptosis responsible for phospholipid peroxidation within membranes of subcellular organelles. All topics are covered in this review article, in addition to the diagnostic and therapeutic issues of Wilson disease. Excess Cu2+ primarily leads to the generation of reactive oxygen species (ROS), as evidenced by early experimental studies exemplified with the detection of hydroxyl radical formation using the electron spin resonance (ESR) spin-trapping method. The generation of ROS products follows the principles of the Haber–Weiss reaction and the subsequent Fenton reaction leading to copper-related cuproptosis, and is thereby closely connected with ROS. Copper accumulation in the liver is due to impaired biliary excretion of copper caused by the inheritable malfunctioning or missing ATP7B protein. As a result, disturbed cellular homeostasis of copper prevails within the liver. Released from the liver cells due to limited storage capacity, the toxic copper enters the circulation and arrives at other organs, causing local accumulation and cell injury. This explains why copper injures not only the liver, but also the brain, kidneys, eyes, heart, muscles, and bones, explaining the multifaceted clinical features of Wilson disease. Among these are depression, psychosis, dysarthria, ataxia, writing problems, dysphagia, renal tubular dysfunction, Kayser–Fleischer corneal rings, cardiomyopathy, cardiac arrhythmias, rhabdomyolysis, osteoporosis, osteomalacia, arthritis, and arthralgia. In addition, Coombs-negative hemolytic anemia is a key feature of Wilson disease with undetectable serum haptoglobin. The modified Leipzig Scoring System helps diagnose Wilson disease. Patients with Wilson disease are well=treated first-line with copper chelators like D-penicillamine that facilitate the removal of circulating copper bound to albumin and increase in urinary copper excretion. Early chelation therapy improves prognosis. Liver transplantation is an option viewed as ultima ratio in end-stage liver disease with untreatable complications or acute liver failure. Liver transplantation finally may thus be a life-saving approach and curative treatment of the disease by replacing the hepatic gene mutation. In conclusion, Wilson disease is a multifaceted genetic disease representing a molecular and clinical challenge.
... Different analytical techniques such as flame atomic absorption spectrometry [FAAS (13)(14)(15)(16)(17)(18)], graphite furnace atomic absorption spectrometry [GFAAS (19)], high-resolution continuum source atomic absorption spectrometry [HR-CS-AAS (20)], and inductively coupled plasma optical emission spectrometry [ICP-OES (21)(22)(23)] are widely used to determine element concentrations in chocolate samples. A wide variety of sample preparation methods, including dry ashing (24,25), wet digestion (10,(25)(26)(27) and microwave-assisted acid digestion (20)(21)(22)(23)28), emulsification (16,18), slurry sampling (17,27), and extraction methods (3,14,15,19), have been applied to chocolate samples prior the use of atomic spectrometric-based techniques. The sample preparation methodology is key to ensuring the maximum detection of the target analyte by spectrometric detection (29). ...
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Background: Chocolate is a rich source of essential and non-essential elements. A new liquid-liquid extraction approach, extraction induced by emulsion breaking (EIEB), is proposed in which the analyzed elements are transferred from the organic phase to the aqueous phase before measurement by flame atomic absorption spectrometry (FAAS). Objective: To compare EIEB to microwave digestion (MWD) for extraction of elements from chocolate prior to FAAS. Methods: EIEB parameters were varied to optimize the procedure. EIEB-FAAS was then compared to MWD-FAAS for the analysis of Ca, Cu, Fe, Mn, Ni, and Zn in milk and dark chocolate samples. A certified reference material (NIST 2384, baking chocolate) was analyzed to determine recoveries of Ca, Cu, Fe, Mn, and Zn by the two methods. Results: The optimized EIEB extraction method involves dilution of tempered chocolate with toluene, ultrasonic emulsification with acidified Triton X-114, breaking the emulsion by heating, and centrifugation to produce two well-defined phases. Analysis of dark and milk chocolate samples showed similar repeatability by EIEB-FAAS (RSDr 0.3 to 6.6% in dark and 0.5 to 8.7% in milk) and MWD-FAAS (RSDr 0.5 to 5.4% in dark and 0.7 to 10.2% in milk), with no significant difference detected between methods for analysis of Ca, Cu, Fe, Mn, Ni, and Zn based on Student's t-test. Analysis of NIST 2384 baking chocolate certified reference material for Ca, Cu, Fe, Mn, and Zn demonstrated recoveries of 98.6 to 99.5% for EIEB-FAAS compared to 95.8 to 98.6% for MWD-FAAS. Conclusion: EIEB-FAAS was shown to provide high recovery and excellent repeatability for accurate determination of Ca, Cu, Fe, Mn, Ni, and Zn from dark and milk chocolates. Highlight: The EIEB-FAAS method is simpler and requires fewer reagents compared to other sample preparation methods and allows the calibration to be carried out using aqueous calibration solutions.
... Some scientific literature, similar to the proposed method, FDA and CAC per serving, CAC per 100 g, and CAC per 100 kcal, defined liver 13,14,15,16,17,18,19,20,21,22,23,24 , kidney 15,20 , oyster 14,15,17,19,20,21,22,23,24,25,26 , lobster 17,19 , cocoa 17,19,27 , cocoa-rich chocolate 15,17,19,20,21,28 , potatoes 17,29 , Brazil nuts 25 , cashew nuts 17,23,25 , hazelnuts 25 , walnuts 25 , sesame seeds 19,23 , peanuts 25 , soybeans 23 , lentils 25 , kidney beans 29 , barley 25 , and oats 25 as foods containing appropriate copper levels (to achieve adequate copper intake). ...
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... The International Agency for Research on Cancer (IARC) classifies Cd and Pb as elements that are carcinogenic (Group 1) and possibly carcinogenic (Group 2B) for humans, respectively (IARC 2019). On the other hand, Cu is an essential micronutrient and functions as a cofactor for more than 30 enzymes (Weber and Solioz 2014). ...
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In this work, an effective and simple method is proposed for the simultaneous determination of cadmium, lead and copper in chocolate samples by Square Wave Anodic Stripping Voltammetry (SWASV). An ultrasonic bath was used for the extraction of cadmium, lead and copper from fourteen chocolate samples using HNO3 solution (7 mol L⁻¹). The electrochemical system consisted of a cell with three electrodes and HCl solution (10 mmol L⁻¹) as the supporting electrolyte. An efficient extraction of the metals (~100%) was attained after 1 h of ultrasonic pre-treatment. Quantitative analysis was carried out by the standard addition method. Good linearity, precision and accuracy were obtained in the range of concentrations examined. The accuracy was evaluated by means of a reference sample of spiked skim milk powder (BCR 151) to prove the reliability of the method. Detection limits (LOD) of 0.089, 0.059 and 0.018 µg g⁻¹ were found for cadmium, copper and lead, respectively, in the chocolate samples. Concentrations in chocolate samples were 4.30–138 µg g⁻¹ for Cu and 0.83–27.9 µg g⁻¹ for Pb, with no significant Cd. The simultaneous determination brings advantages to other methods already reported for chocolate analysis and the samples preparation proposed avoids the traditional sample mineralization step. These characteristics show this new method is especially attractive for case studies and routine analysis.
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A theme that emerges from this year's Update is that of ‘green’ chemistry. This, in part, explains the larger than usual number of publications focusing on sample preparation, especially those concerned with the analysis of foods. Procedures that involved dilute acids while still achieving digestion of the specimens were reported by various workers. Meanwhile the trend towards smaller and smaller volumes continues with developments on the microscale. These aspects were noted in both the original work and in reviews. Last year saw the large number of papers concerned with metallic prostheses and this topic continues to attract interest. In possibly the first publication in which ICP-MS/MS was used for a clinical application, concentrations of Ti were determined in serum from healthy subjects and patients with hip implants. Concern is evident over the toxicological implications of consumption of rice grown in regions where water is contaminated with As. This has led to several reports of analytical methods and of concentrations in foods and total diets. Localisation of the As into different parts of the plant and the rice was also investigated and, in some reports this included speciation as well as the total As concentrations. Compared with the last few years, Se longer dominates the speciation work reported in this Update and there are more reports relating to As and Hg. A new class of arsenolipids, cationic trimethylarsenio fatty alcohols, were discovered in Capelin Oil. The number of publications applying XRF spectrometry to imaging elements within tissues appears to be increasing with localisation in bone of particular interest. Laser ablation ICP-MS in combination with other techniques, TOF-SIMS, XRD or XPS was also noted, to increase the information obtained.
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A theme that emerges from this year's Update is that of ‘green’ chemistry. This, in part, explains the larger than usual number of publications focussing on sample preparation, especially those concerned with the analysis of foods. Procedures that involved dilute acids while still achieving digestion of the specimens were reported by various workers. Meanwhile the trend towards smaller and smaller volumes continues with developments on the micro-scale. These aspects were noted in both the original work and in reviews. Last year saw the large number of papers concerned with metallic prostheses and this topic continues to attract interest. In possibly the first publication in which ICP-MS/MS was used for a clinical application, concentrations of Ti were determined in serum from healthy subjects and patients with hip implants. Concern is evident over the toxicological implications of consumption of rice grown in regions where water is contaminated with As. This has led to several reports of analytical methods and of concentrations in foods and total diets. Localisation of the As into different parts of the plant and the rice was also investigated and, in some reports this included speciation as well as the total As concentrations. Compared with the last few years, Se longer dominates the speciation work reported in this Update and there are more reports relating to As and Hg. A new class of arsenolipids, cationic trimethylarsenio fatty alcohols, were discovered in Capelin Oil. The number of publications applying XRF spectrometry to imaging elements within tissues appears to be increasing with localisation in bone of particular interest. Laser ablation ICP-MS in combination with other techniques, TOF-SIMS, XRD or XPS was also noted, to increase the information obtained.
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Unlabelled: Copper (Cu) deficiency has been reported to influence lipid metabolism, but the effects in humans are controversial. To evaluate the effects of 8 mg Cu/day supplementation (as copper sulfate) for 6 months on the lipid profile and hepatic function of apparently healthy men. The design was randomized double-blind placebo-controlled clinical trial. Subjects and methods: 60 apparently healthy males aged 18-51 years were randomly assigned to Cu supplementation (n = 30) or placebo (n = 30). There was a nonsignificant reduction of 17 % in total cholesterol in both groups after supplementation. A 23 % nonsignificant reduction was observed in LDL cholesterol levels in the supplemented group. There was a nonsignificant increase of HDL cholesterol of 47 and 66 % in the control and supplemented groups, respectively. Triglyceride levels over 150 mg/dl were found in 17 subjects supplemented and 13 controls at baseline and decreased after supplementation to seven and eight subjects, respectively. There were no effects on serum Cu concentration or ceruloplasmin (protein) and hepatic transaminases. Supplementation of 8 mg Cu for 6 months had no effect on lipid profile of apparently healthy Chilean men with adequate Cu status.
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Moderate/severe obesity is on the rise in the United States. Weight management includes bariatric surgery, which is effective and can alleviate morbidity and mortality from obesity-associated diseases. However, many individuals are dealing with nutritional complications. Risk factors include: 1) preoperative malnutrition (e.g., vitamin D, iron); 2) decreased food intake (due to reduced hunger and increased satiety, food intolerances, frequent vomiting); 3) inadequate nutrient supplementation (due to poor compliance with multivitamin/multimineral regimen, insufficient amounts of vitamins and/or minerals in supplements); 4) nutrient malabsorption; and 5) inadequate nutritional support (due to lack of follow-up, insufficient monitoring, difficulty in recognizing symptoms of deficiency). For some nutrients (e.g., protein, vitamin B-12, vitamin D), malnutrition issues are reasonably addressed through patient education, routine monitoring, and effective treatment strategies. However, there is little attention paid to other nutrients (e.g., zinc, copper), which if left untreated may have devastating consequences (e.g., hair loss, poor immunity, anemia, defects in neuro-muscular function). This review focuses on malnutrition in essential minerals, including calcium (and vitamin D), iron, zinc, and copper, which commonly occur following popular bariatric procedures. There will be emphasis on the complexities, including confounding factors, related to screening, recognition of symptoms, and, when available, current recommendations for treatment. There is an exceptionally high risk of malnutrition in adolescents and pregnant women and their fetuses, who may be vulnerable to problems in growth and development. More research is required to inform evidence-based recommendations for improving nutritional status following bariatric surgery and optimizing weight loss, metabolic, and nutritional outcomes.
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This work reported the results of copper content in the soil profiles of three different aged cocoa plantations subjected to copper- fungicide application and the various vegetational components (pod, beans, leaves, trunk bark, lateral root and twig). Soil copper at various depth considered ranged from 5.0 -42.0 μgg-1. Copper contents in both fresh and dry leaves of cocoa and banana were consistently high in all the three plantations. The copper contents ranged from 56-300μgg-1 (dry wt.) in cocoa trunk bark and 86-161μgg-1 in banana trunk bark. There was evidence of age-dependent accumulation of copper in cocoa pod and beans; hence it can be used to assess the degree of copper contamination. Copper contents from roots ranged from 408-2, 203μgg-1 (dry wt.). The soil did not appear contaminated by copper but alternative fungicide is recommended since copper accumulation in the cocoa beans was evident. Bangladesh J. Sci. Ind. Res. 41(3-4), 129-140, 2006
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Digestion methods were validated using standard certified reference materials (BCR-185R, SRM-1577b and BCR-679). The microwave - assisted digestion was found the most reliable and accurate method for chocolate samples. The recovery rates were 96-102 %, 92-98 % and 90-96 % for the microwave digestion, the wet digestion and the dry ashing, respectively. The results obtained using certified reference materials were in a good agreement with certified values. Flame atomic absorption spectrometry (FAAS) was used for the determination of Fe, Cu, Zn, As and Fig. Graphite furnace atomic absorption spectrometry (GFAAS) was also used for the determination of Ni, Cd and Pb in chocolate with pistachio belonging to the same brand sold in different markets in Bursa, Turkey. In total, twelve chocolate samples were analysed for this purpose. Cu, Zn, Fe, Cd, Ni, Pb, As and Hg levels ranged from 9.15 to 10.61 mg..kg(-1), 14.05 to 16.68 mg.kg(-1), 2.31 to 3.67 mg.kg(-1), 0.01 to 0.03 mg.kg(-1), 0.33 to 1.52 mg.kg(-1), 0.001 to 0.04 mg.kg(-1), 0.004 to 0.02 mg.kg(-1) and 0.008 to 0.02 mg.kg(-1), respectively. The elemental contents of the analysed samples were within the ranges reported by the legal authorities for chocolate and other foods.
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The levels of cadmium, lead, copper and arsenic were determined in two batches of raw cocoa and semifinished chocolate products sampled at various intermediate stages of the manufacturing process. The metal contents of eighteen chocolate bars produced by four chocolate making factories were also determined. A nalyses of the metal contents in cocoa containing samples were effected by dry ashing of the samples at 450°C, followed by inductively coupled plasma atomic emission spectrometry. Average recoveries of 90 to 97% were obtainedfor the metals when the samples were spiked with known concentrations of metals. The variations in the metal contents of raw cocoa, semi-finished and finished products show that there were no effective contaminations of metals during the manufacturing process; the amount of metals in the finished products corresponded to the fraction of cocoa mass present. The metal contents of locally produced chocolates were within acceptable levels except for arsenic which bordered on the limit.
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Different chocolate types belonging to plain chocolate, milk chocolate and chocolate with pistachio that were supplied from different markets in Bursa, Turkey were investigated for trace element contents. Determinations of mercury (Hg), arsenic (As), iron (Fe), copper (Cu) and zinc (Zn) were performed by using Flame Atomic Absorption Spectrometry (FAAS), while the other elements (lead (Pb), cadmium (Cd) and nickel (Ni)) were determined by Graphite Furnace Atomic Absorption Spectrometry (GFAAS). According to chocolate types, contents ranged from 0.03 to 0.04 (Pb), 0.02 to 0.04 (Hg), 0.02 to 0.03 (Cd), 0.01 to 0.02 (As), 1.29 to 4.78 (Ni), 5.74 to 10.61 (Cu), 2.52 to 3.67 (Fe) and 12.11 to 16.68 mg kg-1 (Zn), respectively. The levels of Cu, Zn and Fe were highest in chocolate with pistachio samples. The contents of Hg and Ni were highest in milk and plain chocolates, respectively. Arsenic (As) was highest in both chocolate types (milk chocolate and chocolate with pistachio). There was no difference among the chocolate types in terms of Pb and Cd contents (p<0.01). The heavy metal contents of the analyzed samples are within the ranges reported by the WHO and Turkish Food Codex regarding to chocolate and other foods.
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Objectives of this study were to estimate mean daily intake of copper for eight age subgroups of each gender, to examine consumption patterns of chocolate foods in the U.S., and to determine amounts of copper provided by the consumption of chocolate foods by analyzing 3-day dietary records reported by individuals in the 1987–1988 Nationwide Food Consumption Survey. Mean daily copper intake for all age/gender groups of infants and children reached the lower value of the Estimated Safe and Adequate Daily Dietary Intake (ESADDI) range. However, the mean daily copper intake of all age/gender groups of adolescents and adults was below the ESADDI of 1.5 to 3.0 mg/day. Chocolate cookies were most frequently consumed among chocolate foods. Dark chocolate/candy made the highest contribution to mean daily copper intake (22.1% of ESADDI). Other major contributors to the daily copper intake were chocolate pie (17.8% of ESADDI), chocolate milk (13.3%), chocolate topping/syrup/icing (12.0%), milk chocolate/candy (11.3%), and chocolate cake/muffin (11.2%). The total dietary copper intake by males and females was positively associated (p<0.001) with the consumption of chocolate foods. These results indicate that the mean daily copper intake of American adolescents and adults is less than recommended level and chocolate foods can be a good source of American dietary copper.