Environ Monit Assess (2013) 185:9471–9479 DOI 10.1007/s10661-013-3266-4
Investigation of heavy metal content of Turkish tobacco leaves, cigarette butt, ash, and smoke Füsun Okçu Pelit & Ruken Esra Demirdöğen & Emür Henden
Received: 4 December 2012 / Accepted: 17 May 2013 / Published online: 28 May 2013 # Springer Science+Business Media Dordrecht 2013
Abstract A procedure for the determination of cadmium, copper, manganese, and zinc in Turkish tobaccos, which were of different origins, years, and grades, and in the butt, ash, and smoke, which were obtained by smoking the cigarettes that were prepared manually from the said tobaccos in a smoking apparatus, was devised as proposed. The collected samples were digested by wet ashing technique by using HNO3HClO4 and were analyzed by flame atomic absorption spectrometry with satisfactory recoveries (94 % to 98 %). The regression coefficients were above 0.99, and the detection limits were in the range of 0.03– 0.12 mg/L−1. The performance and accuracy of the method was tested by analyzing “Certified Reference Material GBW 08501-Peach Leaves.” The determined values were in agreement with the standard values for the heavy metals analyzed. Thus, it was concluded that the developed method could offer a wide range of application for establishing a relationship between the makeup and composition of tobacco plant, products, ash, smoke, and smoking.
F. O. Pelit (*) : E. Henden Department of Chemistry, Faculty of Science, Ege University, 35100 Bornova-İzmir, Turkey e-mail:
[email protected] R. E. Demirdöğen Department of Chemistry, Faculty of Science, Çankırı Karatekin University, Çankırı, Turkey
Keywords Tobacco . Tobacco smoke . Atomic absorption spectrometry . Heavy metal . Wet ashing
Introduction Great efforts have been devoted to quantifying trace elements in food and environmental samples since they play an important role in the physiological process of all living organisms (Aras and Ataman 2006). Tobacco and its products, which were once conceived as medicine, are now classified among the most dangerous carcinogens due to the results obtained from the investigation of the effects and the toxicities of various constituents (Chiba and Masironi 1993). Tobacco leaves are widely used for manufacturing smoking materials. Smoking of tobacco products has been implicated in the etiology of respiratory diseases, cancer (for approximately 90 % of lung cancers), and cardiovascular diseases (Stavridez 2006; Law and Hackshaw 1996). Studies indicate that there is a definite correlation between the level of heavy metals in the human body and the concentration, which would make them act as poisonous interference to the enzyme systems and metabolism of the body and thus expose some diseases (Nordberg et al. 2007). Most of these heavy metals are present in tobacco plants which can enrich the metals from polluted environments, soil, air, and water (Xiao et al. 2004), and heavy metals are inhaled into the bronchial system during cigarette smoking (Rodgman and Perfetti 2013).
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Therefore, sensitive and simple methods should be developed for the determination of the concentration of these heavy metals in tobacco and smoke. Many methods have been published for the determination of heavy metals in tobacco leaves and in commercially available cigarette samples. The analytical procedures most frequently used are atomic absorption spectrometric methods including graphite furnace (GFAAS; Smith and Sneddon 1999; Yang et al. 2011), flame (FAAS; Sun et al. 2004; Zhu et al. 1999; Lemos et al. 2008; Tüzen and Soylak 2009), and electro thermal (EAAS; Alvarado and Cristiano 1993) atomization techniques; cold vapor generation atomic fluorescence spectrometry (CV-AFS; Gan et al. 2004); instrumental neutron activation analysis (INAA; Wu et al. 1997); inductively coupled plasma optical emission spectrometry (ICP-OES; Jung et al. 1998; Wu et al. 2002); and inductively coupled plasma-mass spectrometry (ICP-MS; Moulin et al. 2006). Spectrophotometric (Chen et al. 2004; Yang et al. 2004), liquid chromatographic (Li et al. 2002; Yang et al. 2003, 2005; Chen et al. 2004; Zhang et al. 2005), and other related techniques (Çevik et al. 2003; Martinez et al. 2008) were also employed. There is relatively less work published regarding determination of heavy metals in ash, butt, and smoke (Bernal et al. 2011; Smith and Sneddon 1999; Pappas et al. 2006). In these studies, ash, butt, and smoke samples were collected by using commercial cigarettes in which the tobacco leaves cannot be characterized due to the mixing of tobacco leaves of different origins, years, and quality during the preparation process of cigarettes. Thus, the aim of this study is to investigate cadmium, copper, manganese, and zinc levels in Turkish tobaccos, which were of different origins, years, and grades, and in the butt, ash, and smoke, which were obtained by smoking the cigarettes manually prepared from the known tobaccos via the devised smoking apparatus. This would also allow an overall assessment and classification of distribution of trace metals in Turkish tobaccos according to their origins, which in turn would potentially be beneficial with respect to forensics and criminology (Bernal et al. 2011). Thus, we could establish a relationship between the makeup and composition of tobacco plant, products, and the parts obtained from their consumption such as ash, smoke, and smoking. The data obtained from this study would enable establishing relations between possible effects of tobacco consumption and the negative effect on the environment and its toxicity or health risk to humans.
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Materials and methods Apparatus and reagents Cu, Zn, Mn, and Cd were determined by using GBC-904PBT Flame Atomic Absorption Spectrometer (FAAS) at 324.8, 213.9, 279.5, and 228.8 nm, respectively. In all FAAS experiments, background correction was made using deuterium lamp. Tobacco samples were dried in WC Heraus Haneau oven at 105 °C until they reached constant weight. For wet ashing procedure, a Stuart Scientific Hotplate SH 3 was used. Distilled water was obtained from Jencons Autostill 4000X. The devised homemade smoking apparatus consisted of the following glass parts: 100-mL Dreschel bottles, connection paths, and manometer, mouth and water vacuum pump parts. Different parts of the smoking apparatus were connected with each other using short PVC tubings. After tobaccos were annealed in non-metallic utensils, homemade cigarettes were prepared via semi-automatic stainless steel utensils. The tobacco samples and the cigarettes were kept in air-tight polypropylene (pp) bottles or bags and were stored in desiccators. All of the glassware and the bottles were soaked in 10 % HNO3 solution for 48 h before usage. Analytical reagent grade HNO3 (65 %), H2O2 (30 %), HCl (37 %), and HClO4 were obtained from Merck, Darmstadt, Germany. All of the solutions were prepared with distilled water. The stock metal solutions (1,000 mg/L) were prepared from metal foils or powders with 99.99 % purity obtained from Merck, Darmstadt, Germany. Of copper and manganese metals, 1.000 g were dissolved in 50 mL of 6 M HNO3 and zinc and cadmium in 5 M HCl and diluted to 1.0 L with distilled water. For accuracy studies for zinc, manganese, and cadmium, peach leaves with the name “Certified Reference Material GBW 08501-Peach Leaves prepared in China” was employed. For accuracy studies for copper, “Certified Reference Material NIST (National Institute of Standards and Technology) SRM (Standard Reference Material) 1547; NIST, Gaithersburg, MD, USA-Peach Leaves” was employed. Sampling of tobacco leaves The tobacco leaves of different years, origins, and grades were obtained from the cigarette factory of İzmir TEKEL (Tobacco, Tobacco Products, Salt and Alcohol Enterprises Incorporation). The tobacco leaf
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samples were dried by the planter on plastic sheets in high tunnels under ambient conditions at temperatures not exceeding 50–55 °C. These samples, which were used to represent tobaccos of different years, were kept under conditions, which were mentioned to be appropriate in the literature (TS ISO 15592–1, 2004; TS ISO 15592–2, 2004). Tobacco leaves were cleaned from dust and broken parts and were annealed, but they were not passed through fermentation. The moisture content of the leaves was optimized as described in the literature (TS 3928, 2006). Determination of moisture content of tobacco leaf samples Of the tobacco leaves, 1.000 g were dried in an oven at 105 °C for 2-h intervals until constant weight was attained. The average moisture content of five different tobacco leaf samples was found to be 86.4±3.1 %. Digestion of tobacco leaves The dried tobacco leaf samples were grounded in agate mortar as to have particle size of 0.3–0.5 mm. Three parallel samples, 1.000 g each, were treated with 10 mL of concentrated HNO3 until gas aggression stopped. Then, tobaccos were wet-digested via heating the mixtures on hot plate at about 100–130 °C. After reaching to near dryness, 2-mL concentrated HClO4 was added, and heating was continued until moist residues were obtained. Onto the residues, 1 mL of 1-M HNO3 and 15 mL of pure water were added and then the solution was heated for 10–15 min to dissolve the salts. The solutions were filtered through black ribbon filter papers, and they were diluted to 25 mL with pure water in volumetric flasks. The solutions were placed in air-tight pp bottles.
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original sample. The minced tobacco leaves were wrapped with ashless cigarette papers with standard dimensions of 65 mm, via semi-automatic cigarette fillers made up of stainless steel. They were separately packaged in pp bags with labels and were kept in desiccators until analysis. The smoking apparatus The smoking apparatus made up of Pyrex glass, which is shown in Fig. 1, was constructed on the basis of the outlines put forward by Wenush (1945). The new setup consisted of four main parts. Part 1 The mouth holds the cigarette butt in any length as to allow the necessary negative pressure of 5 mmHg to be measured on the scale of the manometer. Part 2 The suction path, which is the way between the pump and the mouth part, acts as a transport conduit for the smoke and holds the manometer. Next to the manometer, a glass column protrudes upward. Since its one end is open, it provides regulation of suction and rest periods during smoking, and a real-life smoking manner was obtained. Part 3 The Dreschel bottles with ceramic filters containing 25 ml of 1-mol/L HNO3 were connected to the pump at one end and to the mouth at the other end. The longer arm with ceramic filter was immersed into the HNO3 solution in the bottle and entrapped the particles that came in the cigarette smokes during suction. Part 4 The water suction pump provided the pressure necessary for smoking the cigarette. The pressure was adjusted manually via regulating the faucet. Water flow rate was adjusted to obtain
Preparation of cigarette samples Preparation of the cigarettes from tobacco leaves Tobacco leaves were annealed according to TS 3928Nov.2006 with water vapor in non-metallic utensils so as to have moisture content of 14–16 % (TS 3928, 2006) and then chopped in automatic tobacco mincers made of stainless steel. Each sample was separately packaged in pp bags and were labeled with tags indicating the production year, origin, and grade of the
Fig. 1 The smoking apparatus used in sample preparation
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5 mmHg pressures on the manometer situated on the other side of the suction path. The handmade manometer, which consisted of a U-shape glass tube with both ends open, was scaled on one side and was filled with mercury. Sampling during smoking cigarettes The cigarette, which was positioned into the mouth part of the apparatus, was lit after the pressure on the manometer was adjusted to 5 mmHg as described in Part 4 in “The smoking apparatus” section. This pressure value was chosen since it provided smoking in a more real-life manner for the apparatus. The smoke was sucked into the Dreschel bottles. Five-second intervals of rest were provided via closing the open end of the glass column, which was positioned next to the manometer during smoking and leaving it open for resting periods. The butt of the cigarettes inside the mouth part of the apparatus and the ash, which was collected during smoking, were weighed. Then, buts were wet-ashed via the same procedure explained in “Preparation of cigarette samples” section, while the smoke that was entrapped in the HNO3 solution in the Dreschel bottles was directly analyzed.
Results and discussion Calibration studies Analysis of four metals, copper, zinc, cadmium, and manganese, in tobacco leaves, cigarette ash, butt, and smoke were made by atomic absorption spectrometry. The calibration graphs were constructed, and the method was assessed by calculating the limit of
detection (LOD) and the limit of quantification (LOQ) values, which are given in Table 1. LOD, defined as the concentration equivalent to three times the standard deviation (n=10) of the reagent blank, was calculated for these metals. LOQ was defined as ten times the standard deviation of the reagent blank. Some of the analytical characteristics of related compounds were tabulated in Table 1. Since 1.000 g of sample is present in 25.0-mL sample solution, dilution factor is 25. Therefore, LOD values for solution were multiplied by 25.
Analysis of the samples Tobacco samples under investigation were from different conditions and regions of Turkey with various grades and production years. Differences in metal concentration of tobacco samples may be due to the soil composition on which the plant is grown, to impurities which might have come from processes through which the tobaccos have undergone until they reach TEKEL tobacco units, to materials used while gathering and preserving, and to disobedience to rules which should be obeyed during production and storage. Mean and standard deviation values of the metal content for each tobacco samples with different origins, production years, and grades can be seen in Table 2. The concentration ranges of the metals investigated in the tobacco leaves, which were annealed according to TS 3928-Nov.2006 method and were digested by wet ashing technique, were found to be as follows: for Cd, BLD–5.8 μg g−1; for zinc, 10.7–125 μg g−1; for copper, 9.8–102 μg g−1; and for manganese, 21.2– 233 μg g−1. It was observed from the results that while the tobaccos, which were from Trabzon region, were rich in manganese, tobaccos from Bursa and Balıkesir were rich in copper and zinc, respectively. However,
Table 1 Analytical characteristics of the method Metal
Regression coefficient (R2)
Calibration equation
LOD (mg L−1)
LOQ (mg L−1)
Linear working range (mg L−1)
Cu(II)
0.9992
y=0.0317x − 0.0019
0.06
0.20
1.0–5.0
Mn(II)
0.9956
y=0.1193x − 0.0007
0.12
0.39
0.4–1.5
Zn(II)
0.9911
y=0.2073x + 0.0122
0.08
0.26
0.5–4.0
Cd(II)
0.9997
y=0.4773x − 0.0036
0.03
0.10
0.1–1.7
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Table 2 Metal concentrations of Turkish tobacco leaves with different origins, production years, and grades (n=3) Region
Year
Grade
Metal ion concentration (μg g−1) Cd
Zn
Cu
Mn
İzmir
1992
AG
0.74±0.03
32.8±0.75
35.1±0.72
95.0±1.01
İzmir
1992
BG
1.10±0.07
46.3±1.48
33.8±0.68
77.6±6.13
Kemalpaşa
1998
AG
BLD
48.4±2.66
31.8±0.66
97.0±4.18
Tire
1998
AG
BLD
44.6±2.94
37.2±1.13
43.1±6.85
Söke Kırık
1998
KP
BLD
36.2±1.70
43.2±0.91
60.4±2.72
Ege
1997
AG
BLD
39.2±3.21
35.2±1.16
67.7±6.23
Ayrancılar
1998
AG
0.90±0.13
44.6±1.74
31.5±0.66
55.7±0.67
Balıkesir
1995
AG
2.20±0.18
125±7.25
44.6±1.52
97.9±10.38
Bursa
1996
AG
BLD
68.5±5.34
26.7±0.83
60.9±2.37
Bursa
1997
BG
1.68±0.13
86.8±7.20
102±2.04
50.3±8.25
Bursa
1998
AG
BLD
49.4±3.66
65.5±1.31
45.9±5.37
Bafra
1995
KP
BLD
41.9±1.84
36.3±0.80
55.6±4.78
Bafra
1996
KP
1.28±0.12
42.3±1.48
46.9±1.32
80.2±10.55
Bafra
1997
KP
2.00±0.26
48.4±1.55
34.7±0.93
102±4.59
Bafra
1998
AG
1.40±0.08
46.2±1.29
37.3±0.53
62.4±0.81
Trabzon
1995
KP
2.80±0.20
65.8±3.36
59.4±1.87
65.8±1.51
Trabzon
1996
KP
0.90±0.13
26.7±1.58
20.7±0.76
Trabzon
1997
KP
1.30±0.07
119±9.40
67.1±2.45
60.5±3.57
Trabzon
1998
KP
1.85±0.11
52.5±3.73
44.4±1.68
74.8±1.87
100±16.30
Trabzon
1998
AG
3.63±0.15
30.7±0.99
41.1±1.23
233±8.39
Samsun
1997
AG
1.18±0.03
47.2±1.32
39.6±1.15
44.8±6.94
Basma
1996
BG
1.08±0.07
43.3±2.81
36.9±1.18
56.2±1.57
Bitlis
1993
KP
BLD
26.5±1.88
9.8±0.37
61.1±2.63
Bitlis
1994
KP
5.80±0.22
16.8±1.36
17.4±0.61
36.9±1.07
Bitlis
1995
KP
4.12±0.23
112±8.62
55.9±1.15
77.3±4.02
Yayladağ
1992
AG
1.75±0.12
37.2±1.56
41.2±1.17
42.7±0.90
Yayladağ
1993
AG
BLD
25.7±0.85
12.1±0.47
21.3±1.53
Yayladağ
1994
AG
0.85±0.14
36.1±2.85
23.6±0.86
21.2±1.80
Yayladağ
1995
AG
BLD
47.6±1.71
25.7±1.09
47.4±3.13
Bekirhan
1994
BG
1.50±0.11
29.0±1.28
48.8±1.47
47.4±7.49
Bucak
1998
BG
BLD
19.1±1.41
27.6±0.70
64.3±3.99
Tömbekia
BLD
10.7±0.88
47.4±1.24
31.3±2.28
RekonWinstonb
BLD
47.6±6.33
43.8±1.12
69.2±1.95
BLD: the limit of detection for Cd is 0.75 μg g−1 sample AG A grade, BG B grade, KP KP grade a
Blend of tobaccos from different areas of Turkey
b
Blend of imported tobaccos from foreign countries
no meaningful relation could be established among the year, grade, and the metal content of tobaccos. The concentration of four metals measured in tobacco, ash, butt, and smoke of the nine sample selected are shown in Table 3.
In cigarette butts, which were also digested by wet ashing technique, the metal ion concentration ranges were found to be BLD–1.65 μg g−1 for cadmium, 3.93–23.9 μg g−1 for zinc, 1.47–7.45 μg g−1 for copper, and 10.1–104 μg/g for manganese. It was
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Table 3 Heavy metal ion content of cigarette ash, butt, and smoke (n=3) Region
Year
Grade
The metals present in the parts of the cigarette (μg g−1)
Metal ion concentration (μg g−1) Cd
İzmir
Balıkesir
Bafra
Bafra
Bafra
Trabzon
Trabzon
Trabzon
Trabzon
1992
1995
1995
1996
1997
1995
1996
1997
1998
AG
KP
KP
KP
KP
KP
KP
KP
KP
Zn
Cu
Mn
Tobacco leaf
0.74±0.03
32.8±0.75
35.1±0.72
95.0±1.01
Cigarette butt
BLD
11.0±2.42
4.88±1.54
16.7±4.89
Cigarette ash
BLD
23.0±4.14
10.6±0.84
41.8±5.02
Smoke (%)
BLD
7.0±1.4
57.0±15.67
18.0±4.50
Tobacco leaf
2.20±0.18
125±7.25
44.6±1.52
97.9±10.38
Cigarette butt
1.00±0.16
21.7±4.57
6.30±1.76
21.1±5.91
Cigarette ash
BLD
45.8±5.49
13.2±1.84
68.9±8.27
Smoke (%)
21.0±2.52
86.0±2.15
57.0±5.58
32.0±3.84
Tobacco leaf
BLD
41.9±1.84
36.3±0.80
55.6±4.78
Cigarette butt
BLD
10.6±2.00
3.66±0.77
11.2±1.97
Cigarette ash
BLD
23.5±4.7
9.49±1.42
28.9±3.47
Smoke (%)
BLD
28.0±5.08
74.0±10.36
6.00±1.86
Tobacco leaf
1.28±0.12
42.3±1.48
46.9±1.32
80.2±10.55
Cigarette butt
0.84±0.14
8.70±1.62
4.21±1.11
10.8±2.85
Cigarette ash
0.26±0.02
20.7±3.72
12.1±1.45
32.1±3.53
Smoke (%)
64.0±10.94
12.0±2.18
52.0±5.72
6.00±1.78
Tobacco leaf
2.00±0.26
48.4±1.55
34.7±0.93
102±4.59
Cigarette butt
1.65±0.15
14.2±2.19
5.92±1.66
21.4±5.84
Cigarette ash
0.25±0.03
19.9±3.98
7.71±0.93
25.4±1.52
Smoke (%)
76.0±6.68
6.00±1.39
49.0±7.31
42.0±6.89
Tobacco leaf
2.80±0.20
65.8±3.36
59.4±1.87
65.8±1.51
Cigarette butt
0.45±0.08
15.3±2.71
4.91±1.46
104±2.61
Cigarette ash
0.05±0.03
28.5±3.14
9.95±0.45
41.6±2.49
Smoke (%)
77.0±10.47
19.0±0.58
61.0±9.69
26.0±7.33
Tobacco leaf
0.90±0.13
26.7±1.58
20.7±0.76
Cigarette butt
0.15±0.03
3.93±0.67
1.47±0.43
100±16.30 17.5±4.48
Cigarette ash
0.06±0.04
7.97±1.51
3.58±0.61
50.7±2.79
Smoke (%)
70.0±7.71
20.0±1.60
44.0±6.68
23.0±3.59
Tobacco leaf
1.30±0.07
119±9.40
67.1±2.45
60.5±3.57
Cigarette butt
1.61±0.05
23.9±3.05
7.45±1.65
12.2±1.68
Cigarette ash
0.58±0.05
49.3±6.41
16.3±0.82
24.6±2.35
Smoke (%)
BLD
22.0±2.11
55.0±6.16
23.0±0.91
Tobacco leaf
1.85±0.11
52.5±3.73
44.4±1.68
74.8±1.87
Cigarette butt
0.11±0.03
9.47±0.87
3.42±0.56
10.1±0.95
Cigarette ash
0.78±0.03
14.0±3.08
7.80±1.32
16.7±2.42
Smoke (%)
BLD
17.0±2.89
45.0±5.27
30.0±2.08
observed that the metal ion concentration of the butts were generally lower than that of the leaves. Thus, it was concluded that butts are not the part of the cigarette where heavy metals accumulated during smoking.
In cigarette ashes, upon digestion via wet ashing technique, the metal ion concentration ranges were found to be BLD–0.78 μg g−1 for cadmium, 7.97– 49.3 μg g−1 for zinc, 3.58–16.3 μg g−1 for copper, and 16.7–68.9 μg g−1 for manganese.
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Table 4 Average concentrations (micrograms per gram) and relative standard deviations of the analysis (n=5) Sample
Region, year, grade
Cd
Zn
Cu
Mn
% RSD Average % RSD Average % RSD Average % RSD Average concentration concentration concentration concentration (μg g−1) (μg g−1) (μg g−1) (μg g−1) –
28.5
2.39
11.3
3.70
53.5
Bekirhan, 1994, BG 1.50
15.7
29.0
8.29
48.8
2.05
47.4
Tobacco leaves Yayladağ, 1992, KP BLD Cigarette ash Cigarette butt
Ege Söke, 1998, KP BLD
–
73.5
24.4
12.0
Bafra, 1996, KP
BLD
–
20.7
23.8
12.1
Bafra, 1996, KP
0.84
18.2
8.70
Investigation of the percent amount of metals that passed into smoke, which was obtained via the newly devised smoking apparatus used, were found to be as follows: for cadmium, up to 77.0 %; for zinc, 6.0–86.0 %; for copper, 44.0–74.0 %; and for manganese, 6.0–42.0 %. Precision study Tobacco leaves, cigarette butts, and ashes of five parallel samples of two different samples were digested by the same procedure. The relative standard deviation of the five parallel analysis found for the leaves, the butt, and the ash are presented in Table 4. Accuracy study The accuracy of the method for determination of metals is strongly dependent on the sample preparation techniques rather than the actual detection technique. For the accuracy study, 0.500 g of five parallel certified reference peach leaf samples were digested with the same procedure. The moisture content of standard peach leaf samples was also measured. For this purpose, 0.500 g of peach leaf samples were dried in oven at 105 °C for 2 h and weighed until the water content was completely removed and constant weight was obtained. As a result, the average dry material content of the leaves was found to be 95.2 %. Mean recovery data obtained by the analyses of standard peach leaf samples CRM GBW 08501 and NIST SRM 1547 including relative standard deviation values obtained by five parallel sampling was given in Table 5. It can be deduced from the results that theoretically acceptable recovery values can be obtained by using the method described.
23.2
5.20
4.21
1.28 16.4
20.4
13.3
17.3
32.1
14.8
31.7
10.8
31.3
Conclusions Through the precision, accuracy, and recovery studies, it was concluded that the accuracy and the precision of the digestion process was efficient and acceptable for all metals except cadmium. The method based on wet sample digestion using HNO3 +HClO4 would be appropriate for the determination of metals in tobacco. It was observed that the metal ion concentration of butts was lower than the leaves. Thus, the butt, where metal ion accumulation was thought to occur dominantly, was not observed to be the part where accumulation occurred as compared to the other studies (Wu et al. 1997; Jung et al. 1998). On the contrary, our results showed that this part has the least metal content as reported earlier (Kazi et al. 2009). Comparing concentration of metals in tobacco plants of different regions, manganese concentration in the leaves gathered from Trabzon region was found to be higher than those of other regions. However, copper and zinc content of the leaves gathered from Bursa and Balıkesir were richer than the rest. Table 5 Accuracy results of standard peach leaf samples CRM GBW 08501 and NIST SRM 1547 (n=5) Metal
Value in the certificate (mg kg−1)
Experimentally found concentration (mg kg−1)
Mean recovery (%)
RSD (%)
Mn
75.4 ± 5.4
74.5 ± 1.9
98.8
2.06
Zn
22.8 ± 2.5
21.7 ± 0.45
95.2
1.29
Cu
3.70 ± 0.40
3.51 ± 0.26
94.8
Cd
0.018 ± 0.008
a
a
BLD
Results for copper is for NIST SRM 1547
–
3.74 –
9478
No correlation could be found between the metal contents and the production year and grade of the tobaccos. Only in the tobacco leaves of Bafra, which is in the Black Sea region, Mn, Cu, and Zn concentration increased with the production year. In general, cigarettes are a blend of several tobaccos from several different sources, and it would be difficult to pinpoint the sources of metals. It is interesting to note that no study was done in the literature for the determination of metal content of cigarette ash, butt, and smoke by the preparation of known tobacco samples in the cigarette. In our study, the metal content of those samples can be evaluated more reliably. Our results are not appropriate for the evaluation of human exposure, but give useful information about the possible human exposure. Therefore, further studies and standardization is needed. Evaluation of the overall results shows that due to smoking, heavy metal exposure of the smokers and non-smokers living in the same area may cause a serious health risk. Smoking can thus be one of the major sources of heavy metal intake to humans. Consequently, heavy metals are present in tobacco smoke and have long been associated with various diseases.
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