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Stainless Steel as a Source of Potential Hazard due to Metal Leaching into Beverages

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Stainless steel is a widely used material in cookware. Stainless steel is readily attacked by organic acids, particularly at storage time. Hence iron, chromium, and nickel are investigated on their leaching potential from the cookware into food. Toxicological studies reveal that increased doses of metals such as Ni and Cr can cause adverse reaction such as dermatitis. In this study the effect of different pH and various periods of storage times for four types of juices (lemon, orange, mango and strawberry) are examined on the leaching of metals from new stainless steel cookware. One type of stainless steel grade 201 is chosen from the local market. Samples are analyzed by Atomic absorption spectroscopy for Ni, Cr and Fe, Weight loss (WL) and electrochemical polarization measurements as well as environmental scanning electron microscopy (ESEM). Surprisingly, the human intake of Ni, Cr and Fe after 5 days of lemon juice storage is found to be 3.96, 0.48, and 36.57 mg/person, respectivetly. This metal intake is higher than the permissible limit set by the world health organization WHO. Stainless steel utensils have been considered as an ignored source of nickel, chromium and iron, where the contribution is dependent on stainless steel grade and period stored.
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Int. J. Electrochem. Sci., 10 (2015) 3792 - 3802
International Journal of
ELECTROCHEMICAL
SCIENCE
www.electrochemsci.org
Short Communication
Stainless Steel as a Source of Potential Hazard due to Metal
Leaching into Beverages
Ghada Bassioni1,*, Ali Korin2, Alaa El-Din Salama2
1 Chemistry Department, Faculty of Engineering, Ain Shams University, P. O. Box 11517, Cairo,
Egypt.
2 Food Science and Technology Department, Faculty of Agriculture, Al-Azhar University, Cairo,
Egypt
*E-mail: ghada_bassioni@eng.asu.edu.eg
Received: 26 December 2014 / Accepted: 28 February 2015 / Published: 23 March 2015
Stainless steel is a widely used material in cookware. Stainless steel is readily attacked by organic
acids, particularly at storage time. Hence iron, chromium, and nickel are investigated on their leaching
potential from the cookware into food. Toxicological studies reveal that increased doses of metals such
as Ni and Cr can cause adverse reaction such as dermatitis. In this study the effect of different pH and
various periods of storage times for four types of juices (lemon, orange, mango and strawberry) are
examined on the leaching of metals from new stainless steel cookware. One type of stainless steel
grade 201 is chosen from the local market. Samples are analyzed by Atomic absorption spectroscopy
for Ni, Cr and Fe, Weight loss (WL) and electrochemical polarization measurements as well as
environmental scanning electron microscopy (ESEM). Surprisingly, the human intake of Ni, Cr and Fe
after 5 days of lemon juice storage is found to be 3.96, 0.48, and 36.57 mg/person, respectivetly. This
metal intake is higher than the permissible limit set by the world health organization WHO. Stainless
steel utensils have been considered as an ignored source of nickel, chromium and iron, where the
contribution is dependent on stainless steel grade and period stored.
Keywords: stainless steel, cookware, leaching, toxicity
1. INTRODUCTION
Stainless steel is an iron-based alloy containing at least 10.5 % chromium and maximum of 1.2
% carbon. Other alloying elements may be added during melting such as nickel, molybdenum,
columbium or titanium that serve to change certain properties.Stainless steel cookware account for
43% of cookware [1, 2].
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Actually, most of the stainless steel used in cookware contains around 18% of chromium that
give optimum corrosion resistance. In addition to nickel with a percentage of around 8-10%, both Cr
and Ni enhance the corrosion resistance, and durability [3].
The world health organization (WHO) reported in 1989 that Provisional Tolerance Weekly
Intake (PTWI) is 1.0 and 45 mg/kg bw/week for Ni and Fe, respectively. For Cr WHO (1993) has set a
maximum of 0.05 mg/l in drinking water
However, food standard regulation and tables of food composition are of limited assistance to
the toxicologist investigating dietary intake of metals by individuals. So that during the cooking and
the storage of food in metallic cookware significant quantities of toxic elements may leach out and
increase the uptake of metal above the admissible daily intake (ADI) values even in well regulated and
hygienic household [4].
The release of appreciable quantities of metals such as Cr, Ni and Fe and consequent excessive
intake of these metals cause health hazards. It has been reported that chromium and nickel are released
from stainless steel pans, bowls and tumblers using 0.1 N acetic acid, tartaric acid, lactic acid and some
Indian juices and boiling for different periods of time and stored for 10 min to 1 hour. The results were
60-130, 20-70 µg/L for chromium and nickel, respectively in acid solution and 170-560, 120-200 µg/L
for chromium and nickel, respectively in Indian juice [5].
In the study of Bost et al. in alkaline solution (5% of sodium carbonate) of a pH of 11.50 the
concentration of chromium, nickel and iron are found to be 5-12, 5-310 and 5-310 µ/L, respectively.
[6]. At low pH for stainless steel pans (19% Cr and 9% Ni) containing apricot, lemon, rhubarb,
marmalade, metal leaching is found to be negligible. [7].
In this study, leaching of Cr, Ni and Fe from stainless steel cookware in some fruit juice is
evaluated during storage at different periods of time. The fruit juices are prepared using typical
household recipes. The results obtained from this study will be of great benefit to the consumer and
regulatory agencies for laying down consumer protection standards to those types of juice that are
stored in stainless steel. This study focuses on selected juices (lemon, orange, mango and strawberry)
since they are assumed to be aggressive to stainless steel due to their low pH that ranges from 2.8 to
4.35. Chromium is an essential nutrient to stimulate protein, carbohydrate, and lipids metabolism and
is known for its protective action towards diabetes and arteriosclerosis in humans [8].Chromium (III)
in oxidation state is known to be less harmful but Cr (VI) entangled in digestive system causes cancers,
especially increased risk lung cancer [9]; its LD50 for rats is 20 - 50 mg of Cr (VI) 185 - 615 per kg of
body weight, respectively [10].
Nickel a is metal frequently responsible of allergic skin reactions and has been reported to be
the most common cause of allergic contact dermatitis. The general population (approximately 8 - 10%
of women and 1.2% of men) demonstrate a sensitivity to nickel. Many studies have also demonstrated
skin effects in sensitive human results from ingested nickel. Several studies have shown that oral
exposure may be worsening of eczema in nickel sensitive individuals. Nickel compound have been
well established as carcinogenic in animal species and many modes of human exposure but the
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3794
mechanism is still not fully understood. Not all nickel compounds are equally carcinogenic, so the
carcinogenic potency is directly related to their ability to enter cells [11].
Iron is essential to life and health but toxic in excess causing organ damage [12]. A study
estimates iron increase in daily iron intake using iron pots to be 14.5 and 7.4 mg for adults and child,
respectively. [13]. The impact factor of the various food components on the amount of iron leached
from iron pots during cooking is largely unknown, except for an effect of pH and moisture content of
the raw food [14].
This study aims to access the factors affecting the leaching of Cr, Ni and Fe from stainless steel
cookware during storage of different fruit juice.
Lemon juice (citrus limon L.) is also a rich source of nutrients, including flavonoids, citric acid,
minerals (e.g. potassium) and ascorbic acid (vitamin C) which provide numerous health promoting
characteristics. Lemon juice has particularly high concentration of citric acid, which can constitute as
much 8% of dry weight of these fruits (about 97 g/L in the juice) [15].
Mango fruit is one of the nutritionally rich fruits with unique flavor, fragrance and taste that
promotes health benefits to humans because it is a rich source of carotenoids and provides high
contents of ascorbic acid and phenolic compounds [16]
Orange juice provides a variety of vitamin and minerals. It is healthy and naturally sweet with
any sugar. A cup serving of raw fresh orange juice, amounting to 248 g has 124 mg of vitamin C (>
100% RDI) and has 20.8 g sugar. It also supplies potassium, thiamin and folate [17].
Strawberries are a common and important fruit in the Mediterranean diet because of their high
content of essential nutrients and beneficial phytochemicals, which seem to have relevant biological
activity in human health. Among these phytochemicals, anthocyanin and ellagitannins are the major
antioxidant compounds [18].
2. EXPERIMENTAL
2.1. Materials
2.1.1. Cookware and lacquer
Stainless steel cookware is purchased from the local market, Egyptian origin. The bulk
composition of the stainless steel is given in table 1 [19]. The utensils are cut into square shaped
coupons of dimensions (5.0×5.0×0.3) cm. The utensils two surfaces are treated as a matt interior
surface of roughness of 430-450 πm (measured with a surface roughness tester model TR 100, China)
and a glossy external one. The glossy surface is covered with a commercial lacquer that is used in
covering the metal packages food contact according to Herting [9].
Table 1. Chemical composition of stainless steel grade 201 (WT %).
C
Cr
Ni
S
P
Si
Mn
N
0.15 max
16.0-18.
3.50-5.5
0.03 max
0.060
max
1.00 max
6.50-7.5
0.25 max
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3795
AISI and ACI standard composition ranges for wrought and cast chromium nickel stainless
steel American Iron and Steel Institute.
2.1.2 Preparation of test solution (Fruit juice)
Mango, strawberry, lemon and orange juices are prepared from fruit, deionized water and
sugar:
Lemon juice: 20 ml. lemon + 300 ml. deionized water + 60 gm sugar (pH 2.63)
Orange juice: 300 ml orange (pH 3.60)
Mango juice: 104.26 gm mango + 200 ml. deionized water + 60 gm sugar (pH 4.43)
Strawberry juice: 110gm strawberry + 200 ml. deionized water + 60 gm sugar (pH 3.64)
The coupons are immersed for different storage periods at refrigerator temperature for 1 - 5
days.
2.2. Methods
2.2.1 (Weight loss)
The stainless steel coupons are cleaned by water, dried and weight using a four digits balance,
and reweight again after the test. Juice solutions have been stored at various periods of 1 - 5 days .The
pH of the juice is also measured before the experiment. The reading is recorded to the nearest 0.001
mg on an electronic weighing balance. Corrosion rate in mm year-1 is calculated using the following
equation:
Corrosion Rate mm/Y
where, W= weight loss in mg,
A = Total surface area of sample in cm2
T = Exposure time in hours, in various media.
D = density of stainless steel in g/cm3 (7.81 g/cm3)
2.2.2 Atomic Absorption Spectroscopy
The total metal concentration of leaching from stainless steel is analyzed by Atomic Absorption
Spectroscopy (AAnalyst 400). This instrument is used to analyze concentrations of chromium, nickel,
iron and manganese using graphite furnace with a detection limit of 0.19, 3.6, and 0.18 pg for
chromium, nickel, and iron, respectively. The relative analytical error is 2%. Quality control tests are
performed throughout the experiment by analyzing samples with a known concentration at regular
intervals. After preparation, the samples are subjected to dry digestion in pre-heated porcelain
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3796
crucibles and later in a muffle furnace at 500 °C 550 °C between 3 - 4 hours. This is followed by
cooling in a desiccator and subsequently digested with 5 ml of 5 M HNO3 prepared solution to dissolve
the ash. The dissolved ash solutions are steam heated to remove any adhered metal, cooled and
individually filtered through a Whatmann filter paper into a 25 ml standard flask and made up to the
mark with distilled water. The extracts are transferred quantitatively into pre-heated plastic sample
bottles, tightly closed and kept in a refrigerator at a temperature around 4 °C before analyses are done.
The maximum absorbance is obtained by adjusting the cathode lamps at specific slit widths and
definite wavelengths as follows: 4.25.4, 372.0 and 341.5 nm for chromium, iron and nickel,
respectively and at a slit setting of 0.2 nm.
2.2.3 Surface analysis
Environmental Scanning Electron Microscopy (ESEM) and-Energy Dispersive X-Ray Analysis
(EDAX) measurements examined the surface morphology of the stainless steel samples before and
after immersion in fruit juices. This test gives an indication about leaching of the metals compared to
the initial condition.
2.2.4 Electrochemical (polarization) measurements
Measurements were obtained using a IVIUMSTAT potentiostat-galvanostat operated under
computer control combined with easy corrosion program (IVIUMSTAT soft). All potentials were
measured against SCE. The Potentiodynamic current-potential curves are recorded by changing the
electrode potential automatically with a scan rate of 2 mVs-1 from a low potential of -800 to -300 mV
(SCE). Before each run, the working electrode is immersed in the test solution for 30 min to reach
steady state. Before the measurements, the working electrode is degreased with acetone and rinsed
with distilled water. The stainless steel cookware is cut into circular disks of 1.4 cm diameter and an
exposed area of 1 cm2. The stainless steel coupon (as the working electrode) is fitted into a thermo
stated sample holder cell. The reference electrode is SCE and the auxiliary electrode is Platinum. All
electrochemical experiments are performed in aerated solutions at 25°C. After performing open circuit
potential for 1 h, polarization measurements are done to obtain corrosion current density from Tafel
method.
3. RESULTS AND DISCUSSION
Some assumptions are made: Assuming a family of three persons using a stainless steel utensil
of medium size with a diameter of 10 cm and height of 14 cm, the internal area of the stainless steel
utensil exposed to leaching is about 520 cm2. The metals intake per person is equivalent to:
x Internal Area / Number of personnel [20, 21].
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Figure 1. Comparison of Nickel intake in mg/ person from stainless steel samples in different juices
during various storage periods.
Figure (1) shows the nickel intake in mg/person for different types of juices at different storage
time. In case of lemon, orange, mango and strawberry juices it is found that there is a liner increase in
Ni leaching from the first day to the fifth day for all samples compared to the blank sample.
Figure 2. Comparison of Chromium intake in mg/ person from stainless steel samples in different
juices during various storage periods.
In the first day, the intake of nickel in presence of lemon juice is found to be 1.817 mg/person
and increased until it reaches 3.96 mg/person on the fifth day as the highest value that is attributed to
the pH value of 2.63. As for the orange juice the percentage intake is 66.58, 96.87, 72.06 and 84.13%
for the second day, the third, fourth and fifth day, respectively. In the case of the mango juice the
nickel intake is 1.885 mg/person on day 1 that increases by 77.05% on the second day following an
increase until it reaches 96.14% on the fifth day.
For the strawberry juice the intake value increases to 1.7, 2.252, 2.353, 3.235 and 3.01 mg/ kg
for first, second, third, fourth and fifth day, respectively.
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Figure (2) shows the chromium intake in mg/ person for different types of juices at different
storage time. In case of lemon juice, an increase of chromium intake is seen starting from 0.0070
mg/person in the blank sample that increases to 0.481 mg/person on the fifth day. The percentage of
chromium intake increased from 60.75% on the second day to reach 93.34% on day 5. For orange
juice, the intake of chromium in the blank sample is 0.0193 mg/person and increases on the fifth day to
5.922 mg/person.
Figure 3. Comparison of Iron intake in mg/ person from stainless steel samples in different juices
during various storage periods.
Figure 4. Corrosion rate of the stainless steel cookware samples in different juices for various storage
periods.
The highest percentage of chromium leaching and consequently reflected in human intake is in
mango juice which increases the content of the element chromium naturally found in mango of 0.03
mg/L. The chromium leaching in strawberry juice is less than in the rest of the juices where the intake
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in the blank sample is 0.0056 mg/ person and becomes on the fifth day to 0.213 mg/person. Figure (3)
shows the iron intake in mg/person in different types of juices under investigation at various storage
periods. The quantity of iron leaching is found to be higher than for chromium and nickel. Iron intake
in mg/ person is found to be 36.57 in lemon juice after 5 days storage time as compared to 0.785 in the
blank sample. As for the orange juice increased intake of iron is found with a 70.08% increase in the
second day and further increases by 86.71, 92.57, 101.4 % for the third, fourth, and fifth day,
respectively. Therefore, leaching of iron in the mango and strawberry juices is of 23.24 fold and 26.07
fold, respectively.
Figure 5. (A) ESEM images of stainless steel grade 201 without treatment (blank), B-E ESEM images
of stainless steel sample after 5 days of exposure to juices at refrigerator temperature (B)
lemon juice, (C) orange juice, (D) Mango juice, (E) strawberry juice.
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Figure (4) shows the variation of corrosion rate in stainless steel cookware in different juices
for various storage periods. It shows a relatively low corrosion rate in mango juice; the corrosion rate
is on the first day 0.0093 mm/y and decreases gradually until it reaches 0.0061 mm/ y. While in orange
and lemon juices the corrosion rate is on the first day 0.0275 and 0.0248 mm/ y, respectively, the
corrosion in the orange and lemon medium is very substantial because citric acid (80 and 90% of the
total acids) is recognized as an oxidizing agent. An autocatalytic mechanism has generally been
proposed to explain the high rates of corrosion in acids with primary displacement of H+ ions from
solution; followed by acid reduction rather than hydrogen evolution as acid reduction leads to a
manifest decrease in free energy. [22]
Figure (5) shows environmental scanning electron micrographs of stainless steel grade 201
with and without treatment. Figure (5A) is the blank sample without treatment, while Figure (5B)
shows the stainless steel coupon that has been immersed in lemon juice for 5 days. Pitting corrosion is
observed on some parts. Figure (5C) shows the stainless steel coupon after immersion in orange juice
for 5 days. The figure shows that the damage caused is nearly homogenous throughout the sample.
Leaching of the metal after 5 days exposure to Mango juice is reflected in Figure (5D). Significant
damage is observed on the metal’s surface indicating pitting corrosion. The effect of strawberry juice
on metal leaching can be clearly seen in Figure (5E). In Figure (6) the polarization curves are
represented. The purpose for using this method is to detect any small changes in stainless steel
leaching. However, it does not reflect the natural tendency of stainless steel dissolution as the weight
loss method. The electrochemical parameters of stainless steel in fruit juices solution are listed in
Table (2). It is shown that values of current density (Icorr) are in general less than 0.60 µA/cm2.
Log (current /pA)
1e+3 1e+4 1e+5 1e+6 1e+7 1e+8
potential
-0.6
-0.4
-0.2
0.0
0.2
0.4
0.6
Lemon juice
Mango juice
Orange juice
Strawberry
Figure 6. Polarization curves of the stainless steel sheets grade 201 in different fruit juices.
Int. J. Electrochem. Sci., Vol. 10, 2015
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All experiments are performed in freshly prepared fruit aerated solutions at 25°C. After running
open circuit potential measurements for an hour to attain equilibrium (not shown), Tafel plots are
obtained (Figure 6). From Tafel results the order of corrosion rate from stainless steel alloy in fruit
juices appeared to be: Mango < Strawberry < Lemon < Orange which lies in perfect agreement to the
results obtained for the corrosion rates in Figure (4).
Table 2. Electrochemical parameters for stainless steel dissolution in different media from fruit juices.
Fruit juices
- Ecorr
(mV)
I corr.
(µA cm-2)
βa V.dec-1
- βc V.dec-1
Corrosion Rate
(mmy-1)
Mango
356.1
0.2312
2.054
0.068
0.0017
Strawberry
123.4
0.4271
1.484
0.303
0.0320
Lemon
154.6
0.4528
0.246
0.259
0.0034
Orange
147.5
0.5912
16.03
0.044
0.0044
4. CONCLUSION
The results of the present work clearly indicate that stainless steel utensils in stored juice
(lemon, orange, mango and strawberry) contribute significantly to the total daily intake of nickel,
chromium and iron increasing the concentration of metals. The amount of Cr, Ni and Fe leaching from
stainless steel cookware into food depends on the pH and exposure time. Increasing the storage period
enhances the leaching of metals in all the fruit juices under investigation. The obtained results
necessitate increased societal awareness towards the use of stainless steel with highly corrosive juices
and accompanied possible health hazards.
ACKNOWLEDGEMENT
In memory of Prof. Dr. Hassan Abdeldayem, the authors wish to thank him for his support and
extended care throughout his life and as a co-supervisor in the beginning of his work. A special thanks
to Ms. Sabana Khadar for conducting the ESEM measurements at The Center for Applied and
Environmental Chemistry at The Petroleum Institute in Abu Dhabi, UAE.
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© 2015 The Authors. Published by ESG (www.electrochemsci.org). This article is an open access
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(http://creativecommons.org/licenses/by/4.0/).
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Heavy metals are elements present in trace quantities in the environment and, in small concentrations, they play important roles for the living organisms yet it can cause toxicity if exceeded the recommended levels. Toxic metals contamination is an important environmental problem that was mainly manifested in the growing industrial cities where the levels in toxic metals exceeded the recommended levels leading to the increase of several health problems (that vary from memory disorder to carcinogenic diseases). The main sources of food contamination by toxic metals are the increase in petroleum fuels exhausts, addition of fertilizers and metal based pesticides during farming processes. Nowadays, the non-alcoholic drinks represent one of the highest consumption groups worldwide especially in the Middle East and Islamic countries. The current work aims to investigate the safety of some non-alcoholic beverages (carbonated drinks, flavored yogurt drinks and juice drinks) from toxic metal contamination in the Egyptian market. The study revealed that non-alcoholic beverage samples (juices, flavored yogurts and carbonated drinks) in the Egyptian market are mostly free of lead (Pb), cadmium (Cd) and chromium (Cr) contamination. On the other hand, the results of current beverage samples indicate that iron (Fe), manganese (Mn) and nickel (Ni), except Mn in juices and carbonated drinks, were presented in concentrations above the recommended permissible limits of both the World Health Organization (WHO) and Egyptian Ministry Health (EMH). Meanwhile, Cu was found in concentrations below the recommended permissible limits.
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Oral administration of nickel is thought to be responsible for type-IV-mediated mechanism of immune response. Alternative type-I IgE-dependent mechanism is occasionally postulated, given relatively fast onset of symptoms, reports on spontaneous sensitisation and recurring mentions in scientific literature. In this paper, we make an insight into this hypothesis by performing immunisation using nickel(2+) chelates conjugated to carrier proteins, namely nickel coordinated by bifunctional ethylenediaminetetraacetic acid or bifunctional nitrilotriacetic acid, using bovine serum albumin as a carrier (Ni-(ITCB)EDTA-BSA; Ni-(ITCB)NTA-BSA), and nickel coordinated by bifunctional diethylenetriaminepentaacetic acid using bovine serum albumin or keyhole limpet haemocyanin as a carrier (Ni-p-SCN-Bn-DTPA-BSA; Ni-p-SCN-Bn-DTPA-KLH). Antibody raised in mouse as a reaction to Ni-p-SCN-Bn-DTPA-KLH was identified as the most capable of binding Ni(2+)-DTPA with 0.17 nmol nickel recovered per 0.2 nmol pAb, compared to 0.06 nmol Ni purified using reference antibody. Immunoassay methodology was applied upon several modifications to increase antibody contact surface and physical availability of antigen for more efficient binding. Magnetic beads dispersed in free solution were used as a medium for immobilisation and eluted nickel was subject to Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) instrumental quantitative analysis for more precise output reading. The antibody was tested for selectivity against other divalent metals coordinated with DTPA, i.e. Fe, Pb, Zn, Cu, Co and Mn. While Co and Mn were not detected, four other metals, Fe, Pb, Zn and Cu, were eluted in corresponding amounts greater than nickel at 4.15, 1.58, 3.11 and 3.54 nmol. Pb and Ni were the only two antigens whose binding surpassed the level showed by control antibody. We conclude that nickel-based immunogen may show little suitability for in vivo immunisation assays, which reinforces further question about physiological occurrence of potential nickel-responsive IgE antibodies as mediators in type-I hypersensitivity.
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1.1 Scope and purpose of the document: The purpose of this document is to assess, evaluate, and give guidance on the role of elemental speciation and speciation analysis in hazard and risk assessment, rather than to present a review of each element and its speciation. The effects on the environment are not considered in this document, as this has been the topic of a recent conference and associated documentation (SGOMSEC, 2003). However, exposure of the human population through environmental routes is considered. This document is directed at risk assessors and regulators, to emphasize the importance of consideration of speciation in their deliberations. Until now, this issue has not been a part of most hazard and risk assessments. Further, one of the aims of the document is to encourage the analysis of speciation of elements to increase knowledge on the effect of speciation on mode of action and understanding of health effects. The emphasis is not on nutritional requirements, but on the toxicity of elements to humans. Consideration is made not only of consumer/general exposure but also of occupational exposure. 1.2 Definitions: A chemical "species" is the "specific form of an element defined as to isotopic composition, electronic or oxidation state, and/or complex or molecular structure". "Speciation" can be defined as the distribution of an element among defined chemical species in a system, and "speciation analysis" as the analytical activities of identifying and/or measuring the quantities of one or more individual chemical species in a sample. 1.3 Structural aspects of speciation: The definitions of species and speciation of elements are based on several different levels of atomic and molecular structure where species differences are manifest. Here, we consider differences at the levels of 1) isotopic composition, 2) electronic or oxidation state, 3) inorganic and organic compounds and complexes, 4) organometallic species, and 5) macromolecular compounds and complexes. Some of these structural levels are more important for risk assessment than others. Thus, stable isotope composition, while important both from a theoretical point of view and in physical and environmental chemistry, is generally of minimal importance in risk assessment concerning human health. Likewise, elemental speciation at the macromolecular level has biological significance in physiology, biochemistry, and nutrition, but its importance in occupational or environmental toxicity is less well understood. Organic complexation is of intermediate importance; as most chelates are labile relative to covalent complexes, they influence bioavailability and cellular uptake. However, they form and exchange in relation to the availability of ligands in the local milieu, and their trafficking to cellular targets is somewhat unpredictable. On the other hand, valence state and inorganic and covalent organometallic speciation are of great importance in determining the toxicity of metals and semi-metals. 1.4 Analytical techniques and methodology: Remarkable advances in the performance of elemental speciation analysis have been made during the past 20 years. Speciation analysis can now be performed for nearly every element, but not for every species of every element. Insight has been acquired into sample collection and storage so as to avoid contamination and to preserve the species intact. Available knowledge allows for sample preparation in order to identify and quantify species in biological fluids, tissues, water, and airborne dust. Sample preparation may include an additional cleanup step, extraction procedures, or preconcentration and derivatization of the species, prior to their separation. The most widely used separation techniques are liquid chromatography, gas chromatography, capillary electrophoresis, and gel electrophoresis. If the species are too complex, groups of species can be isolated by applying sequential extraction schemes. This is most used in the fractionation of sediments, soils, aerosols, and fly ash. The detection is usually that of the element, although molecular detection is gaining ground, especially in clinical and food analysis. Commonly used elemental detection methods are atomic absorption spectrometry, atomic fluorescence spectrometry, atomic emission spectrometry, and inductively coupled plasma mass spectrometry. Additionally, plasma source time-of-flight mass spectrometry and glow discharge plasmas can be used as tunable sources for elemental speciation. Electrospray mass spectrometry and matrix-assisted laser desorption ionization mass spectrometry are ideal to obtain structural information about the molecular species. Electrochemical methods are further powerful tools for speciation analysis. Calibration in elemental speciation analysis still remains challenging, especially so in the case of unknown species. There exists a limited choice of reference materials for elemental speciation. A growing number of them are certified. Direct speciation analysis of elements in particles is of great interest in assessing environmental health hazards. It provides valuable information on the elemental species in the superficial layers of the particles, allowing deductions about the origin, formation, transport, and chemical reactions. In most cases, it necessitates highly sophisticated apparatus. 1.5 Bioaccessibility and bioavailability: Substances must be bioaccessible before they can become bioavailable to human beings. A substance is defined as bioaccessible if it is possible for it to come in contact with a living organism, which may then absorb it. Bioaccessibility is a major consideration in relation to particulates, where species internal to the particles may never become bioaccessible. Elemental species that are accessible on the surface of particles or in solution may be bioavailable if mechanisms exist for their uptake by living cells. The rate of this uptake into cells is usually related to the external concentration of either free ions with appropriate properties or kinetically labile inorganic species (free ions plus inorganic complexes). Organic complexation and particulate binding often decrease elemental uptake rates by decreasing the concentrations of free ions and labile inorganic complexes. However, in certain circumstances, organic complexes of an element may facilitate its uptake. In addition, the site at which particulates have prolonged contact with tissues, such as lung alveolar epithelia, may become a focus of chronic exposure and toxicity. Uptake systems are never entirely specific for a single element, and these systems often show competition between similar chemical species of different elements, resulting in inhibition of uptake of essential elements and uptake of competing potentially toxic elements. Because of these competitive interactions, ion ratios often control the cellular uptake of toxic and nutrient elements. Such interactions also result in inherent interrelationships between toxicity and nutrition. It is important to define chemical species interactions clearly before carrying out risk assessment because of such profound effects on availability and toxicity. 1.6 Toxicokinetics and biomonitoring: 1.6.1 Toxicokinetics: Various aspects of speciation of the elements (e.g. the unchanged forms, the biological mechanisms changing species, the different valence states, and the metal-ligand complexes) must be considered when evaluating absorption, mechanisms of binding to proteins, distribution, storage, metabolism, excretion, reactivity, and toxic activity of the metallic elements themselves. Absorption through the respiratory tract is conditioned by size, solubility, and chemical reactivity of elemental species inhaled as particles. The absorption of elemental species in the gastrointestinal tract varies depending on their solubility in water and gastrointestinal fluids, their chemical and physical characteristics, the presence of other reacting compounds, and the period of ingestion (fasting, for instance). The skin may also be an important absorption route for some elemental species. After absorption, the elemental species can form complexes with proteins, including enzymes, such as the essential elements associated with ferritin (iron, copper, zinc), α-amylase (copper), alcohol dehydrogenase (zinc), and carbonic anhydrase (copper, zinc). In general, the removal of electrons from or addition of electrons to the atom influences the chemical activity and therefore the ability of metallic elements to interact with tissue targets (ligands). Examples of charge relevance in crossing lipid barriers are represented by chromate/dichromate, Fe2+Fe3+, and Hg +/H0 passages. Among the other metabolic transformations, the most important is bioalkylation, which, for example, mercury, tin, and lead undergo in microorganisms, whereas arsenic and selenium are additionally bioalkylated as part of their metabolic pathways in higher organisms. Alkylation produces species at a higher hydrophobic level, leading to an increased bioavailability, cell penetration, and accumulation in fatty tissues. Bioalkylation is important for some metals, since the alkylated metal species also interact with DNA. Alkylated metal species penetrate the blood-brain barrier more readily, and it is for this reason that such alkylated species are important neurotoxicants. Metallic elements may be stored in tissues/organs as both inorganic species or salts and species chelated or sequestered to proteins and other organic compounds. Excretion depends on the speciation, the route of absorption, and other toxicokinetic phases. The excreted species are either inorganic or organic and frequently at the lowest oxidation state.
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The increased aluminum concentrations in the human body have been a huge concern due to its health effects. Aluminum utensils are believed to be the primary source of the aluminum metal to humans. In the present work, leaching of aluminum from aluminum utensils in different food solutions was examined. Three aluminum utensils of different origins were chosen from the local market. Different vegetables (green cabbage, red cabbage, and eggplants) were used to prepare different food solutions. Two techniques for analysis were used, weight loss (W L) measurement and environmental scanning electron microscopy (ESEM). The results clearly indicate that the leaching of aluminum from the aluminum utensils, through the cooking process of each vegetable, participated a lot to the daily human intake of aluminum. The amount of leaching was found to be high in the food solutions after the cooking process. According to the World Health Organization (WHO), the obtained values are considered above their limitation values which might lead to several health effects.
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A great need exists for valuable information on factors affecting the quality of animal related products. The second edition of Handbook of Meat, Poultry and Seafood Quality, focuses exclusively on quality aspects of products of animal origin, in depth discussions and recent developments in beef, pork, poultry, and seafood quality, updated sensory evaluation of different meat products, revised microbiological aspects of different meat products. Also, included are new chapters on packaging, new chapters and discussion of fresh and frozen products, new aspects of shelf life and recent developments in research of meat tainting. This second edition is a single source for up-to-date and key information on all aspects of quality parameters of muscle foods is a must have. The reader will have at hand in one focused volume covering key information on muscle foods quality.
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