Uptake of thallium from naturally-contaminated soils into vegetables

Abstract

Thallium transfer from naturally (pedogeochemically) contaminated soils into vegetables was studied. Three different types of top-soil (heavy, medium, and light) were used for pot experiments. The soils were collected from areas with low, medium, and high levels of pedogeochemical thallium (0.3, 1.5 and 3.3 mg kg(-1)). The samples of vegetables were collected and analysed. The total content of thallium in soil and the type of soil (heavy, medium and light), plant species and plant variety were found to be the main factors influencing thallium uptake by plants. The uptake of thallium from soils with naturally high pedogeochemical content of this element can be high enough to seriously endanger the food chain. These findings are very important because of the high toxicity of thallium and the absence of threshold limits for thallium in soils, agricultural products, feedstuffs and foodstuffs in most countries, including the Czech Republic.

Full text

For Peer Review Only
Tl uptake from contaminated soils into vegetables
Journal:
Food Additives and Contaminants
Manuscript ID:
TFAC-2005-330.R1
Manuscript Type:
Original Research Paper
Date Submitted by the
Author:
06-Dec-2005
Complete List of Authors:
Pavlíčková, Jana; MZLU Brno
Zbíral, Jiří; UKZUZ Brno, Soil Sci.
Smatanová, Michaela; UKZUZ Brno, Soil Sci.
Habarta, Petr; MZLU Brno
Houserová, Pavlína; MZLU Brno
Kuban, Vlastimil; Mendel University, Chemistry and Biochemistry
Methods/Techniques:
Metals analysis - ICP, ICP/MS, Risk assessment
Additives/Contaminants:
Environmental contaminants, Toxic elements
Food Types:
Vegetables
http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk
Food Additives and Contaminants
peer-00577579, version 1 - 17 Mar 2011
Author manuscript, published in "Food Additives and Contaminants 23, 05 (2006) 484-491"
DOI : 10.1080/02652030500512052

For Peer Review Only
1
Uptake of Thallium from Naturally Contaminated Soils into Vegetables 1
2
3
Jana Pavlíčková
1†
Jiří Zbíral
2†
Michaela Smatanová
2†
Petr Habarta
1†
Pavlína Houserová
1†
4
& Vlastimil Kubáň
13†
* 5
6
1
Department of Chemistry and Biochemistry,
Mendel University of Agriculture and 7
Forestry, Zemědělská 1, CZ-613 00 Brno, Czech Republic,
2
Central Institute for 8
Supervising and Testing in Agriculture, Hroznova 2, CZ-656 06 Brno, Czech Republic
3
9
Corresponding author* 10
11
12
* Phone (+420) 545 133 285, fax (+420) 545 212 044; E-mail address: kuban@mendelu.cz 13
†
These authors contributed equally to this work 14
15
Received xx. November 2005 Accepted in revised form……. 16
17
Key words: thallium; uptake; contamination; vegetables; kale; rape; kohlrabi; cucumber; 18
onion; parsley; celery; pot tests; pot trials 19
20
21
Abstract 22
Thallium transfer from naturally (pedogeochemically) contaminated soils into vegetables 23
was studied. Three different types of top-soil (heavy medium and light) were used for pot 24
experiments. The soils were collected from areas with low, medium and high levels of 25
pedogeochemical thallium (0.3 1.5 and 3.3 mg kg
-1
). The samples of vegetables were 26
collected and analysed. The total content of thallium in soil and the type of soil (heavy, 27
medium, and light), plant species and plant variety were found to be the main factors 28
influencing thallium uptake by plants. The uptake of thallium from soils with naturally high 29
pedogeochemical content of this element can be high enough to seriously endanger food 30
chain. These findings are very important because of the high toxicity of thallium and the 31
absence of threshold limits for thallium in soils, agricultural products, feedstuffs and 32
foodstuffs in most countries, including the the Czech Republic 33
Page 1 of 19
http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk
Food Additives and Contaminants
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
peer-00577579, version 1 - 17 Mar 2011

For Peer Review Only
2
34
Introduction 35
36
Thallium is a rare and dispersed element with a geochemical behaviour very near to K and 37
Rb (Rehkämper and Nielsen 2004). Thallium can mimic potassium in metabolic processes 38
(Tremel et al. 1997a) because of similar ionic radii (Tl 170 pm K 164 pm and Rb 172 pm) 39
and it can be found in micaceous minerals (Shannon 1976). But thallium displays also 40
chalcogenic behaviour and can be found in some sulphide minerals and in sulphur 41
containing ores (Merian 1991; Sager 1998; Jones et al. 1990). 42
43
The acute and chronic toxicity of thallium (Tl) is similar to the toxicity of cadmium, mercury 44
and lead (Sager 1998; Sáňka et al. 2000). Thallium is toxic to all organisms in both, 45
monovalent and trivalent form. Human exposure to this element can result in harmful 46
effects including death. Intoxication is associated with disorders of the nerve and digestion 47
systems and Na/K metabolism. Symptoms include polyneuropathy and loss of hair 48
(Repetto et al. 1998). In adults oral lethal doses of thallium are estimated to range 49
between 6 and 40 mg kg
-1
with an average dose of 10-15 mg kg
-1
(ATSDR 1999; Ewerts 50
1988). In spite of the potential toxicity to animals and humans thallium has received only 51
little attention. 52
53
Common thallium contents in mafic rocks range from 0.05 to 0.4 mg kg
-1
and in acid rocks 54
from 0.5 to 2.3 mg kg
-1
. Calcareous sedimentary rocks contain as little as 0.01 to 0.14 mg 55
kg
-1
Tl (Kabata-Pendias and Pendias 2001). The median content of thallium 0.29 mg kg
-1
56
and the maximum more than 50 mg kg
-1
were found for French soils (Tremel et al. 1997a; 57
Tremel et al. 1997b). Content of thallium in soils in the range from 1.5 to 6.9 mg kg
-1
was 58
reported in China in the area of natural Tl-rich sulphide mineralization (Xiao et al. 2004). It 59
was found that pedogeohemical concentration of thallium in some areas of the Czech 60
Republic is more than ten times higher than the median of the values (maximum 3.7 mg 61
kg
-1
; median 0.25 mg kg
-1
). No anthropogenic contamination was proved and higher 62
thallium contents were only of pedogeochemical origin (Zbíral et al. 2000; Zbíral et al. 63
2002; Pavlíčková et al. 2003; Bunzl 2001; Dmowski and Budarek 2002; Medek et al. 64
2001). The highest contents of this element were found in soils derived from granite (2 - 4 65
mg kg
-1
) or paragneiss (0.5 - 1 mg kg
-1
). 66
67
Page 2 of 19
http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk
Food Additives and Contaminants
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
peer-00577579, version 1 - 17 Mar 2011

For Peer Review Only
3
Anomalous levels of thallium in soils are derived from soil substrate or from an 68
anthropogenic contamination (LaCoste et al. 1991). Ore smelting (Olkusz and Bokowo, 69
Poland; Lanmuchang Metallogenic Belt, China), cement production (Lengerich, Germany) 70
and combustion of fossil fuels are the main anthropogenic sources of soil contamination 71
(Jones et al. 1990; Kemper et al. 1991; Lustigman et al. 2000; Lin et al. 1999a; Lin et al. 72
1999b; Sager 1986; Wierzbicka et al. 2004). 73
74
Uptake of thallium by different plants was studied mainly on anthropogenically 75
contaminated soils or in the field and pot experiments after addition of thallium. It was 76
found that plants exhibit species dependent preferences (Xiao et al. 2004) and particularly 77
brassicaceous plants can reach very high concentrations of thallium in their tissues without 78
any symptoms of phytotoxicity. Iberis intermedia Guers. and Biscutella laevigata L. can 79
have thallium concentration above 1 % dry matter (DM) and can be used for 80
phytoremediation or phytomining of thallium (Anderson et al. 1999). Kale (Brassica 81
oleracea acephala L. cv. Winterbor) was found to have behaviour of thallium 82
hyperaccumulating plant (Husam et al. 2003). Selection of suitable cultivars with low 83
thallium uptake can contribute to reduce the food chain contamination. There were 84
observed only small differences between the studied varieties for rape but there were 85
differences more than twenty fold for the kale varieties (Kurz et al. 1999). Some authors 86
studied equilibrium establishment between plant available and plant non-available 87
fractions of thallium in soils (Pavlíčková et al. 2005). They proved that the equilibrium is 88
soil dependent and diffusion driven process. Plants (especially brassicaceous) can 89
accumulate much more thallium than determined as a plant available fraction by extraction 90
of soil with some weak extractants. 91
92
LaCoste et al. (LaCoste et al. 1991) tested 11 vegetables in pot trials for two levels of soil 93
Tl. 36 crops including 3 wild plants were planted on soils with the thallium content from 1.5 94
to 6.9 mg kg
-1
(soils were derived from the thallium rich sulphide ores). In both cases 95
authors proved very strong species dependent preferences in thallium uptake. Contents up 96
to 495 mg kg
-1
were found in green cabbage (Xiao et al. 2004). Tremel and Mench (Tremel 97
and Mench 1998) recommended monitoring of rape cattle cakes and brassicacea fodders 98
for thallium content because their study demonstrated strong possibility of plant 99
contamination by thallium of pedogeochemical origin. Rape (Brassica napus L.) was tested 100
on soils with different content of added thallium and also on soils with higher 101
Page 3 of 19
http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk
Food Additives and Contaminants
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
peer-00577579, version 1 - 17 Mar 2011

For Peer Review Only
4
pedogeochemical content of this element. Higher transfer of thallium was observed in the 102
case of artificially contaminated soils. But the uptake of thallium from soils with naturally 103
high content of thallium was found to be high enough to seriously endanger food chain 104
(Zbíral et al. 2000; Zbíral et al. 2002; Pavlíčková et al. 2003; Medek et al. 2001; Pavlíčková 105
et al. 2005). 106
107
No recommended maximum values are available at the present time in most countries. In 108
Germany 0.46 – 2.24 mg kg
-1
DM (or 0.4 - 2 mg kg
-1
88% DM) was established for feed 109
(anonymous 1997; ananymous 1998). We can take thallium concentration 0.4 - 2 mg kg
-1
110
DM for fodder crops and 0.25 – 0.5 kg
-1
DM for food as a provisional working limit. The 111
values 0.25 and 0.4 mg kg
-1
DM were used for the evaluation of our results. Our study was 112
focused on two areas in the Czech Republic with naturally higher contents of thallium 113
found in our preliminary studies (Sáňka et al. 2000; Zbíral et al. 2000; Zbíral et al. 2002; 114
Pavlíčková et al. 2003; Medek et al. 2001; Pavlíčková et al. 2005). The main goal was to 115
find suitable crops that can be planted in these areas without contamination of food chain 116
by thallium and also to find plants that should be avoided in the areas because of their 117
ability to accumulate thallium in their tissues. 118
119
MATERIALS AND METHODS 120
121
Instruments 122
Plant samples (except rape seeds) were finely ground using a high-speed mill Grindomix 123
(Retsch, Germany) and digested by nitric acid in the closed high-pressure microwave 124
system (Ethos SEL, Milestone, Italy). Dry matter (DM) was determined (2 g of a sample 125
105 ºC) using a MA 30 moisture analyser (Sartorius GmbH, Goetingen, Germany). A 126
sixteen-position double heating block with digestion tubes and coolers MB 422 BH (Uni 127
Elektro, Hradec Králové, Czech Republic) was applied for soil digestion. A sub-boiling 128
distillation unit BSB-939-IR (Berghof BSB-939-IR, Germany) was used for purification of 129
nitric acid. ICP-MS ELAN 6000 (Perkin-Elmer SCIEX, Norwalk, USA) with a cross flow 130
nebulizer Scott’s type spray chamber and Gilson 212 peristaltic pump was used for 131
determination of Tl. The MS part was regularly checked by a calibrating solution (Perkin-132
Elmer SCIEX, Norwalk, USA). The operating parameters were identical with those given in 133
the previous papers (Zbíral et al. 2000; Zbíral et al. 2002; Pavlíčková et al. 2003; Medek et 134
Page 4 of 19
http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk
Food Additives and Contaminants
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
peer-00577579, version 1 - 17 Mar 2011

For Peer Review Only
5
al. 2001; Pavlíčková et al. 2005). Operational parameters of the instruments are given in 135
Table 1. 136
Reagents. 137
All reagents and standard solutions were prepared using Milli Q deionised water (Millipore, 138
Bedford, USA). All chemicals were of reagent grade purity purchased from (Analytika, 139
Prague, Czech Republic) and Merck (Darmstadt, Germany). Stock standard solutions 140
1000 ± 2 mg L
-1
Tl in 2% (v/v) nitric acid and 1000 ± 2 mg L
-1
Lu in 2% (v/v)
nitric acid 141
(Analytika, Prague, Czech Republic) were used for preparing of calibrating standard 142
solutions. 143
Pot experiments 144
Soils with different pedogeochemical contents of Tl. Three different soils were collected - 145
Nivnice (heavy soil - HS 0.3 mg Tl kg
–1
DM), Heřmanice (medium soil - MS 1.5 mg Tl kg
–1
146
DM) and Lužice (light soil - LS 3.3 mg Tl kg
–1
DM). The content of thallium (expressed as 147
mg Tl kg
–1
of dry matter - DM) in all cases was only of pedogeochemical origin. Basic 148
characteristics of the soils are summarised in Table 2. 7.5 kg of air-dried soil (particles less 149
than 2 cm) were used for filling a pot. Six replicates for each soil and each plant (90 pots 150
for the experiment) were used. Five crops - spring rape, winter rape, kale, kohlrabi and 151
maize were tested in the first year and celery, parsley, carrot, and onion were tested in the 152
same pots next year (for the scheme of the experiment see Table 3). Winter rape was 153
sowed in each pot in August. Normally developed plants were singled out in September. 154
Other crops were sowed in April and singled out in May. The fully matured plants were 155
harvested in July. The soils were fertilized with N (NH
4
NO
3
), P (CaHPO
4
.2 H
2
O) and K 156
(KCl) according to the individual demands of each crop to provide a sufficient nutrient 157
supply. The pots were protected against rain during the whole period. Soil moisture was 158
adjusted to 60% of maximum water capacity by daily watering with deionized water. During 159
the harvest the plant parts were collected separately weighed and stored for analysis. 160
Sample preparation and digestion. 161
Plant samples were mechanically cleaned immediately after the harvest and subsequently 162
by a quick washing with deionised water to remove the rest of soil and dust particles. Plant 163
samples were dried and finely ground. The rapeseeds were analysed without grinding. The 164
all samples (1 g) were digested by nitric acid (8 ml HNO
3
and 10 ml H
2
O) in the microwave 165
digestion system at 145 ºC and 700 W for 5 min 180 ºC and 600 W for another 5 min and 166
finally at 180 ºC and 1000 W for the next 5 min. The digests were adjusted to the final 167
volume of 50 ml with deionized water. The digests were further diluted 1-20 times by 168
Page 5 of 19
http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk
Food Additives and Contaminants
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
peer-00577579, version 1 - 17 Mar 2011

For Peer Review Only
6
deionized water before the ICP/MS measurement. Each series consisted of a suitable 169
amount of samples given by the procedure one internal reference standard and two 170
blanks. 171
Soil samples were air-dried gently crushed and sieved. Fraction < 2 mm according 172
to ISO 11464 was used for the analysis. Soils were digested (Pavlíčková et al. 2003) by 173
HNO
3
-H
2
O
2
(2 g soil sample 10 ml HNO
3
and 20 ml H
2
O
2
were used boiling for four hours 174
under cooler). Soil extracts were diluted 5 - 10 times by deionized water before the 175
ICP/MS determination. Each series consisted of a suitable number of samples given by 176
the procedure two internal reference standards and two blanks. 177
Determination of thallium by ICP/MS. 178
Single element calibrating standard solutions were used for calibration of the ICP/MS 179
instrument at five different concentrations of thallium (0, 1, 5, 10 and 50 µg L
-1
). Lutetium 180
at the concentration 10 µg L
-1
was used as an internal standard (
175
Lu signals). The 181
extraction agents acids and lutetium concentrations in the standard calibrating solutions 182
matched their concentrations in the sample solutions. The calibration curve was linear in 183
the whole calibrating range (r 0.9999). Limit of detection 1.2 µg kg
-1
was achieved for the 184
samples (3 S/N criterion). Thallium content was determined from
205
Tl signal. 185
186
RESULTS AND DISCUSSION 187
188
The results of the pot experiments are given in Tables 4 and 5 for Brassicaceous plants 189
and the other crops respectively. The contents of thallium in different parts of the crops for 190
all three investigated soils are given in Figure 1. Average total uptake of thallium from the 191
experimental pot did not follow exactly the concentration of thallium in soil. Uptake of 192
thallium from the light soil (Lužice) with the highest content of thallium (3.3 mg kg
-1
) was 193
ten times higher than from both other soils. 194
195
The bioaccumulating factor - BAF (concentration of thallium in plant (or its 196
part)/concentration of thallium in soil) reflects thallium availability from the given soil. The 197
highest bioaccumulating factors were found for the light soil (Lužice) and than for the 198
heavy soil (Nivnice). Thallium in medium soil (Heřmanice) in spite of its relatively high level 199
(1.5 mg kg
-1
) was found to be less available. BAFs for non-brassicaceous plants were 200
usually below 0.1 even for the soil from Lužice. Higher BAFs for these plants were 201
observed for green parts of vegetables (onion, carrot, parsley) than for other parts. Celery 202
Page 6 of 19
http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk
Food Additives and Contaminants
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
peer-00577579, version 1 - 17 Mar 2011

For Peer Review Only
7
was the only exception of this rule. The situation was substantially different for plants of 203
the Brassicaceae family. BAFs for spring and winter rape were near 1 as found also in the 204
previous studies focused on this crop (Zbíral et al. 2000; Zbíral et al. 2002; Pavlíčková et 205
al. 2003; Medek et al. 2001; Pavlíčková et al. 2005). BAFs higher than 0.4 were found for 206
the other tested brassicaceous plants (except for stalk of kale and kohlrabi). BAF 2.6 was 207
observed as high as for the green part of kohlrabi. 208
209
The translocation factor – TLF (the ratio of thallium concentration in different parts of the 210
plant) shows that for most crops (brassicaceous and others) higher thallium concentration 211
is located in the green part of the plant. The highest TLF was found for kohlrabi (19), kale 212
(10), but also for onion (10) and carrot (8). Concentration of thallium in celeriac part of 213
celery was found to be higher than in the green part. 214
215
If we take thallium concentration 0.4 - 2 mg kg
-1
DM for fodder crops and 0.25 – 0.5 kg
-1
216
DM for food as a provisional working limit and adopt 0.25 and 0.4 mg kg
-1
for the 217
evaluation (anonymous 1997; anonymous 1998) it can be concluded that for heavy soils 218
from Nivnice, and (a bit surprisingly) medium soils (Heřmanice) most crops and their parts 219
were below the limit. Straw of spring rape was above the limit and leaves of kale just on 220
the limit for food on medium soil (Heřmanice). The green part of kohlrabi was able to 221
accumulate thallium even from soil with only a background content of thallium and this part 222
of plant proved to be unsuitable for food or feed for all investigated soils. Brassicaceous 223
plants grown on light soil (Lužice) substantially exceeded the limits with only one exception 224
– stalk of kale. Non-braccicaceous crops showed also relatively high concentration of 225
thallium on light soil (Lužice). The celeriac part of celery and the green part of parsley 226
exceeded the limit for food and the green parts of carrot and onion exceeded the limit for 227
feed. 228
229
CONCLUSIONS 230
231
The total content of thallium in soil, physico-chemical form and form of binding to soil 232
particles seem to be the main factors influencing the uptake by a plant. From the data 233
presented hereby it can be seen that thallium is an exception since the values obtained for 234
other elements in all vegetables are significant smaller than the corresponding plant-soil 235
concentration ratios for the uncontaminated soil. These results demonstrate quantitatively 236
Page 7 of 19
http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk
Food Additives and Contaminants
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
peer-00577579, version 1 - 17 Mar 2011

For Peer Review Only
8
that the ability of a plant to accumulate a metal compared to a control soil might not exist 237
for an anthropogenically contaminated soils and vice-versa. In addition thallium can be 238
present as Tl(I) or Tl(III) which makes it necessary to distinguish between these two 239
species (Lin et al. 1999a; Lin et al. 1999b). Without this specification a correct toxicological 240
evaluation is not possible particularly since Tl(I) possibly occurs in soluble whereas T(III) in 241
colloidal form. 242
243
Uptake of thallium by plants is species dependent. Plant varieties and plant parts differ in 244
the degree of uptake and accumulation of Tl. Some brassicaceous plants commonly grown 245
as vegetables behave as hyperaccumulators of Tl. Content of thallium in different aerial 246
parts of tested plants can differ substantially (nearly 20 times in maximum). The highest 247
concentration was observed mainly in the green parts of the particular plants. Green part 248
of kohlrabi can contain thallium in concentration exceeding the provisional limit even if 249
grown on soil with very low natural content of Tl. 250
251
The concentration of thallium in vegetables in many cases can substantially exceed the 252
concentration of thallium in soils. Thus thallium content should be monitored and the plants 253
with high thallium accumulation power should be excluded from growing for human or 254
animal nutrition in contaminated areas. The above mentioned facts are often neglected 255
because legal measures are usually taken only for the areas anthropogenically 256
contaminated as a result of a human activity. Uptake of thallium from soils with naturally 257
high content of thallium can be high enough to seriously endanger food chains (directly by 258
consumption of plants grown on contaminated soils indirectly by consumption of meat from 259
animals feed by rape cattle cakes a by-product of rapeseed oil production). 260
261
Acknowledgments 262
263
Financial support from the Grant Agency of the Czech Republic, grant No. GA ČR 264
525/01/0908, and from the Ministry of Education Youth and Sports of the Czech Republic, 265
grant No. MSM 43210001 is gratefully acknowledged. 266
Page 8 of 19
http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk
Food Additives and Contaminants
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
peer-00577579, version 1 - 17 Mar 2011

For Peer Review Only
9
REFERENCES 267
268
Anderson CWN, Brooks RP, Chiarucci A, LaCoste CJ, Leblanc M, Robinson BH, Simcock 269
R, Stewart RB. 1999. Phytomining for nickel, thallium and gold. J. Geochem. Explor. 270
67:407-415. 271
272
Anonymous. 1997. Anlage 5 (zu §§ 23 24 und 25) der Futtermittelverordnung in der 273
Fassung vom 19. November 1997. BGBL I Nr. 77 vom 24. November 1997 2714. 274
275
Anonymous. 1998. Maximale Immissions-Werte főr Thallium zum Schutz der 276
Landwirtschaftlichen Tiere. VDI – Richtlinie 2310 Blatt 29 (E). VDI/DIN – Handbuch 277
Reinhaltung der Luft. Band 1a. 278
279
ATSDR Toxicological Profiles for Thallium. 1999. Roper WL. (Ed.). CRC Press, Boca 280
Raton: p. 57. 281
282
Bunzl K, Trauttmannsheimer M, Schramel P, Reifenhauser W. 2001. Availability of arsenic 283
copper lead thallium and zinc to various vegetables grown in slag-contaminated soils. 284
J. Environ. Qual. 30:934-939. 285
286
Dmowski K, Badurek M. 2002. Thallium content in selected plants and fungi in the vicinity 287
of the Boleslaw zinc smelter in Bukowo (Poland). A preliminary study. Acta Biol. 288
Cracov. Bot. 44:57-61. 289
290
Ewers U. 1988. Environmental exposure to thallium. Sci. Total Environ. 71:285-292. 291
Husam Al Najar, Schulz R, Rımheld V. 2003. Plant availability of thallium in the 292
rhizosphere of hyperaccumulator plants: a key factor for assessment of 293
phytoextraction. Plant Soil 249:97-105. 294
295
Jones KE, Lepp NW, Obbard JP. 1990. Thallium. In: Alloway JB. (Ed.) Heavy Metals in 296
Soils. J. Wiley & Sons, New York: pp. 304 - 309. 297
298
Kabata-Pendias A, Pendias H. 2001. Trace elements in soils and plants. CRC Press, LLC 299
3
rd
Ed. Florida: pp. 183-185. 300
Page 9 of 19
http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk
Food Additives and Contaminants
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
peer-00577579, version 1 - 17 Mar 2011

For Peer Review Only
10
301
Kemper FH, Bertram HP. 1991. Thallium. In Metals and their Compounds in the 302
Environment. Merian E. (Ed.). VCH. Weinhaim (FRG): pp. 1227-1241. 303
304
Kurz H, Schulz R, Rımheld V. 1999. Selection of cultivars to reduce the concentration of 305
cadmium and thallium in food and fodder plants. J. Plant Nutr. Soil Sci. 162:323-328. 306
307
LaCoste Ch, Robinson B, Brooks R. 2001. Uptake of thallium by Vegetables: Its 308
significance for human health phytoremediation and phytomining. J. Plant Nutr. 309
24:1205-1215. 310
311
Lin TS, Nriagu J. 1999a. Thallium speciation in the Great Lakes. Environ. Sci. Technol. 312
33:3394-3397 313
314
Lin TS, Nriagu J. 1999b. Thallium speciation in river waters with Chelex-100 resin. Anal. 315
Chim. Acta 395:301-307. 316
317
Lustigman B, Lee HL, Morata J, Khan F. 2000. Effect of Thallium on the Growth of 318
Anacystis nidulans and Chlamydomonas reinhardtii. Bull. Environ. Contam. Toxicol. 319
64:565-573. 320
321
Medek P, Pavlíčková J, Zbíral J, Čižmárová E, Kubáň V. 2001. Inductively Coupled 322
Plasma Mass Spectrometric Determination of Thallium in Soils and Winter Rapeseeds. 323
Intern. J. Environm. Anal. Chem. 81:207-219. 324
325
Merian E (Ed.).1991. Metals and Their Compounds in the Environment. Occurrence 326
Analysis and Biological Relevance. VCH Weinheim, New York. 327
328
Pavlíčková J, Zbíral J, Čižmárová E, Kubáň V. 2003. Comparison of Aqua Regia and 329
HNO
3
+H
2
O
2
Procedures for Extraction of Twenty One Elements from Soils. Anal. 330
Bioanal. Chem. 376:118-125. 331
332
Page 10 of 19
http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk
Food Additives and Contaminants
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
peer-00577579, version 1 - 17 Mar 2011

For Peer Review Only
11
Pavlíčková J, Zbíral J, Smatanová M, Houserová P, Čižmárová E, Havlíková Š, Kubáň V. 333
2005. Uptake of Thallium from Artificially and Naturally Contaminated Soils into Rape 334
(Brassica napus L.). J. Agric. Food Chem. 53:2867-2871. 335
336
Rehkämper M, Nielsen SG. 2004. The mass balance of dissolved thallium in oceans. Mar. 337
Chem. 85:125-139. 338
339
Repetto G, del Peso A, Repetto M. 1998. Human thallium toxicity. In: Nriagu JO. (Ed.). 340
Thallium in the Environment. Wiley, New York: pp. 167-199. 341
342
Sager M. 1998 Thallium in agricultural practice. In: Nriagu JO. (Ed.). Thallium in the 343
Environment. Wiley, New York: pp. 59-87. 344
345
Sager M. 1986. Trace Analysis of Thallium. (In German). Georg Thieme Vrlg: Stuttgart 346
FRG. 347
348
Sáňka M, Němec P, Havlíková Š. 2000. Evaluation of thallium content in arable spoil and 349
its influence on quality of agricultural production. (In Czech). ÚKZÚZ, Brno, Czech 350
Republic. 351
352
Shannon RD. 1976. Revised effective ionic radii and systematic studies of interatomic 353
distances in halides and chalcogenides. Acta Crystallogr. A 32:751-767. 354
355
Tremel A, Masson P, Sterckeman T, Baize D, Mench M. 1997a. Thallium in French 356
Agrosystems - I. Thallium Contents in Arable Soils. Environ. Pollut. 95:293-302. 357
358
Tremel A, Masson P, Garraud H, Donard OXF, Baize D, Mench M. 1997b. Thallium in 359
French agrosystems - II. Concentration of thallium in field-grown rape and some other 360
plant species. Environ. Pollut. 97:161-168. 361
362
Tremel A, Mench M. 1998. Study of the mobility bioavailability and phytotoxicity of thallium 363
from non-point sources. INRA, Villenave d'Ornon (France). 364
365
Page 11 of 19
http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk
Food Additives and Contaminants
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
peer-00577579, version 1 - 17 Mar 2011

For Peer Review Only
12
Wierzbicka M, Szarek-Lukaszewska G, Grodzińska K. 2004. Highly Toxic Thallium in 366
Plants from The Vicinity of Olkusz (Poland). Ecotox. Environm. Safety 59:84-88. 367
368
Xiao T, Guha J, Boyle D, Liu C-Q, Chen J. 2004. Environmental Concerns related to high 369
Thallium Levels in Soils and Thallium uptake by Plants in Southwest Guizhou China 370
Sci. Tot. Environm. 318:223-244. 371
372
Zbíral J, Medek P, Kubáň V, Čižmárová E, Němec P. 2000. Determination of Thallium in 373
Aqua-regia Soil Extracts by ICP-MS. Commun. Soil. Sci. Plant Anal. 31:2045- 2051. 374
375
Zbíral J, Pavlíčková J, Havlíková Š, Čižmárová E, Němec P, Sáňka M, Kubáň V, Medek P. 376
2002. Comparison of Several Soil Extractants for Determination of Thallium. Commun. 377
Soil Sci. Plant Anal. 33:3303-3312. 378
Page 12 of 19
http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk
Food Additives and Contaminants
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
peer-00577579, version 1 - 17 Mar 2011

For Peer Review Only
13
Caption to figure 379
Fig. 1. Relationship between content of thallium [in mg kg
-1
DM] in the soil and its uptake 380
by separate parts of the test plants [in mg kg
-1
DM] for Brassicaceous family (bottom) and 381
the other crops (top) respectively. 382
383
384
385
Page 13 of 19
http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk
Food Additives and Contaminants
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
peer-00577579, version 1 - 17 Mar 2011

For Peer Review Only
14
Table 1. Operational parameters of Elan 6000 ICP-MS 386
387
Parameter Value Parameter Value
Rf Power 1050 W Readings/Replicate 1
Nebulizer Gas Flow 0.94 L min
-1
Number of Replicates 5
Lens Voltage 7.3 V Measurement Mode Peak hopping
Detector Dual mode Sample Flow Rate 1 mL min
-1
Sweeps/Readings 10
Dwell Time of Isotopes
100 ms
388
Page 14 of 19
http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk
Food Additives and Contaminants
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
peer-00577579, version 1 - 17 Mar 2011

For Peer Review Only
15
Table 2. Basic Characteristics of Topsoils
a
Used for Pot Experiments (All Data Given for DM) 389
390
Parameter Unit Nivnice Heřmanice Lužice
Tl
b
mg kg
-1
0.3 1.5 3.3
pH/CaCl
2
6.9 6.1 6.4
P
c
mg kg
-1
105 310 62
K
c
mg kg
-1
798 702 174
Mg
c
mg kg
-1
281 152 636
Ca
c
mg kg
-1
4730 2260 2520
Fraction < 10 µm % 54.3 22.1 17
Fraction < 1 µm % 32.5 7.2 5.2
Fraction 1-10 µm % 21.8 14.9 11.8
Fraction 10-50 µm % 20.8 16.9 16.3
Fraction 50-250 µm % 17.7 18.9 27.4
Fraction 0.25-2 mm % 7.2 42.1 39.3
Nitrogen (tot.) % 0.25 0.18 0.17
Cox
d
% 1.79 2.29 1.72
TEC
e
mM.kg
-1
410 405 368
391
a
Nivnice (heavy soil) Heřmanice (medium soil) and Lužice (light soil). 392
b
Content in H
2
O
2
- HNO
3
extract.
c
Content according to Mehlich 3.
d
oxidized forms of carbon.
e
393
total exchange capacity of the soils394
Page 15 of 19
http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk
Food Additives and Contaminants
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
peer-00577579, version 1 - 17 Mar 2011

For Peer Review Only
16
Table 3. Species and Cultivars Used in Experiments 395
396
Plant
1
Species Cultivar
2
Pot
3
Symbol
4
Maize
5
Zea mays L. Cemilk H285 12/4 A
Celery
6
Apium graveolens var. Rapaceum Maxim -/2 A
Parsley
6
Petroselinum crispum cvar. Erfurtense Dobra 20/8 B
Carrot
6
Daucus carota L. Berjo 20/8 C
Onion
7
Allium cepa L. Všetana -/6 D
Spring rape
8
Brassica napus L. cvar. Napus
9
Golda 20/10 E
Winter rape
8
Brassica napus L. cvar. Napus Zoro 20/10 D
Kale
8
Brassica oleracea L. var. Acephala Winterbor F1 6/2 B
Kohlrabi
8
Brassica oleraceae L. cvar. Gongylodes Olmia 6/2 C
397
1
family
2
cultivar/trade name
3
number of seeds/plants per pot
4
sequence of the tests in 2002/2003 398
years A/A B/B C/C and D/D
5
Maize
6
Apiaceae
7
Liliaceae
8
Brassicaceae
9
form annua 399
400
401
Page 16 of 19
http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk
Food Additives and Contaminants
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
peer-00577579, version 1 - 17 Mar 2011

For Peer Review Only
17
Table 4. Non-Brassicaceous Plants. Average Yield of Vegetables (Plants) [g DM] Average Total 402
Uptake of thallium [µg] by Vegetables from One Pot The Biological Absorption Coefficients (BAC 403
= plant/soil concentration quotient) The Translocation Factor (TLF = Leaves (Straw)/Root (Stalk 404
Seeds) thallium Concentration). 405
406
Maize Celery Parsley Carrot Onion
Site
b
Leaves Root
(celeriac)
Leaves
(tops)
Root Leaves Root Leaves Onion Tops
Average Yield in One Pot [g DM]
Nivnice 75.6 (3) 34.8 (12) 26.5 (16) 27.5 (16) 21.8 (10) 27.7 (24) 17.0 (19) 12.7 (26) 2.9 (19)
Heřmanice
63.8 (8) 18.2 (27) 13.8 (16) 22.7 (14) 16.3 (6) 15.3 (15) 8.9 (16) 8.0 (14) 2.3 (12)
Lužice 65.6 (9) 3.8 (42) 4.7 (27) 3.4 (33) 3.8 (28) 5.6 (64) 5.4 (35) 7.0 (24) 1.6 (25)
Average Total Uptake of Thallium from One Pot [µg]
Nivnice 0.13 (3) 0.37 (20) 0.19 (18) 0.12 (12) 0.14 (28) 0.09 (15) 0.40 (30) 0.02 (21) 0.05 (19)
Heřmanice
0.20 (22) 0.79 (25) 0.24 (31) 0.40 (19) 0.53 (24) 0.18 (19) 0.86 (32) 0.05 (17) 0.09 (15)
Lužice 1.99 (7) 1.21 (41) 0.78 (20) 0.67 (36) 1.41 (37) 1.02 (38) 2.84 (25) 0.91 (32) 1.33 (33)
Average BAC
Nivnice 0.006 (0.3)
0.036 (22)
0.024 (20)
0.015 (16)
0.021 (20)
0.011 (18)
0.079 (32)
0.006 (22)
0.057 (24)
Heřmanice
0.002 (21) 0.029 (14)
0.011 (22)
0.012 (11)
0.022 (23)
0.008 (16)
0.066 (35)
0.004 (6) 0.027 (11)
Lužice 0.008 (8) 0.098 (17)
0.051 (16)
0.061 (23)
0.111 (22)
0.071 (14)
0.165 (15)
0.040 (16)
0.243 (14)
Average TLF
Nivnice _ 0.7 (34) 1.5 (29) 7.1 (36) 10.1 (15)
Heřmanice
_ 0.8 (34) 1.8 (19) 8.3 (31) 6.5 (16)
Lužice _ 0.4 (31) 1.8 (21) 2.3 (16) 6.2 (11)
407
a
RSD [%] is given in parenthesis (n = 6).
b
Nivnice (heavy soil) Heřmanice (medium soil) and 408
Lužice (light soil). 409
410
411
Page 17 of 19
http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk
Food Additives and Contaminants
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
peer-00577579, version 1 - 17 Mar 2011

For Peer Review Only
18
Table 5. Brassicaceous Plants. Average Yield of Vegetables (Plants) [g DM], Average Total Uptake 412
of Thallium [µg] by Vegetables from One Pot, the Biological Absorption Coefficients (BAC = 413
plant/soil concentration quotient), and the Translocation Factor (TLF = Leaves (Straw)/Root (Stalk 414
Seeds) Thallium Concentration). 415
kale spring rape winter rape (17) kohlrabi
site
b
stalk leaves seeds straw seeds straw root leaves
Average Yield in One Pot [g DM]
Nivnice 3.3 (21) 14.7 (28) 10.7 (18) 34.7 (11) 7.4 (26) 15.4 (26) 9.4 (49) 20.1 (15)
Heřmanice 1.9 (9) 8.2 (14) no seed 24.7 (14) 5.7 (23) 13.4 (22) 7.3 (13) 10.9 (16)
Lužice 2.4 (20) 11.7 (7) 2.2 (46) 30.0 (9) 4.2 (16) 14.2 (18) 7.0 (20) 11.8 (6)
Average Total Uptake of Thallium from One Pot [µg]
Nivnice 0.06(32) 2.23 (26) 1.64 (18) 3.13 (9) 1.21 (37) 2.27 (22) 0.32 (36) 12.0 (17)
Heřmanice 0.05 (16) 2.04 (14) no seed 9.58 (22) 1.13 (26) 2.45 (15) 0.45 (23) 12.2 (23)
Lužice 0.36 (23) 18.1 (7) 5.50 (35) 42.6 (16) 14.7 (29) 36.1 (18) 4.46 (38) 96.4 (31)
Average BAC
Nivnice 0.065 (13) 0.515 (13) 0.511 (5) 0.303 (11) 0.539 (23) 0.500 (13) 0.096 (18) 1.94 (8)
Heřmanice 0.017 (18) 0.166 (6) no seed 0.261 (9) 0.132 (19) 0.124 (13) 0.043 (26) 0.70 (14)
Lužice 0.046 (12) 0.470 (2) 0.804 (21) 0.432 (17) 1.07 (24) 0.743 (24) 0.192 (29) 2.60 (20)
Average TLF
Nivnice 8 (14) 0.6 (12) 1 (21) 19 (17)
Heřmanice 10 (17) No seed 1 (20) 17 (16)
Lužice 10 (12) 0.5 (11) 0.7 (12) 14 (14)
a
RSD [%] is given in parenthesis (n = 6).
b
Nivnice (heavy soil) Heřmanice (medium soil) and Lužice (light soil). 416
Page 18 of 19
http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk
Food Additives and Contaminants
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
peer-00577579, version 1 - 17 Mar 2011

For Peer Review Only
19
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
0.3 1.5 3.3 0.3 1.5 3.3 0.3 1.5 3.3 0.3 1.5 3.3 0.3 1.5 3.3
Tl in soil mg.kg
-1
Tl in plant
mg.kg
-1
root
leaves, tops
417
418
419
420
421
422
423
0.0
2.0
4.0
6.0
8.0
10.0
0.3 1.5 3.3 0.3 1.5 3.3 0.3 1.5 3.3 0.3 1.5 3.3
Tl in soil mg.kg
-1
Tl in plant
mg.kg
-1
stalk, seeds, root
leaves, straw
424
Fig 1. Relationship between the content of thallium [in mg kg
-1
DM] in the soil and its uptake by separate parts of test 425
plants [in mg kg
-1
DM] for Brassicaceous plants (bottom) and the other crops (top) respectively. 426
427
spring rape
maize
celery
parsley
carrot
onion
kale
winter rape
kohlrabi
Page 19 of 19
http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk
Food Additives and Contaminants
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
peer-00577579, version 1 - 17 Mar 2011