Beruflich Dokumente
Kultur Dokumente
www.elsevier.com/locate/jgeoexp
Dipartimento di Scienze Ambientali, Sezione di Geochimica Ambientale, University of Siena, Via del Laterino 8, I-53100 Siena, Italy
b
Dipartimento di Scienze Ambientali, Sezione di Botanica, University of Siena, Via Mattioli 4, I-53100 Siena, Italy
Received 27 February 2003; accepted 16 June 2003
Abstract
Arsenic contents of soils and higher plants were surveyed in two former Sb-mining areas and in an old quarry once used for
ochre extraction. Total As in the soils ranged from 5.3 to 2035.3 mg kg 1, soluble and extractable As from 0.01 to 8.5 and from
0.04 to 35.8 mg kg 1, respectively. The As concentrations in the different fractions of soil were correlated significantly or very
significantly. Sixty-four plant species were analyzed. The highest As contents were found in roots and leaves of Mentha
aquatica (540 and 216 mg kg 1, respectively) and in roots of Phragmites australis (688 mg kg 1). In general, the As contents
of plants were low, especially in crops and in the most common wild species. In the analyzed species, roots usually showed the
highest content followed by leaves and shoots. Arsenic levels in soils and plants were positively correlated, while the ability of
the plants to accumulate the element (expressed by their Biological Accumulation Coefficients and Concentration Factors) was
independent of the soil As content. Comparison with the literature data, relationships between the As contents in plants and
soils, and biogeochemical and environmental aspects of these results are discussed.
D 2003 Elsevier B.V. All rights reserved.
Keywords: Arsenic; Plant accumulation; Mining area; Soil contamination
1. Introduction
The average arsenic content in the Earths crust
(clarke) was estimated by Greenwood and Earnshaw
(1984) to be as high as 1.8 mg kg 1. A rather similar
value of 1.5 mg kg 1 was suggested by Wedepohl
(1970) for igneous rocks on the basis of the average
values of granites, basalts and gabbros. Decidedly
higher As values were detected in sedimentary rocks
and a value as high as 13 mg kg 1 (Wedepohl, 1970)
3. Sampling surveys
Plant and soil samples were collected in 1996,
1997 and 1998 from the three localities described
above. Wild plant species were usually sampled,
except in area A where specimens of cultivated plants
were also collected.
Sampling was carried out in area A in the surroundings of the small lake in the open pit of the old
Tafone Mine and along a length of the Chiarone
stream where mining works were intensive. In this
area, six sampling sites were established (S1 S6). S1
and S2 were located in cultivated fields, S3 in a
vegetable garden, S4 in an old field, S5 on mine
dumps and S6 at a mineral processing tailing pond.
In area B, plant specimens were collected from the
dumps and from the area used to roast sulfide minerals. In area C, plant species were sampled from the
slopes of a quarry and from adjacent pastures.
Plant and soil samples were collected according to
the following criteria. Cultivated plant species were
selected to represent the ones most commonly sown in
the sampling areas. Wild species were selected on the
basis of their potential use as phytoremediators,
according to their:
5. Results
5.1. Soils
In the Tafone Chiarone district (area A), the total
arsenic contents in soils of the cultivated and uncultivated fields averaged from 5 to 40 mg kg 1 d.w. The
mine dumps and the tailing ponds showed mean values
of 266 and 1226 mg kg 1, respectively (Table 1).
However, the arsenic content was highly variable,
ranging from 1.3 to 55 mg kg 1 in the fields, from
38 to 899 mg kg 1 in the dumps and from 2 to 2466 mg
kg 1 in the tailings. Similar contents were found in the
soils above the mine dumps of area B and high values
were recorded in the quarry slopes and the pastures of
area C, where a mean content exceeding 2000 mg kg 1
and a range from 1037 to 3133 mg kg 1 were found.
Table 1
As content and some edaphic parameters of soils (mean F S.E.). In each column, the values followed by the same letter are not significantly
different (Tukey test; p < 0.05)
Sampling
sites
As (total)
(mg kg 1)
As (soluble)
(mg kg 1)
As (extractable)
(mg kg 1)
Organic matter
(%)
pH
Pavailable
(mg kg 1)
CEC
(meq/100 g)
Area A
S1 (n = 4)
S2 (n = 4)
S3 (n = 4)
S4 (n = 5)
S5 (n = 9)
S6 (n = 6)
14.60 F 1.00a
5.30 F 2.17b
39.90 F 2.85c
40.00 F 3.81c
265.60 F 88.26cd
1225.60 F 351.70d
0.01 F 0.01a
0.01 F 0.01a
0.02 F 0.01a
0.02 F 0.01a
0.01 F 0.01a
0.04 F 0.02a
0.10 F 0.03a
0.08 F 0.03a
0.04 F 0.02a
0.08 F 0.02a
0.66 F 0.23b
1.50 F 0.33c
4.37 F 0.66a
4.82 F 0.80a
5.25 F 1.27a
4.59 F 0.30a
3.03 F 0.40ab
1.68 F 0.39b
5.8 F 0.2a
5.5 F 0.1a
5.4 F 0.3a
5.0 F 0.1a
7.3 F 0.2ab
7.2 F 0.5ab
0.13 F 0.07a
0.15 F 0.05a
0.18 F 0.12a
0.11 F 0.10a
0.14 F 0.03a
0.11 F 0.02a
5.34 F 1.39a
5.51 F 1.08a
5.97 F 0.42a
5.19 F 1.54a
5.83 F 1.54a
4.06 F 0.96a
372.83 F 77.25
0.03 F 0.02
0.52 F 0.18
3.06 F 0.55ab
8.2 F 0.6b
0.08 F 0.04a
5.49 F 1.63a
753.82 F 34.55a
2035.32 F 297.12b
1.82 F 0.27a
8.48 F 1.40b
7.60 F 0.91a
35.80 F 2.98b
2.80 F 0.22ab
5.05 F 1.41a
5.8 F 0.7a
6.2 F 0.9ab
0.97 F 0.89bb
0.83 F 0.39bb
6.04 F 0.59a
6.66 F 1.04a
Area B
(n = 4)
Area C
Quarry slopes (n = 4)
Pasture (n = 4)
Table 2
Sampling area A. Arsenic content in crops and vegetables of cultivated sites (S1, S2, S3) and in plant species growing in the old field S4
(mean F S.E.; mg kg 1)
Sampling sites and
plant species
Leaves
S1
Zea mays
Triticum aestivum
< 0.02
S2
Helianthus annus
Medicago sativa
0.04 F 0.01
S3
Lactuca sativa
Solanum melangena
Cucurbita pepo
Capsicum annuum
Lycopersicon esculentum
S4
Rubus ulmifolius
Sonchus asper
Medicago hispida
Bromus hordeaceus
Bromus madritensis
Helichrysum italicum
Phalaris coerulescens
Avena fatua
Achillea ageratum
Brassica napus
Lupinus albus
Urospermum dalechampii
Coleostephus myconis
Rumex crispus
Anchus italica
Leaves and
shoots
Shoots
Roots
Flowers and
inflorescences
Fruits and
seeds
0.03 F 0.02
< 0.02
0.03 F 0.02
0.04 F 0.03
0.13 F 0.11
0.11 F 0.09
0.23 F 0.12
0.27 F 0.18
0.07 F 0.03
0.23 F 0.11
< 0.02
< 0.02
0.86 F 0.19
0.11 F 0.05
0.62 F 0.14
< 0.02
0.04 F 0.02
2.53 F 1.99
0.54 F 0.09
0.44 F 0.15
6.95 F 1.72
0.19 F 0.13
2.54 F 1.79
0.07 F 0.06
0.62 F 0.21
0.48 F 0.33
1.39 F 0.74
0.21 F 0.19
1.24 F 0.73
1.14 F 0.27
0.02 F 0.01
0.81 F 0.13
0.04 F 0.03
< 0.02
0.09 F 0.02
1.05 F 0.05
5.14 F 1.42
6.21 F 2.37
0.47 F 0.31
0.34 F 0.26
2.89 F 0.95
2.20 F 1.14
13.25 F 3.71
0.05 F 0.01
0.79 F 0.26
0.53 F 0.17
0.22 F 0.09
0.31 F 0.12
< 0.02
0.04 F 0.01
0.44 F 0.17
0.24 F 0.81
0.59 F 0.09
0.29 F 0.11
0.69 F 0.30
Table 3
Sampling area A. Arsenic content in plant species growing on mine waste dumps S5 (mean F S.E.; mg kg
Plant species
Leaves
Achillea ageratum
Plantago lanceolata
Mentha aquatica
Galactites tomentosa
Silene vulgaris
Coleostephus myconis
Sylibum marianum
Trifolium pratense
Conyza bonariensis
Dorycnium hirsutum
Melilotus officinalis
Lepidium campestre
Dipsacus fullonum
Reichardia picroides
Ranunculus velutinus
Sinapis arvensis
Hedysarum coronarium
Inula viscosa
Hypericum perforatum
Ulmus minor
Sambucus ebulus
Cistus salvifolius
Trifolium incarnatum
Rosa canina
Dactylis hispanica
Medicago sativa
Lotus corniculatus
Sanguisorba minor
Spartium junceum
Foeniculum vulgare
Quercus ilex
Quercus cerris
Holoschoenus vulgaris
Agrostis stolonifera
1.81 F 0.52
9.35 F 1.70
216.35 F 19.36
4.40 F 1.62
5.82 F 1.09
10.85 F 4.52
5.19 F 2.07
0.50 F 0.13
7.70 F 3.28
3.11 F 0.09
0.67 F 0.27
1.44 F 0.35
0.24 F 0.09
1.51 F 0.68
2.14 F 0.88
1.67 F 0.41
0.47 F 0.15
2.97 F 1.31
1.23 F 0.08
0.16 F 0.05
0.59 F 0.16
1.29 F 0.37
0.38 F 0.09
0.39 F 0.21
0.16 F 0.04
Shoots
0.07 F 0.04
37.44 F 9.26
1.15 F 0.07
2.54 F 1.74
2.40 F 0.08
2.16 F 0.49
0.08 F 0.03
2.54 F 0.72
3.24 F 1.04
0.13 F 0.05
0.15 F 0.07
0.09 F 0.02
0.72 F 0.28
0.44 F 0.13
0.06 F 0.02
0.37 F 0.11
0.06 F 0.04
0.87 F 0.09
0.14 F 0.03
0.97 F 0.26
0.22 F 0.07
0.89 F 0.39
0.19 F 0.05
< 0.02
Roots
Inflorescences
0.70 F 0.19
62.18 F 9.74
540.16 F 23.08
16.18 F 3.21
6.68 F 2.76
22.83 F 5.29
5.53 F 0.99
4.46 F 1.72
4.00 F 1.37
2.81 F 0.15
0.86 F 0.17
1.22 F 0.29
5.36 F 0.77
0.83 F 0.25
2.35 F 0.86
0.44 F 0.08
0.66 F 0.24
0.24 F 0.06
1.12 F 0.09
3.32 F 0.73
Seeds
4.50 F 1.08
0.12 F 0.04
0.79 F 0.16
0.21 F 0.04
0.09 F 0.04
0.34 F 0.05
2.81 F 1.04
0.09 F 0.07
0.09 F 0.01
< 0.02
0.08 F 0.03
3.34 F 0.58
0.99 F 0.15
0.17 F 0.02
3.32 F 0.35
0.10 F 0.03
0.05 F 0.01
2.55 F 0.27
< 0.02
6.87 F 1.73
10.13 F 1.08
Table 4
Sampling area A. Arsenic content in plant species growing on mineral processing tailing ponds S6 (mean F S.E.; mg kg
Plant species
Leaves
Shoots
Roots
Achillea ageratum
Silene vulgaris
Plantago lanceolata
Phragmites australis
Dorycnium hirsutum
Aster squamatus
Atriplex patula
Inula viscosa
Melilotus alba
15.29 F 3.94
82.77 F 25.07
24.00 F 7.02
3.71 F 0.95
33.95 F 16.82
6.89 F 1.64
73.64 F 25.09
12.27 F 2.71
52.46 F 5.27
56.06 F 21.03
688.24 F 64.00
16.11 F 3.72
9.63 F 2.19
21.91 F 7.16
5.77 F 1.49
3.58 F 0.85
37.63 F 14.67
47.33 F 9.32
5.74 F 1.07
1.52 F 0.08
54.23 F 3.49
1.49 F 0.07
10.44 F 3.47
5.14 F 0.94
1.05 F 0.05
Leaves
Shoots
Area B
Dactylis hispanica
Helichrysum italicum
Plantago lanceolata
Cichorium intybus
Calluna vulgaris
Hypericum perforatum
Reichardia picroides
Area C
Quarry slopes
Cytisus scoparius
Euphorbia cyparissias
Medicago sativa
Plantago lanceolata
Pasture
Silene dioica
Medicago sativa
)
Inflorescences
34.58 F 7.03
5.07 F 1.09
2.92 F 0.81
Table 5
Sampling areas B and C. Arsenic content in plant species (mean F S.E.; mg kg
Sampling area and site
Rhizomes
)
Leaves and shoots
0.06 F 0.04
0.33 F 0.18
0.26 F 0.10
0.55 F 0.21
0.38 F 0.12
< 0.02
0.77 F 0.25
0.96 F 0.17
Roots
1.74 F 0.59
0.05 F 0.04
0.06 F 0.02
61.3 F 10.62
1.14 F 0.48
3.61 F 0.83
0.67 F 0.22
41.42 F 7.31
2.21 F 0.97
37.79 F 9.18
2.23 F 0.74
3.07 F 0.73
5.51 F 1.46
176.27 F 21.31
) in the more common plant species of the main habitats occurring in the sampling area A
Roots
Shoots
Leaves
< 0.02
0.06 5.00
0.20
3.00 47.00
2.53
0.90
3.00 54.00
0.10
Table 7
Sampling area A. Arsenic content (mean or range; mg kg
leaves and shoots of the most pabular species for livestock
Avena fatua
Bromus hordeaceus
Dactylis hispanica
Hedysarum coronarium
Lotus corniculatus
Medicago sativa
Plantago lanceolata
Sanguisorba minor
Trifolium incarnatum
Trifolium pratense
Sonchus asper
Medicago hispida
Phalaris coerulescens
Brassica napus
Reichardia picroides
Cichorium intybus
Shoots
< 0.02
0.10
3.00
9.00 24.00
0.10
0.40
0.50
0.90
0.08
0.11
0.62
0.54
0.19
1.51
0.02
0.72
) in
Shoots and
leaves
0.40
< 0.02
0.20
0.50
Fruits
< 0.02
Leaves
3.00 34.00
0.05
0.10
0.20
Lake (ex open mine pit) shores and wet surfaces neighbouring to the tailing ponds
Agrostis stolonifera
Mentha aquatica
540.16
37.44
216.35
Phragmites australis
688.00
2.00
4.00
Species
0.77
0.55
< 0.02
3.00
10.00
10
6. Discussion
6.1. Relationships between As contents of soils and
plants
When compared to the As contents of soils at
several mining sites, where total As ranged from 2
to 17,000 mg kg 1 and available As from < 1 to 390
mg kg 1 (de Koe, 1994; Bech et al., 1997; Flynn et
al., 2002; Jung et al., 2002; Madejon et al., 2002;
Visoottiviseth et al., 2002), the values of our soils can
be considered intermediate or moderately low. Nevertheless, in some agricultural soils (pasture of area C
and part of the fields of area A), the arsenic contents
exceeded the Italian legal limits, even for garden or
park (20 mg kg 1) and industrial sites (50 mg kg 1;
DM 471/99, 1999).
The highest values of soluble and extractable As in
area C can be explained by the highest values of total
As in the soils. However, they may also be influenced
by the likely presence of the iron arsenate scorodite
and its stability relationships driven by Eh pH conditions (Vink, 1996).
Our results clearly showed that when the concentration of arsenic in the soil was not particularly high
(as in the fields and vegetable garden of area A), its
availability to plants strongly depended on the total
soil As content. Soluble and extractable As in soils
were positively correlated to the As contents in plants.
This relationship could be perceived throughout the
entire study areas when the mean concentrations for
each sampling site were considered.
This finding agrees with previous results for grass
growing near smelters (Temple et al., 1977), for
Urtica dioica and P. australis growing on experimental soils (Otte et al., 1990) and for Agrostis species
growing at mining sites (de Koe, 1994). We must
11
7. Conclusions
The soil levels of organic matter, available phosphorus, pH and CEC had no effect on soil As content
and its bioavailability to plants. Tissues of the 64 plant
species generally exhibited an As content positively
correlated to that of the soil. Nevertheless, the As
content in plants was always low, even in the most
contaminated conditions, with two exceptions: M.
aquatica and P. australis. In spite of the long contamination history of the surveyed areas, there is an evident
lack of effective pressure toward As tolerance by the
plant species through accumulation of the element.
With few exceptions, the As concentration was
higher in roots than in leaves and shoots. This
decidedly decreases the risk of food chain contamination via herbivores.
Arsenic concentrations were also low in the most
common herbaceous species (crops and wild plants),
in the main chamaephytic and shrubby colonizers and
in the main forest trees. This means that it is likely
that plants play a minor role in superficial geochemical cycling of arsenic. Nevertheless, the arsenic levels
above the legal limits in agricultural soils suggest that
a wider survey of As contents in crops, fodders and
vegetables should be carried out.
12
Acknowledgements
This paper is a contribution to the research project:
Dispersion and transfer of metals to the biosphere in
mining areas, supported by Ministero dellUniversita`
e della Ricerca Scientifica e Tecnologica (MURST)
and the University of Siena.
References
Alloway, B.J., 1990. Soil processes and the behaviour of metal. In:
Alloway, B.J. (Ed.), Heavy Metals in Soils. Chapman & Hall,
Glasgow, pp. 7 28.
Baroni, F., Boscagli, A., Protano, G., Riccobono, F., 2000a. Antimony contents in plant species growing in an Sb-mining district
(Tuscany, Italy). In: Markert, B., Friese, K. (Eds.), Trace Elements in the EnvironmentTheir Distribution and Effects.
Elsevier, Amsterdam, pp. 341 361.
Baroni, F., Boscagli, A., Protano, G., Riccobono, F., 2000b. Antimony accumulation in Achillea ageratum, Plantago lanceolata
and Silene vulgaris growing in an old Sb-mining area. Environmental Pollution 109, 347 352.
Bech, J., Poschenrieder, C., Llugany, M., Barcelo, J., Tume, P.,
Tobias, F.J., Barranzuela, J.L., Vasquez, E.R., 1997. Arsenic
and heavy metal contamination of soil and vegetation around
a copper mine in Northern Peru. The Science of the Total Environment 203, 83 91.
Bhumbla, D.K., Keefer, R.F., 1994. Arsenic mobilization and bioavailability in soils. In: Nriagu, J.O. (Ed.), Arsenic in the Environment (Part I). Wiley, New York, pp. 51 82.
Bowen, H.J.M., 1979. Environmental Chemistry of the Elements.
Academic Press, London.
Carbonell, A.A., Aarabi, M.A., DeLaune, R.D., Gambrell, R.P.,
Patrick Jr., W.H., 1998. Arsenic in wetland vegetation:
availability, phytotoxicity, uptake and effects on plant growth
and nutrition. The Science of the Total Environment 217,
189 199.
Carobbi, G., Rodolico, F., 1976. I minerali della Toscana. Olschki,
Firenze.
Chaney, R.L., 1989. Toxic element accumulation in soils and crops:
protecting soil fertility and agricultural food-chains. In: BarYosef, B., Barrow, N.J., Goldshmid, J. (Eds.), Inorganic Contaminants in the Vadose Zone. Springer, Berlin, pp. 140 158.
Cipriani, C., Franzini, M., Malesani, P., Sabatini, G., 1971. I giacimenti di materiali litoidi. Rendiconti Societa` Italiana Mineralogia e Petrologia 27, 317 355 (special issue).
Daget, P., Poissonet, J., 1971. Une metode danalyse phytologique
des prairies. Annales Agronomiques 22, 5 41.
de Knecht, J.A., van Baren, N., Ten Bookum, W.T., Wong Fong
Sang, H.W., Koevoets, P.L.M., Schat, H., Verkleij, J.A.C.,
1995. Synthesis and degradation of phytochelatins in cadmiumsensitive and cadmium-tolerant Silene vulgaris. Plant Science
106, 9 18.
de Koe, T., 1994. Agrostis castellana and Agrostis delicatula on
13
Protano, G., Riccobono, F., 1997. Environmental levels of antimony, arsenic and mercury in the Tafone mining area (southern Tuscany, Italy). Atti Societa` Toscana Scienze Naturali 104,
75 83.
Protano, G., Riccobono, F., Sabatini, G., 1998. La cartografia
geochimica della Toscana meridionale. Criteri di realizzazione
e rilevanza ambientale attraverso gli esempi di Hg, As, Sb,
Pb e Cd. Memorie Descrittive Carta Geologica dItalia 55,
pp. 119 140. With English Abstr.
Protano, G., Riccobono, F., Sabatini, G., 1999. Geochemical
anomalies for toxic heavy elements in southern Tuscany (Italy):
anthropogenic and natural sources. Proc. 2nd Conf. Environmental Geochemical Baseline Mapping in Europe, Vilnius, Lithuania, pp. 71 75.
Qian, J.H., Zayed, A., Zhu, Y.L., Yu, M., Terry, N., 1999. Phytoaccumulation of trace elements by wetland plants: III. Uptake and
accumulation of ten trace elements by twelve plant species.
Journal of Environmental Quality 28, 1448 1455.
Riccobono, F., 1993. I giacimenti minerari. In: Giusti, F. (Ed.), La
Storia Naturale della Toscana Meridionale. Amilcare Pizzi, Milano, pp. 107 139.
Robinson, B., Outred, H., Brooks, R., Kirkman, J., 1995. The distribution and fate of arsenic in the Waikato River system, North
Island, New Zealand. Chemical Speciation and Bioavailability
7, 89 96.
Schmoger, M.E.V., Oven, M., Grill, E., 2000. Detoxification of
arsenic by phytochelatins in plants. Plant Physiology 122,
793 801.
SISS Societa` Italiana per la Scienza del Suolo, 1985. Metodi normalizzati per lanalisi del suolo. Edagricole, Bologna.
Sneller, F.E.C., Van Heerwaarden, L.M., Kraaijeveld-Smit, F.J.L.,
Ten Bookum, W.M., Koevoets, P.L.M., Schat, H., Verkleij,
J.A.C., 1999. Toxicity of arsenate in Silene vulgaris, accumulation and degradation of arsenate-induced phytochelatins. New
Phytologist 144, 223 232.
Sostaric-Pisacic, K., Kovacevic, J., 1974. Evaluation of quality and
total value of grassland and leys by the Complex Method.
Agriculturae Conspectus Scientificus, University of Zagreb,
14 102 (in Croatian, with English Abstr).
Storer, D.A., 1984. A simple high volume ashing procedure for determining soil organic matter. Communications in Soil Science
and Plant Analysis 15, 759 772.
Temple, P.J., Linzon, S.N., Chai, B.I., 1977. Contamination of vegetation and soil by arsenic emission from secondary lead smelters. Environmental Pollution 12, 311 320.
Thornton, I., Abrahams, P.W., 1983. Soil ingestiona major pathway of heavy metals into livestock grazing contaminated land.
The Science of the Total Environment 28, 287 294.
Ure, A.M., Quevauviller, P., Muntau, H., Griepink, B., 1993. Speciation of heavy metals in soils and sediments. An account of
the improvement and harmonization of extraction techniques
undertaken under the auspices of the BCR of the Commission
of the European Communities. International Journal of Environmental Analytical Chemistry 51, 135 151.
Vink, B.W., 1996. Stability relations of antimony and arsenic compounds in the light of revised and extended Eh pH diagrams.
Chemical Geology 130, 21 30.
14
Visoottiviseth, P., Francesconi, K., Sridokchan, W., 2002. The potential of Thai indigenous plant species for the phytoremediation
of arsenic contaminated land. Environmental Pollution 118,
453 461.
Warren, H.V., Delavault, R.E., Barasko, J., 1968. The arsenic content of Douglas Fir as a guide to some gold, silver and base
metal deposits. Canadian Mining Metallurgical Bulletin 7, 1 9.
Wedepohl, K.H., 1970. Handbook of Geochemistry. Springer,
Berlin.
Wenzel, W.W., Jockwer, F., 1999. Accumulation of heavy metals in
plants grown on mineralised soils of the Austrian Alps. Environmental Pollution 104, 145 155.