Professional Documents
Culture Documents
SUBMITTED TO
DEPARTMENT OF CHEMISTRY, ST. JOHNS COLLEGE, AGRA
SUBMITTED BY:
SAURAV K. RAWAT
Associate Professor
Department of Chemistry
St. Johns College, Agra
M Sc Final
Physical Chemistry
2013-14
CERTIFICATE
Associate Professor
Department of Chemistry
St. Johns College, Agra
(Supervisor)
HEAD
Department of Chemistry
St. Johns College, Agra
ACKNOWLEDGEMENT
It is my proud privilege to express my profound sense of gratitude and
sincere indebtedness to honorable Dr Alexander Lal, Principal of St. Johns
College, Agra, for providing infrastructure for the completion of this project. I
am thankful to Dr Hemant Kulshreshtha, Head of the Chemistry Department;
he was always affectionate, pain taking and source of inspiration to me. I am
highly obliged to him for their guidance, constructive criticism and valuable
advice which they provided to me throughout the tenure of my project. The
project work could not have been possible without his worthy suggestions
and constant co-operation.
I am also thankful to my supervisor Dr Susan Verghese to guide me on the
various sides of this project and her help and guidance she provided to me
for the initiation of this project. My heart is filled with deep sense of
thankfulness and obeisance to my teachers Dr. R P Singh, Dr. H B Singh, Dr. P
E Joseph, Dr. Raju V John, Dr. Shalini Nelson, Dr. Mohd. Anis, Dr. Anita Anand,
Dr. Padma Hazra, and Dr. David Massey for their valuable suggestions and
lively moral boosting during the progress of this investigation.
I am also thankful to Ms. Nisha Siddhardhan (Instrumentation in-charge) for
their kind support during the project work. I also place my sincere thanks to
non-teaching staff for their support and co-operation.
I am highly grateful to my parents for their affectionate and moral support.
They have always been source of inspiration for me.
Above all, I thank The Almighty for giving me strength to complete this
project.
Last but not the least I extend my sincere thanks to all those who have
helped me in one or the other way during my project work.
Saurav K. Rawat
M Sc Final (Physical Chemistry)
ABBREVIATIONS
RDA = Recommended Dietary Allowance
AI = Adequate Intake
UL = Upper Limit
DDI = Daily Dietary Intake
DRI = Dietary Reference Intakes
MAL = Maximum Acceptable Limit
SAM = Standard Addition Method
AA = Atomic Absorption
FAAS = Flame Atomic Absorption Spectroscopy
HCL = Hollow Cathode Lamp
MIBK = Methyl isobutyl ketone
APDC = Ammonium pyrrolidine dithiocarbamate
ND = Non Detectable
PMT = Photomultiplier tubes
LPG = Liquefied petroleum gas
ppm = Parts per million
Cu = copper
Cr = chromium
Pb = Lead
Ni = Nickel
Na = Sodium
Fe = Iron
Ca = Calcium
UL = The maximum level of daily nutrient intake that is likely to pose no risk
of adverse effects. Unless otherwise specified, the UL represents total intake
from food, water, and supplements.
ND = Non detectable.
INDEX
1. Introduction
2. Review of Literature
3. Sources of metals in alcoholic beverages
3.1. Raw materials
3.2. Substances added during brewing
3.3. Process type
3.4. Process equipment
3.5. Bottling process
3.6. Aging/storage
3.7. Adulteration
4. Effects of metals present in alcoholic beverages
4.1. Effects on the beverages
4.1.1. Positive aspects
4.1.2. Negative aspects
4.2. Effects on humans
5. Metal concentrations and limits
6. Metal removal
7. Speciation
8. Determination of metals in alcoholic beverages
9. Results and Discussion
10. Conclusion
(TABLE-I to TABLE IX)
References
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33-41
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1. Introduction
The concentration of metals in many alcoholic beverages can be a
significant parameter affecting their consumption and conservation. This
derives from the negative and positive effects caused directly or indirectly by
the presence of metals. Negative effects include beverage spoilage and
hazing, as well as sensorial and health consequences.
Positive effects include the removal of bad odors and tastes, participation in
fermentative processes, provision of pathways for dietary intake of some
essential minerals, and usefulness for authentication purposes.
Because of all this, many metals are carefully monitored and regulated,
which has resulted in the development of a plethora of analytical techniques
for their analysis. Metals in alcoholic beverages are often determined by
atomic absorption or emission techniques; however, the high cost of the
instruments involved and the long sample-preparation times required often
preclude their widespread use. Electrochemical methods are an option for
such analyses.
In the manufacturing process employed for most alcoholic beverages we
distinguish between fermentation and distillation. In the second process, the
distillate is sometimes obtained directly from a previously fermented
product, which carries over the volatile compounds (water, alcohols,
aromatic substances like acids, aldehydes, ketones, esters, etc.) and modifies
the composition previously existing in the raw product. Due to the low
volatility of the seven elements considered in this project (Fe, Cu, Ni, Cr, Pb,
Ca, Na), their levels in the resulting distilled alcoholic beverages have to be
lower. In the distillation process copper still is usually employed because
copper is very malleable, a good heat conductor, and resistant to corrosion,
as well as playing a role as catalyser in certain chemical reactions and of
complexing molecules unpleasant from the organoleptical point of view.
Consequently, an increase in the Cu levels of the resulting distilled brandy
would be expected.
Additionally, it is known that in the ageing of brandies obtained via
distillation, the activation of chemical reactions that require oxygen are
probably enhanced by the existence of ions of heavy metals like Cu.
Several techniques have been employed for the determination of minerals in
wines and beverages:
inductively coupled plasma mass spectrometry (ICP-MS) using a doublefocusing sector fields; AAS with flame or electro thermal atomization; or
electro analytical methods such as differential pulse anodic stripping
voltammetry (DPASV).
In the available food composition and nutrition tables, the levels of the
essential minerals studied, especially those for the trace elements Cu and Ni
are not usually collected.
Therefore, the aim of this project was to review the various sources and
concentrations of metals (e.g., Ca, Cr, Cu, Fe, Pb, Ni and Na) in 6 alcoholic
beverages (Whisky, Vodka, Rum, Brandy, Spirit and Deshi liquors), most
commonly consumed in India and over the world their effects, speciation,
removal methods and detection by FAAS technique and flame photometer.
2. Review of Literature
Akrida-Demertzi, K., Koutinas, A.A., 1992 estimated the effect of copper,
potassium, sodium and calcium on alcoholic fermentation of raisin extract and
sucrose solution.
Almeida Neves, et al 2007. Studied about the elimination of copper(II) in
sugar-cane spirits.
Bakalov, N., Angelov, V., Gidov, G., Angelov, B., Bolgurov, S., 1989.
Worked on the technology for the removal of metals from fresh wine distillate
and brandy.
Dugo and Salvo, et al, 2004. Determined the concentration of Ni(II) in
beverages.
Cyro, T.N., 1976. Determined the level of calcium, magnesium, iron, copper,
and zinc levels in distilled, fermented beverages-using atomic absorption
spectrometry.
Mekhuzla, N.A., Panasyuk, A.L., Temkina, V.Y., 1978. Used the trisodium
salt of nitrilotrimethylphosphonic acid for the demetallization of brandies.
Mena, et al, 1997. Determined the level of lead contamination in wines and
other alcoholic beverages by atomic absorption spectrometry..
Pohl, et al. 2007. Studied the Fractionation analysis of metals in dietary
samples using ionexchange and adsorbing resins.
Reilly, C., 1972. Zinc, iron, and copper contamination in home-produced
alcoholic drinks.
Reilly, C., 1973. Heavy metal contamination in home-produced beers and
spirits
10
3.6. Aging/storage
Possible effects caused by metals during these stages are multiple. For example,
Fe(III) and Mn(II) affect the stability of old wines and modify their sensorial quality
after bottling since they are believed to activate molecular oxygen by forming
reactive oxygen species (e.g., hydroxyl radicals); this is possible due to their
electronic configurations involving unpaired electrons that may interact quantum
mechanically with the dioxygen triplet. Likewise, Fe catalyses the oxidation of
polyphenolic substances and Mn facilitates acetaldehyde formation; the products
of these reactions yield undesirable precipitates. Metal complex formation is also
common at this aging/storage state, which may alter a significant number of
beverage parameters. Customeraccessible containers for alcoholic beverages
include metal cans, glass bottles, plastic containers, and paperboard cartons, and
the containers themselves sometimes are a source of metal ions in the beverage.
For example, Cu and Zn can be introduced into beer by welded cans (Mayer et al.,
2003). In fact, the Zn concentration in a specific brand of bottled beer was
measured at 0.33 ppm, whereas in canned beer it reached 0.87ppm (Weiner and
Taylor, 1969). On the contrary, the Ni content in canned beer as compared with
glass-bottled beer is not higher (Dugo et al., 2004).
3.7. Adulteration
This term comes from the Latin word adulterare (i.e., to defile or falsify), and
means to make something impure by the addition of extraneous, inferior, or
improper ingredients. As far back as 1875, legislation has prohibited the
adulteration of drinks (MacRae and Alden, 2002). Unfortunately, Pb and other
metallic impurities can enter beverages during adulteration practices (Ijeri and
Srivastava, 2001). For example, adulterated vodka has been found to contain an
excess of Ca and Mn ions (Servadio et al., 1975).
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The health hazards associated with exposure to chromium are dependent on its
oxidation state. The metal form (chromium as it exists in this product) is of low
toxicity. The hexavalent form is toxic. Adverse effects of the hexavalent form on
the skin may include ulcerations, dermatitis, and allergic skin reactions. Inhalation
of hexavalent chromium compounds can result in ulceration and perforation of the
mucous membranes of the nasal septum, irritation of the pharynx and larynx,
asthmatic bronchitis, bronchospasms and edema. Respiratory symptoms may
include coughing and wheezing, shortness of breath, and nasal itch.
Carcinogenicity- Chromium and most trivalent chromium compounds have been
listed by the National Toxicology Program (NTP) and International Agency for
Research on Cancer (IARC) as having inadequate evidence for carcinogenicity in
experimental animals. According to NTP, there is sufficient evidence for
carcinogenicity in experimental animals for the following hexavalent chromium
compounds; calcium chromate, chromium trioxide, lead chromate, strontium
chromate,and zinc chromate. (TABLE-2)
Iron- Hemoglobin is the oxygen carrying iron protein in mammalian blood.
Chromatin material of nucleus having iron is an essential part in metabolic
oxidations occurring in nucleus. Though essential, excess iron intake can cause
acidity, vomiting and coma conditions. Excess metal gets deposited in different
parts of the body, like liver, kidney and brain and can lead to their failure.
(TABLE-3)
Sodium- People who regularly eat foods high in sodium risk having diseases such
as hypertension, Type II diabetes mellitus, respiratory complications, Dislipidemia,
Gallbladder disease, osteoarthritis and some cancers (endometrial, breast, colon).
Most of the daily sodium intake comes from salt.
The DRI Upper Limit (UL) for Sodium in adults is 2300 mg/day.
Calcium- The level of calcium in the body is usually controlled by vitamin D and
parathyroid hormones. But, if there is a metabolic imbalance of calcium regulation,
it gets deposited in the tissues, leading to their calciferation. Formation of stones
cataract are due to calcium salt deposition. (TABLE-4)
Nickel- it is an essential trace element for several hydrogenases and ureases
enzymes. Its deficiency in food slows down the functioning of the liver in chicks.
It is highly toxic to plants and moderately toxic to mammals. It is carcinogenic if
present in higher concentrations in biological systems.
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Note that limits imposed for alcoholic beverages are higher than those established
for water utilized in human consumption. This reflects the lower intake of the
former (Green et al., 1997). For example, alcoholic drinks usually contribute only
marginally to typical dietary Cu intakes (0.05 mg/day) (Sadhra et al., 2007).
Regrettably, marked absences in legislation do exist (Baldo and Daniele, 2005).
Metal ion concentrations in wastewaters of breweries and alcoholic beverage
factories are typically below the limits established for the introduction of such
concentrations into municipal treatment systems. Metals that are sometimes
present in concentrations near the upper regulation limits include Hg and Cu
(Koller and Sahlmann, 1987).
6. Metal removal
Methods for metal removal from alcoholic beverages can be exemplified by the
following cases:
An alternative metal removal scheme consists in raising the pH (e.g., in wine
and brandy) with NaHCO3 or CaCO3 to ca. 4.55, then adding tannins or tannic
acids and allowing the mixed substances to react for several days. Finally, gelatin
and bentonite are added to react with the metal tannates and the mixture is
stirred, decanted, and filtered. Large reduction factors in Cu, Fe, and Zn
concentrations are thus obtained.
Ion exchange resins decrease the metal content of certain distillates to the
allowable limits (Hodejeu et al., 1972). (As a case in point, we have obtained up to
99.6% removal of Cu from tequila.)
MgCO3 and CaCO3 can act as cationic exchangers to remove Cu(II) from sugar
cane spirits.
Cu is removed from spirituous beverages by precipitation with rubeanic acid.
Some metal ions (e.g., Cu and Fe) are removed from alcoholic beverages by
adding polymers that contain metal-binding groups (Detering et al., 1991; Kern,
1987).
Certain chelating agents (e.g., the trisodium salt of nitrilo trismethylenephosphonic acid) in wine and cognac can precipitate Fe, Al, and Cu
within 1 week (Romantseva et al., 1982). The same compound can be used in
brandy to precipitate Fe and Al (Cu does not precipitate here) (Mekhuzla et al.,
1978).
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7. Speciation
The chemical form in which an element, ion or compound is found in a given
medium depends on the physicochemical conditions of the system. Thus, the
distribution of species in an aqueous medium (e.g., an alcoholic beverage) is
contingent on pH, composition, temperature, and the oxidation-reduction
potential of the solution. These variables define precipitation, dissolution, redox,
and complexation reactions. Biological phenomena (e.g., bioaccumulation)
frequently depend on the chemical form or speciation of a metallic ion.
The redox environment can determine some properties of metallic and nonmetallic species. For example, when arsenic is present in oxidizing environments as
As(V), its toxicity is very low; however, its reduced form, As(III) is highly poisonous.
The opposite occurs with Cr(VI), which is much more toxic than its reduced
counterpart, Cr(III). Solubility can also be severely affected by the redox
environment. Examples of this are Fe(II) and Mn(II) species, typically soluble in
aqueous solutions deficient in dioxygen, whose oxidized forms precipitate quite
easily. Similarly, ligand speciation may drastically affect the nature and
physicochemical properties of the metallic complexes they form. Bioavailability
and toxicity of metal ions in aqueous systems are often proportional to the
concentration of the free metal ion and thus decrease upon complexation.
However, some metal compounds are more dangerous than the metallic element
itself (e.g., methyl mercury vs. mercury). Because of the aforementioned reasons,
determination of the total concentration of a metal in a given matrix often does
not adequately or effectively characterize it; as a result, speciation has gained
considerable ground.
Speciation is the process that yields evidence of the atomic or molecular form of
an analyte. It can be defined either functionally (e.g., the determination of species
that have certain specific functions), or operationally (e.g., the determination of
the extractable forms of an element from a given matrix) (Ibanez et al., 2007).
Examples of the importance of speciation in alcoholic beverages include the
following:
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EXPERIMENTAL
Sampling
The samples of alcoholic beverages analysed in the present study (n = 6)
were purchased from the locality of Agra, Uttar Pradesh. Distilled alcoholic
beverages (n = 6) were selected from the most popular brands consumed by
the local inhabitants taking into consideration their food habits. The samples
were brought to the laboratory of the Department of Chemistry of St. Johns
College, Agra where they were stored at 18 0C until analysed.
Materials and methods
Apparatus
A Perkin-Elmer AAnalyst100 double beam atomic absorption
spectrophotometer (Perkin-Elmer corp., CT) was used at a slit width of 0.7
nm, with hollow cathode lamps for mineral measurements by FAAS. Samples
were atomized for Cr, Cu, Fe, Pb, and Ni. All analyses were performed in peak
height mode to calculate absorbance values.
SYSTRONICS Flame photometer 130 was used for the estimation of Ca and
Na.
Sample preparation
All solutions were prepared from analytical reagent grade reagents, for e.g.,
Commercially available 1,000 g/mL Cu [prepared from Cu(NO3)2.3H2O in
0.5 M HNO3] were used. The water employed for preparing the standards for
calibration and dilutions was ultra pure water with a specific resistivity of 18
m_ cm-1 obtained by filtering double-distilled water through a Milli-Q
purifier (Millipore, Waters, Mildford, MA) immediately before use.
Sample treatment and analysis
Cu, Fe and other elements in spirits, gin, vodka, whisky, rum and similar
beverages can be analysed by atomic absorption. It is accurate, fast and
needs no special sample preparation. The samples are aspirated directly and
standards are made up in alcohol to match the content of the particular
sample.
Calcium and sodium can be easily analysed by Flame Photometer. Standards
can be prepared as follows-
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Applying the Beer-Lambert law directly in AAS is difficult due to the variations in
the atomization efficiency from the sample matrix, and non uniformity of
concentration and path length of analyte atoms (in graphite furnace AA).
Concentration measurements are usually determined from a working curve after
calibrating the instrument with standard of known solution.
INSTRUMENTATION
Light source- The light source is usually a hollow cathode lamp of the element that
is being measured. Lasers are also used in research instruments. Since laser are
intense enough excite atoms to higher energy levels, they allow AA and atomic
fluorescence measurements in a single instrument. This disadvantage of these
narrow-band light sources is that only one element is measurable at a time.
Atomizer- AA spectroscopy requires that the analyte atoms be in the gas phase.
Ions or atoms in a sample must undergo desolvation and vaporization in a high
temperature source such as a flame or graphite furnace. Flame AA can only
analyze solutions, while graphite furnace AA can accept solutions, slurries or solid
samples.
Flame AA uses a slot type burner to increase the path length, and therefore to
increase the total absorbance (see Beer-Lambert law).
Sample solutions are usually aspirated with the gas flow into a nebulizing/mixing
chamber to form small droplets before entering the flame.
The graphite furnace has several advantages over a flame. It is much more
efficient atomizer than a flame and it can directly accept very small absolute
quantities of sample.
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Samples are placed directly in the graphite furnace and the furnace is electrically
heated in several steps to dry the sample, ash organic matter, and vaporize the
analyte atoms.
Light separation and detection- AA spectrometers use monochromators and
detectors for UV and visible light. The main purpose of the monochromator is to
isolate the absorption line from background light due to interferences. Simple
dedicated AA instruments often replace the monochromator with a band pass
interference filter. Photomultiplier tubes (PMT) are the most common detectors
for AA spectroscopy.
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AAS AT A GLANCE
Principle- It measures the decrease in light intensity from a source (HCL) when it
passes through a vapour layer of the atoms of an analyte element. The hollow
cathode lamp produces intense electromagnetic radiation with a wavelength,
exactly the same as that absorbed by the atoms, leading to high sensitivity.
Construction- It consists of a light source emitting the line spectrum of the
element (HCL), a device for the vaporizing the sample (usually a flame), a means of
isolating an absorption line (monochromator) and a photoelectric detector with its
associated electronic amplifying equipment.
Operating Procedure- HCL for the desired elements is installed in instrument and
wavelength dial is set according to the table and also slit width is set according to
the manual. Instrument is turned on for about 20 min to warm up. Air flow rate
and acetylene current are adjusted according to the manual. Standard solution is
aspirated to obtain maximum sensitivity for the element is adjusting nebulizer.
Absorbance of this standard is recorded. Subsequent determinations are made to
check the consistency of the instrument and finally the flame is extinguished by
turning off first acetylene flame and then air.
Lamps- Separate lamp (HCL) is used for each element since multi element hollow
cathode lamps generally provide lower sensitivity.
Vent- A vent is paced about 15-30 cm above the burner to remove the fumes and
vapours from the flame.
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Determination of Heavy MetalsReagents1. Air- cleaned and dried through a filter air.
2. Acetylene- standard, commercial grade
3. Metal free water- all the reagents and dilutions were made in metal free water
4. Methyl isobutyl ketone (MIBK)- Reagent grade MIBK is purified by re-distillation
before use.
5. Ammonium pyrrolidine dithiocarbamate (APDC) solution- 4 g APDC is dissolved
in 100 ml water.
6. Conc. HNO3
7. Standard metal solutions: Five standard solutions of 0.01, 0.1, 1, 10 and 100
mg/L concentrations of metals such as Cr, Mn, Fe, Ni, Cu, Zn, Cd and Pb for
instrument calibration and sorption study are prepared by diluting their stock
solution of 1 g/l, i.e., 1 ml = 1 mg metal.
Procedurea. Instrument operation- same as above. Solution is aspirated into flame after
adjusting the final burner position until flame is similar to that before aspiration of
solvent.
b. Standardization- five standard metal solutions in metal free water are selected
for the standardization of the instrument. Transfer standard metal solutions and
blank to a separatory funnel and added 1 ml APDC, 10 ml MIBK and was shaken
vigorously. Aqueous layer is drained off and organic extract was directly aspirated
into the flame.
c. Sample analysis- Atomizer (nebulizer) is rinsed by aspirating water saturated
MIBK and organic extracts obtained by above the method were directly aspirated
into the flame.
d. Calculation- concentration of each metal ion in milligrams per litre is recorded
directly from the instrumentation readout.
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EXPERIMENTAL
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FLAME PHOTOMETER
Flame photometry is an atomic emission method for the routine detection of
metal salts, principally Na, K, Li, Ca and Ba. Quantitative analysis of these species is
performed by measuring the flame emission of solution containing the metal salts.
Solutions are aspirated into the flame. The hot flame evaporates the solvent,
atomizes the metal, and excites a valence electron to an upper state. Light is
emitted at characteristic wavelengths for each metal as the electron returns to the
ground state. Optical filters are used to select the emission wavelength monitored
for the analyte species. Comparison of emission intensities of unknown to either
that of standard solution, or to those of an internal standard, allows quantitative
analysis of the analyte metal in the sample solution.
Introduction- SYSTRONICS flame photometer 130 is an instrument with which it is
possible to estimate, with speed and accuracy, minute quantities of sodium (Na),
Potassium (K), Calcium (Ca) and Lithium (Li).
The principle of operation is simple. The fluid under analysis is sprayed as a fine
mist into a non-luminous (oxidizing or colorless) flame which becomes colored
according to the characteristic emission of the metal. A very narrow band of
wavelength corresponding to the element (Na: 589 nm, K: 768 nm, Ca: 622nm, Li:
671 nm) being analysed is selected by a light filter and allowed to fall on a photodetector whose output is measure of concentration of the element. The output of
photo-detector is connected to an electronic metering unit which provides digital
readouts. Before analyzing the unknown fluids, the system is standardized with
solutions of known concentrations of the element of interest.
The total system consists of two units1- Main unit,
2- Compressor unit. The main unit consists of an atomizer (for aspiration of
solutions), mixing chamber, burner, optical lens, light filters, photodetectors,
control valves and electronic circuit.
Compressed air (oil free) from the compressor unit is supplied to the atomizer.
Due to a draught of air at the tip of the atomizer, the sample solution is sucked in
and enters in the mixing chamber as a fine atomized jet. Liquefied petroleum gas
(LPG) or laboratory gas from a suitable source is also injected into mixing chamber
at a controlled rate. The mixture of gas and atomized sample is passed on to the
burner and is ignited. The emitted light from the flame is collected by a lens and is
passed through an appropriate filter (Selectable for different element). The filtered
light is then passed on to energize a sensitive photo-detector, the output of which
is applied to the electronic circuit for readout.
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10. Conclusions
Levels of iron, copper, chromium, nickel, lead, calcium and sodium were measured
in alcoholic beverages (Whisky, vodka, rum, brandy, spirit and deshi liquors) using
flame atomic absorption spectrometry (FAAS) and flame photometer. A critical
review is offered concerning the different sources, effects, concentrations,
removal methods, speciation, and analysis of metals (e.g., Ca, Cr, Cu, Fe, Pb, Ni and
Na) present in a variety of alcoholic beverages.
Mineral concentrations were found to be significantly different between the six
alcoholic products studied. In distilled alcoholic beverages, Cu measured
concentrations were statistically different for each of the 6 groups of alcoholic
beverages studied. Contrarily, Cu concentrations were statistically lower.
Remarkably, for Cu, the concentration determined in brandy was statistically
higher.
From all studied elements, Cu was the one for which alcoholic beverages
constitute a significant source (more than 10% of recommended daily intake).
These findings are of potential use to food composition tables.
Metals find their way into alcoholic beverages through many possible sources
discussed here. Their effects on the beverages as well as on humans after
consuming such beverages are quite varied. This then necessitates that metals be
subject to regulations. FAAS offers distinct advantages for their analysis.
Caution: Consumption of liquor is injurious to health
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TABLE-I
Nutrient
Copper
Life Stage
Group
Males
14-18 y
19-50 y
Females
14-18 y
19-50 y
Pregnancy
19-30 y
31-50 y
Lactation
19-30 y
31-50 y
RDA/AI
(g/d)
UL
(g/d)
890
900
8,000
10,000
890
900
8,000
10,000
1000
1000
10,000
10,000
1300
1300
10,000
10,000
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TABLE-II
Nutrient
Chromium
Life Stage
Group
Males
14-18 y
19-50 y
Females
14-18 y
19-50 y
Pregnancy
19-30 y
31-50 y
Lactation
19-30 y
31-50 y
RDA/AI
(g/d)
UL
(g/d)
35
35
ND
ND
24
25
ND
ND
30
30
ND
ND
45
45
ND
ND
34
TABLE-III
Nutrient
Iron
Life Stage
Group
Males
14-18 y
19-50 y
Females
14-18 y
19-50 y
Pregnancy
19-30 y
31-50 y
Lactation
19-30 y
31-50 y
RDA/AI
(mg/d)
UL
(mg/d)
11
8
45
45
15
18
45
45
27
27
45
45
9
9
45
45
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TABLE-IV
Nutrient
Calcium
Life Stage
Group
Males
14-18 y
19-50 y
Females
14-18 y
19-50 y
Pregnancy
19-30 y
31-50 y
Lactation
19-30 y
31-50 y
RDA/AI
(mg/d)
UL
(mg/d)
1,300
1,000
2,500
2,500
1,300
1,000
2,500
2,500
1,000
1,000
2,500
2,500
1,000
1,000
2,500
2,500
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TABLE-V
Nutrient
Nickel
Life Stage
Group
Males
14-18 y
19-50 y
Females
14-18 y
19-50 y
Pregnancy
19-30 y
31-50 y
Lactation
19-30 y
31-50 y
RDA/AI
(mg/d)
UL
(mg/d)
ND
ND
1.0
1.0
ND
ND
1.0
1.0
ND
ND
1.0
1.0
ND
ND
1.0
1.0
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TABLE-VI
LEAD
For Whom
Amount Known To
FDAs Recommended Safe
Cause Health Problems Daily Diet Lead Intakes
(g/d)
(g/d)
For children under age 6
60
6
For children 7 and up
150
15
For Adults
750
75
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TABLE-VII
Concentrations of Metals in mg/L Found in Various Alcoholic
Beverages during This ProjectElement Calcium
(mg/L)
Beverage
Brandi
12
Rum
37
Spirit
16
Whisky
20
Vodka
02
Deshi
34
liquor
Chromium Copper
(mg/L)
(mg/L)
Iron
(mg/L)
Nickel
(mg/L)
Sodium
(mg/L)
0.118
-0.011
0.177
-0.144
-0.078
-0.144
2.727
0.474
1.371
0.791
-0.105
-0.229
-1.135
-1.069
-0.468
-1.169
-0.797
-1.383
29
ND
ND
18
ND
ND
0.056
0.009
0.045
0.024
0.016
0.025
39
TABLE-VIII
Examples of metal concentration limits
for selected beverages
Metal Beverage Concentration limit, mg/L Obligatorietya Reference
Cu Wine 0.5 Recommended Green et al. (1997)
Pb Wine 0.2 Recommended Green et al. (1997)
Cu Brandi 0.05 Recommender Mayer et al. (2003)
Cu Rum 0.1 Recommended Richter et al. (2001)
Cu Vodka 0.02 Recommended Green et al. (1997)
Cu Whisky 0.04 Recommended Salvo et al. (2003), Dugo et al. (2005)
Pb Brandi 0.01 MAL Dugo et al. (2005)
Pb Rum 0.01 MAL Dugo et al. (2005)
Pb Vodka 0.01 MAL Dugo et al. (2005)
Pb Whisky 0.01 MAL Dugo et al. (2005)
Cr Brandi 0.02 MAL Soufleros et al. (2004)
Cr Rum 0.01 MAL Salvo et al. (2003), Dugo et al. (2005)
Cr Vodka 0.01 MAL Soufleros et al. (2004)
Cr Whisky 0.01 MAL Richter et al. (2001)
Fe Brandi 3.0 Recommended (Almeida Neves et al., 2007)
Fe Rum 0.8 Recommended (Almeida Neves et al., 2007)
Fe Vodka 0.1 Recommended (Almeida Neves et al., 2007)
Fe Whisky 1.0 Recommended (Almeida Neves et al., 2007)
Cu Beer 0.05 Recommended Mayer et al. (2003)
Cd Wine 0.1 MAL Salvo et al. (2003), Dugo et al. (2005)
Cu Wine 1.0 MAL Richter et al. (2001)
Pb Wine 0.2 MAL Commission of the European Communities (2006),
Dugo et al. (2005)
Cu Brandi 0.8 MAL Richter et al. (2001)
Zn Wine 0.55 MAL Salvo et al. (2003), Dugo et al. (2005)
Cu Cachaza 5 MAL Richter et al. (2001)
Cu Fruit distillate 5 MAL Soufleros et al. (2004)
Ca (g L-1)
Liquor
60.0
Liquor
0.000
Liquor
0.000
Spirit
Trace
Liquor
Spirit
Liquor
Spirit
26.2
0.000
60.0
Trace
Spanish Ministry of
Agriculture (2004,
Spain)
Food Institute
Informatics (2005,
Denmark)
Spirit
0.000
Whisky
Gin
Rum
0.000
0.000
0.000
Ministry of Health
(2005, Canada)
Liquor
Spirit
0.000
0.000
Reference (country)
Souci et al. (1989,
Germany)
15.0
41
REFERENCES
1. Adam, T., Duthie, E., Feldmann, J., 2002. Investigations into the use of
copper and other metals as indicators for the authenticity of Scotch whiskies.
Journal of the Institute of Brewing 108 (4), 459464.
2. Akrida-Demertzi, K., Koutinas, A.A., 1991. Optimization of sucrose
ethanol fermentation for K, Na, Ca, and Cu metal contents. Applied
Biochemistry and Biotechnology 30, 17.
4. Developments in Food Science (Food Science and Human Nutrition) 29,
475489.
8. Commission of the European Communities. Setting maximum levels for
certain contaminants in foodstuffs. 20.12.2006 EN, Official Journal of the
European Union L 364/5, COMMISSION REGULATION (EC) No
1881/2006 of 19 December 2006.
Retrieved 2008-05-25: <http://eur-lex.europa.eu/LexUriServ/site/en/oj/
2006/l_364/l_36420061220en00050024.pdf> (see also European
Commission, 2000, Doc. III/5125/95 Rev.3).
9. Cotton, F.A., Wilkinson, G., 1976. Basic Inorganic Chemistry. Wiley, New
York.
11. Detering, J., Sanner, A., Fussnegger, B., 1991. Polymers for removal of
heavy metals from wine. Ger. Offen. DE 4000978, 8pp.
12. DJC: Dept. of Justice, Canada, 2005. Food and Drugs Act, SOR/93-603, s.
5. Retrieved 2008-05-28: <http://laws.justice.gc.ca/en/F-27/C.R.C.c.870/123616.html>.
14. FSA: Food Standards Agency, UK, 1998. Metals and other Elements in
Beverages.
Retrieved 2008-05-28:
<http://archive.food.gov.uk/maff/archive/food/infsheet/
1998/no159/159bev.htm>.
15. Cu(II) in beer by derivative potentiometric stripping analysis.
Journal of the Institute of Brewing 109 (4), 332336.
20. Pyrzynska, K., 2007. Chemical speciation and fractionation of metals in
wine. Chemical Speciation and Bioavailability 19, 18.
26. UMA: University of Massachusetts Amherst (USA).
Levine Lectures. Retrieved 2005-10-05:
<http://www.nix.oit.umass.edu/_fdsci150/pdfs/food_tox_pdfs/
levinlectures.pdf>.
27. USFDA: US Food and Drug Administration, 2003. Notification for New
Use of a Food Contact Substance, Divergan HM: Environmental Assessment,
BASF Corporation. Mount Olive, N.J. (USA). March 7, 2003.
42
28. Varju, M., 1972. Determination of iron, copper, calcium, magnesium, and
sodium in alcoholic beverages by atomic absorption spectroscopy. Zeitschrift
fuer Lebensmittel-Untersuchung und -Forschung (Germany) 148 (5), 268
274.
29. Weiner, J.P., Taylor, L., 1969. Determination of metals in beverages by
atomic absorption spectrophotometry.
Journal of the Institute of Brewing 75 (2), 195199.
30. www.nap.edu
31. www.wikipedia.com
32. info@analyticalresource.com (Analytical Research Laboratory)
33. http://mc.manuscriptcentral.com/tfac
43