arsenic in soil and vegetation of contaminated areas in southern tuscany_italy
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Arsenic in Soil and Vegetation of Contaminated Areas in Southern Tuscany_ItalyTRANSCRIPT
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Arsenic in soil and vegetation of contaminated areas in
southern Tuscany (Italy)
F. Baronia , A. Boscagli b, L.A. Di Lella a , G. Protanoa , F. Riccobonoa,*
a 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) wasindependent 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 Earth’s 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)
appears appropriate for clayey rocks such as shales.
Since As accumulates during weathering and translo-
cation in colloid fractions, its concentration is usually
higher in soil than in parent rocks (Yan-Chu, 1994). Innature, the element is a fundamental constituent of the
sulfide mineral arsenopyrite (FeAsS), as well as the
minerals lollingite (FeAs), realgar (AsS) and orpiment
(As2S3).
The anthropogenic contribution to As contents of
superficial geochemical environments is also impor-
tant (Nriagu and Pacyna, 1988; Pacyna et al., 1995).
In some cases, mining activity is directly involved in
the release of huge stocks of arsenic into superficial
environments (Murdoch and Clair, 1986).
0375-6742/$ - see front matter D 2003 Elsevier B.V. All rights reserved.doi:10.1016/S0375-6742(03)00208-5
* Corresponding author. Fax: +39-577-233945.
E-mail address: [email protected] (F. Riccobono).
www.elsevier.com/locate/jgeoexp
Journal of Geochemical Exploration 81 (2004) 1–14
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Arsenic exists in soil mainly as pentavalent (AsV)
arsenate (AsO43), which mak es up 90% of dissolved
As species in aerobic soils (O’Neill, 1995), or as
trivalent (AsIII
) arsenite (AsO2
). The latter representsthe most environmentally dangerous form of As.
The chemical similarity of arsenate to phosphate
and the high affinity of arsenite with sulfhydryl groups
of enzymatic and structural proteins are the ultimate
reasons for arsenic toxicity to living organisms.
The arsenate anion is rather easily chemisorbed by
soil colloids and, deriving from the strong arsenic acid
H3AsO4, adsorbs most effectively at low pH. Conse-
quently, arsenate mobility is quite low in acidic soils,
especially where high contents of clay or metal oxide
are involved. Conversely, in alkaline soils, As may be
mobile in the soluble Na-arsenate form (McBride,
1994). Thus, adsorption of arsenate onto soil particles
is dependent on various parameters, but mostly pH.
According to Elkhatib et al. (1984), the pH, the
redox conditions and the Fe-oxide content in soil are
the most important features controlling AsIII adsorp-
tion. The element has a rather long residence time in
soils (from 1000 to 3000 years; Bowen, 1979) and
tends to be enriched into top horizons by cycling
through vegetation, atmospheric deposition and sorp-
tion by soil organic matter (Alloway, 1990). Its
availability for uptake by plants is affected by severalfactors, such as the source, chemical speciation and
soil parameters (pH, Eh, organic matter and colloid
contents, soil texture and drainage conditions; Eisler,
1994; Mitchell and Barr, 1995).
The mobility of arsenic in aqueous solutions in-
creases in the trivalent oxidation state (Hermann and
Neumann-Mahlkau, 1985). However, the conversion
of AsV to AsIII appears rather slow, even under
strongly reducing conditions, as suggested by obser-
vations on a range of redox and pH environments
(Masscheleyn et al., 1991).In terrestrial plants, arsenic uptake is largely spe-
cies specific and arsenic concentrations in plant tis-
sues generally cannot be related to those in the soils
(O’Neill, 1995). In this regard, it is relevant for human
health that As levels in edible plants are usually low,
even when they grow on contaminated soils (NRC,
1977; MAFF, 1982).
Kabata-Pendias and Pendias (1984) reported that
the As background for terrestrial plants growing on
uncontaminated soils ranges from 0.009 to 1.5 mg
kg 1 on a d.w. basis. Some species of the genus
Agrostis growing on contaminated soils have been
found to accumulate and tolerate high As levels: up to
6640 mg kg 1
d.w. in the old leaves of A. canina and A. tenuis (Porter and Peterson, 1975), 1350 mg kg 1
in Agrostis stolonifera (Porter and Peterson, 1977a),
1900 mg kg 1 in Agrostis castellana and 1800 mg
kg 1 in Agrostis delicatula (de Koe et al., 1991; de
Koe, 1994). Pseudosuga taxifolia, Pityrogramma cal-
omelanos and Pteris vittata growing on soils of
mineralized or contaminated areas were even more
able to accumulate As, showing cont ents of 8200,
8350 and 7526 mg kg 1, respectively (Warren et al.,
1968; Ma et al., 2001; Visoottiviseth et al., 2002).
Aquatic plants such as Ceratophyllum demersum,
Egeria densa and Potamogeton pectinatus accumu-
lated arsenic up to 1160, 1120 and 4990 mg kg 1,
respectively, without any apparent damage (Dushenko
et al., 1994; Robinson et al., 1995). In contrast,
wetland plants a ppear unable to accumulate As to
the same extent (Otte et al., 1990; Qian et al., 1999).
The highest concentrations have been found in Spar-
tina alterniflora (550 mg kg 1) by Carbonell et al.
(1998) and in Eichornia crassipes (500 mg kg 1) by
Zhu et al. (1999).
Arsenic is not an essential element for plants, and
once it is taken up, usually only a small proportion istranslocated to the epigeal parts. The result is the
following concentration gradient: roots>stems>leaves.
Nevertheless, concentrations up to 2000, 22,630 and
8350 mg kg 1 were found in foliage of Agrostis
ecotypes, P. vittata and P. calomelanos, respectively,
by Porter and Peterson (1975, 1977a,b), Ma et al.
(2001) and Visoottiviseth et al. (2002).
Inside the plant cell, the two most common chem-
ical species (arsenite and arsenate) strongly induce
phytochelatin synthesis, which has an important role
in detoxification (Schmoger et al., 2000).This paper deals with the impact on vegetation of
As diffusion into the environment related to different
forms of historical mining activities.
2. The study areas
Since the pre-Roman Age, southern Tuscany has
been one of the few important mining districts in Italy.
Epithermal deposits of Hg and Sb were intensely
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exploited until the 1970s. These intensive mining and
smelting activities produced huge quantities of waste
materials which, in the absence of any reclamation,
still release toxic heavy elements into the surroundingenvironment (Protano and Riccobono, 1997; Protano
et al., 1998). Since As is a minor but ubiquitous
constituent of the epithermal mineral assemblage of
these ores (Riccobono, 1993), this element also con-
tributes to the overall pollution of the mining areas.
High resolution geochemical maps of southern Tus-
cany (Protano et al., 1998, 1999) have shown that
strong, extensive As anomalies are present in various
areas of this region where base metal and Sb– Hg
epithermal deposits were exploited in the past.
In addition to the abandoned mining and smelting
areas, other situations with severe arsenic contamina-
tion are known from this region. In the Mt. Amiata
volcanic massif area in the southeastern corner of the
region, there are numerous deposits of yellow-brown
ochre, employed as a dye since the Etruscan Age and
intensely exploited until very recently. These deposits
consist of horizons (3–4 m thick) belonging to the
sedimentary sequence of Quaternary lacustrine basins.
The ochre exhibits extremely high arsenic contents,
ranging (if expressed as As2O3) from 0.59% to 9.04%
by weight (Cipriani et al., 1971). Such high figures are,
at least in part, due to the diffuse presence of ironarsenates (most probably poorly crystalline FeAsO4
2H2O or scorodite).
Fig. 1 shows the location of the three areas of
southern Tuscany (with expected anomalous As con-
tents in the soil) where we chose to investigate the
transfer of this element from soil to plant species.
Area A is in the Sb-mining district of the Tafone
Valley in the Monti Romani area (Protano and Ricco-
bono, 1997; Baroni et al., 2000a). The most important
antimony mines of the region were active there,
together with a plant for Sb-ore smelting and the production of antimony trioxide.
Area B refers to the old antimony mine of Cetine di
Cotorniano near the town of Siena, which was mainly
exploited in the period between the two World Wars.
More than half a century after closure, the mine dumps
and the roasting-plant area are now largely colonized
by several herbaceous plant and shrub species.
Area C is located in the volcanic massif of Mt.
Amiata near the town of Castel del Piano (Grosseto
County). A quarry was active there for the exploita-
tion of an extensive ochre horizon. The central and
deepest part of the quarry is now occupied by a very
small lake, while the surroundings are colonized by
wild vegetation.
The general geology and lithological features of
areas A and B are not identical but rather similar. APaleozoic metamorphic basement, mainly composed
of quartzites and metasandstones, is unconformably
covered by a Triassic succession. The lowest carbon-
ate member (Cavernous Limestone) of the Mesozoic
sequence was widely affected by strong hydrothermal
alterations, which mostly produced limestone siliciza-
tion, and hosts stibnite (Sb2S3)-rich ore bodies.
Area C lies on the lava flows, mostly riodacitic in
composition, present on the western slope of the
inactive Mt. Amiata volcano. The ochre horizons are
Fig. 1. Location of the study areas in southern Tuscany (see text).
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often interlayered with very thin clayey and diatomite
levels, sometimes bearing lenses of yellow opal
(Cipriani et al., 1971). Analyses of ochre samples
revealed very high contents of iron (up to 65% Fe byweight) and arsenic (up to 9% As expressed as As2O3
by weight; Cipriani et al., 1971). The genesis of these
As-rich ochre horizons has still not been satisfactorily
explained. However, according to Carobbi and Rodo-
lico (1976), both inorganic and organic processes
were involved in the formation of this quite peculiar
type of rock.
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 sur-
roundings 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 minedumps 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 miner-
als. 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 thei r potential use as phytoremediators,
according to their:
– adaptation to adverse edaphic conditions
– large biomass allocation in the above-ground part
– fast maximization of above-ground biomass
– frequency in the field
At least three specimens of each selected species
were collected for analysis at each sampling site. In
species where roots were difficult to collect, only the
shoots were collected.
From four to nine soil samples, representative of
the top 20 cm, were collected at each site.
The nomenclat ure of the plant species is according
to Pignatti (1982).
4. Materials and methods
4.1. Analysis of plant tissues and soil
Plant material was carefully washed in tap water
and then processed in an ultrasonic cleaner to remove
soil particles. This was followed by a rinse with
acidified deionized water (HCl 3%) and a final rinse
with ultra-pure water.
Absorbing (roots) and non-absorbing parts of
plants (leaves, shoots, inflorescence, etc.) were usual-
ly separated in order to obtain information about the
species’ ability to transfer As. In some species,
especially those of Gramineae, the leaves and shoots
were analyzed together because of the difficulty in
separating them. The plant material was oven-dried at
40 jC to constant weight, then pulverized. About 0.5
g of dry matter was digested with a Milestone micro-
wave lab-station (Ethos 900) after addition of 5 ml
HNO3 and 2 ml H2O2 (Baker ultra-pure reagents).
Soil samples were air dried, sieved through a 2-mmmesh and pulverized in an agate mortar. They were
then subjected to acid digestion for determination of
total As content: 1 ml HF + 2 ml HNO3 + 2 ml HCl + 1
ml HClO4 were added to 200 mg of powdered soil and
the mixture was processed with an Ethos 900 lab-
station. An estimate of the phytoavailable As content
was obtained by both pure water and gentle acidic
extraction. Water extraction was performed by adding
100 ml of ultra-pure water to 40 g of soil and shaking it
for 24 h; acidic extraction was carried out by adding
200 ml of a 0.43 mol solution of acetic acid to 5 g of soil and shaking it for 16 h (according to the procedure
of Ure et al., 1993). Polyethylene bottles were used to
collect and store the solution after the extraction.
Atomic absorption determination of As contents
was carried out with a Perkin-Elmer 5000 AAS,
equipped with FIAS, employing the hydride genera-
tion method. Working standards for chemical analyses
were prepared from Perkin-Elmer stock solutions.
Reference standards were SV-M (soil) from the Insti-
tute of Radioecology and Applied Nuclear Techniques
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(IRANT), Kosice (Slovakia), 2709 San Joaquin soil
from NIST, BCR 60 (aquatic plant) from the Bureau
of Reference of the EU and GBW-07603 (bush
branches and leaves) from the Institute of Geophysicaland Geochemical Exploration of Langfang (China).
Accuracy of the analytical results was within 7%.
The cation exchange capacity (CEC) was deter-
mined by the compulsive exchange procedure sug-
gested by Gillman and Sumpter (1986); extractable
phosphorus was measured by UV – Visible spectro-
photometry (Hach DR-4000) following the Hach
8190 method; the pH was measured in deionized
water (soil/water ratio = 1:2.5 w/v). Organic matter
contents were estimated through the percentage loss
in weight after ignition at 375 jC for 16 h in a furnace
(Storer, 1984).
4.2. Data analysis
The analytical results were used to check the
relationships between: (i) total, soluble and extract-
able soil arsenic; (ii) soil and plant As contents.
Two coefficients, Biological Absorption Coeffi-
cient (BAC) and Concentration Factor (CF), were
also considered. The former is the ratio of plant
arsenic to total soil arsenic (Edwards et al., 1998),
while the latter is the ratio of plant arsenic to solubleor extractable arsenic in the soil. The CFs for soluble
and extractable soil arsenic were designated as CFsol
and Cf extr , respectively. Relationships were identified
with the non-parametric Spearman Rank Correlation
Coefficient.
The ability of the plant species to translocatearsenic from the roots to shoots was also tested. The
palatability of each plant species to livestock (primar-
ily to sheep, the most common livest ock in the study
areas) was consider ed according to Daget and Pois-
sonet (1971) and Sostaric-Pisacic and Kovacevic
(1974).
5. Results
5.1. Soils
In the Tafone–Chiarone district (area A), the total
arsenic contents in soils of the cultivated and unculti-
vated 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
38to899mgkg 1 in the dumps and from 2 to2466 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 (meanFS.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) 14.60F 1.00a 0.01F 0.01a 0.10F 0.03a 4.37F 0.66a 5.8F 0.2a 0.13F 0.07a 5.34F 1.39a
S2 (n = 4) 5.30F 2.17b 0.01F 0.01a 0.08F 0.03a 4.82F 0.80a 5.5F 0.1a 0.15F 0.05a 5.51F1.08a
S3 (n = 4) 39.90F 2.85c 0.02F 0.01a 0.04F 0.02a 5.25F 1.27a 5.4F 0.3a 0.18F 0.12a 5.97F 0.42a
S4 (n = 5) 40.00F 3.81c 0.02F 0.01a 0.08F 0.02a 4.59F 0.30a 5.0F 0.1a 0.11F 0.10a 5.19F 1.54a
S5 (n = 9) 265.60F 88.26cd 0.01F 0.01a 0.66F 0.23b 3.03F 0.40ab 7.3F 0.2ab 0.14F 0.03a 5.83F 1.54a
S6 (n = 6) 1225.60F 351.70d 0.04F 0.02a 1.50F 0.33c 1.68F 0.39b 7.2F 0.5ab 0.11F 0.02a 4.06F 0.96a
Area B
(n = 4) 372.83F 77.25 0.03F 0.02 0.52F 0.18 3.06F 0.55ab 8.2F 0.6b 0.08F 0.04a 5.49F 1.63a
Area C
Quarry slopes (n = 4 ) 753.82F 34.55a 1.82F 0.27a 7.60F 0.91a 2.80F 0.22ab 5.8F 0.7a 0.97F 0.89bb 6.04F 0.59a
Pasture (n = 4) 2035.32F 297.12b 8.48F 1.40b 35.80F 2.98b 5.05F 1.41a 6.2F 0.9ab 0.83F 0.39bb 6.66F 1.04a
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Water-soluble arsenic gave figures from 2 to 5
orders of magnitude lower than the total As values.
In area A, the mean value (for each sam pling site)
varied from 10 to 40 Ag kg 1
(see Table 1), while thetotal range was from 2 to 70 Ag kg 1. In area C, the
water-soluble arsenic content was very high, especial-
ly in soils of pastures (mean: 8.5 mg kg 1).
There was a rather similar pattern for acid-ex-
tractable arsenic. The As contents reached the high-
est values in C but the extractable fraction still
represented a very small aliquot of the total As
(0.1–1.8%).
A relationship between As contents was only
evident in the case of fields (cultivated and old),
particularly between total and soluble As (r = 0.921;
p < 0.01; n = 17). However, when the high variability
of the data (the coefficients of variation averaged
53%) was smoothed by considering the mean of each
sampling site, the soluble and extractable fractions
were correlated with the total contents (r = 0.887 andr = 0.862, respectively; p < 0.01; n = 9), and a relation-
ship between the soluble and extractable fractions also
appeared (r =0.680; p < 0.05; n =9).
According to SISS (1985) criteria, only the soil of
the area A tailing ponds (S6) can be considered poor
in organic matter (Table 1). The pH was acidic in the
fields of area A (S1–S4) and area C, while it was
neutral or alkaline in the mine wastes of areas A (S5–
S6) and B, respectively.
All sampling sites showed very low levels of avail-
able phosphorus in the soil, as well as low cation
exchange capacities (CEC). The correlation analysis
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
(meanF S.E.; mg kg 1)
Sampling sites and
plant species
Leaves Leaves and
shoots
Shoots Roots Flowers and
inflorescences
Fruits and
seeds
S1
Zea mays < 0.02 0.03F 0.02
Triticum aestivum < 0.02
S2
Helianthus annus 0.04F 0.01 0.03F 0.02 Medicago sativa 0.04F 0.03
S3
Lactuca sativa 0.13F 0.11
Solanum melangena 0.11F 0.09
Cucurbita pepo 0.23F 0.12 0.23F 0.11
Capsicum annuum 0.27F 0.18 < 0.02
Lycopersicon esculentum 0.07F 0.03 < 0.02
S4
Rubus ulmifolius 0.86F 0.19 0.21F 0.19
Sonchus asper 0.11F 0.05 1.24F 0.73
Medicago hispida 0.62F 0.14 1.14F 0.27
Bromus hordeaceus < 0.02 0.53F 0.17
Bromus madritensis 0.04F 0.02 0.22F 0.09
Helichrysum italicum 2.53F 1.99 1.05F 0.05 0.31F 0.12
Phalaris coerulescens 0.54F 0.09 5.14F 1.42 < 0.02
Avena fatua 0.44F 0.15 6.21F 2.37 0.04F 0.01
Achillea ageratum 6.95F 1.72 0.47F 0.31
Brassica napus 0.19F 0.13 0.02F 0.01 0.34F 0.26
Lupinus albus 2.54F 1.79 0.81F 0.13 2.89F 0.95 0.44F 0.17
Urospermum dalechampii 0.07F 0.06 2.20F 1.14 0.24F 0.81
Coleostephus myconis 0.62F 0.21 0.04F 0.03 13.25F 3.71 0.59F 0.09
Rumex crispus 0.48F 0.33 < 0.02 0.05F 0.01 0.29F 0.11
Anchus italica 1.39F 0.74 0.09F 0.02 0.79F 0.26 0.69F 0.30
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showed that the As contents of soil (total, soluble and
extractable) were independent of CEC, pH, content of
available phosphorus and organic matter. All the
edaphic parameters were also independent of eachother.
5.2. Arsenic contents of plant species
In total, 64 plant species were sampled, 59 of them
in the Tafone–Chiarone district (area A). The plant
species were mostly Dicotyledons (54), Compositae
(15), Leguminosae (12) and Gramineae (9), tap-rooted
(42), perennial (41) and herbaceous (54), largely as a
result of the sampling criteria. Some species, such as
Achillea ageratum, Dactylis hispanica, Helichrysum
italicum, Inula viscosa, Medicago sativa, Plantago
lanceolata and Silene vulgaris, were collected in two
or more sampling sites.In area A, crops and vegetables sampled at sites S1,
S2 and S3 showed very low As concentrations,
sometimes below the limit of instrumental detection
(Table 2). In the old field (S4), plants had As contents
of 1–2 mg kg 1 or less and only the weed Coleos-
tephus myconis showed slight accumulation, with 13
mg kg 1 of arsenic in its roots (Table 2). Only 5 ( P.
lanceolata, Mentha aquatica, Galactites tomentosa,
C. myconis and A. stolonifera) of the 34 plant species
sampled on the mine dumps (S5) had at least 10 mg
Table 3
Sampling area A. Arsenic content in plant species growing on mine waste dumps S5 (meanF S.E.; mg kg 1)
Plant species Leaves Shoots Leaves and shoots Roots Inflorescences Seeds
Achillea ageratum 1.81F 0.52 0.07F 0.04 0.70F 0.19 3.32F 0.73
Plantago lanceolata 9.35F 1.70 62.18F 9.74
Mentha aquatica 216.35F 19.36 37.44F 9.26 540.16F 23.08
Galactites tomentosa 4.40F 1.62 1.15F 0.07 16.18F 3.21
Silene vulgaris 5.82F 1.09 2.54F 1.74 6.68F 2.76
Coleostephus myconis 10.85F 4.52 2.40F 0.08 22.83F 5.29 4.50F 1.08
Sylibum marianum 5.19F 2.07 2.16F 0.49 5.53F 0.99
Trifolium pratense 0.50F 0.13 0.08F 0.03 4.46F 1.72
Conyza bonariensis 7.70F 3.28 2.54F 0.72 4.00F 1.37 Dorycnium hirsutum 3.11F 0.09 3.24F 1.04 2.81F 0.15
Melilotus officinalis 0.67F 0.27 0.13F 0.05 0.86F 0.17
Lepidium campestre 1.44F 0.35 0.15F 0.07 1.22F 0.29 0.12F 0.04
Dipsacus fullonum 0.24F 0.09 0.09F 0.02 5.36F 0.77
Reichardia picroides 1.51F 0.68 0.72F 0.28 0.83F 0.25
Ranunculus velutinus 2.14F 0.88 0.44F 0.13 2.35F 0.86
Sinapis arvensis 1.67F 0.41 0.06F 0.02 0.44F 0.08
Hedysarum coronarium 0.47F 0.15 0.37F 0.11 0.66F 0.24
Inula viscosa 2.97F 1.31 0.06F 0.04 0.24F 0.06
Hypericum perforatum 1.23F 0.08 0.87F 0.09 1.12F 0.09
Ulmus minor 0.16F 0.05 0.14F 0.03
Sambucus ebulus 0.59F 0.16 0.97F 0.26 0.79F 0.16
Cistus salvifolius 1.29F 0.37 0.22F 0.07
Trifolium incarnatum 0.38F 0.09 0.89F 0.39 0.21F 0.04
Rosa canina 0.39F 0.21 0.19F 0.05 0.09F 0.04
Dactylis hispanica 0.16F 0.04 < 0.02 0.34F 0.05
Medicago sativa 2.81F1.04 3.34F 0.58
Lotus corniculatus 0.09F 0.07 0.99F 0.15
Sanguisorba minor 0.09F 0.01 0.17F 0.02
Spartium junceum < 0.02
Foeniculum vulgare 0.08F 0.03 3.32F 0.35 2.55F 0.27
Quercus ilex 0.10F 0.03
Quercus cerris 0.05F 0.01 < 0.02
Holoschoenus vulgaris 6.87F 1.73
Agrostis stolonifera 10.13F 1.08
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kg 1 of arsenic in their tissues, mostly in the roots
(Table 3). The M. aquatica specimens collected at the
shores of the small lake had rather high arsenic levels,
both in the leaves (mean: 216 mg kg 1) and roots
(mean: 540 mg kg 1).
Almost all the plant species growing in the tailing
ponds were sampled because of the small number
growing at this site. They generally had higher arsenic
contents than plants at the other sampling sites (com-
pare Table 4 with Tables 2, 3 and 5). However, in five
of the nine collected species, the arsenic concentra-
tions were < 50 mg kg 1 and only the roots of
Phragmites australis (mean: 688 mg kg 1) showed
arsenic accumulation.
In the intensively sampled area A, there were low
or very low arsenic contents in most plant species
growing on the mine dumps, slopes and neighboring
dry badlands. This was es pecially true for the above-
ground biomass (Table 6). In this area, I. viscosa and
Dorycnium hirsutum showed slightly higher arsenic
contents than other species.
Plant species common in wet habitats, such as M.
aquatica and P. australis, showed high arsenic con-
tents mostly in roots but also in leaves ( M. aquatica).
The above-ground tissues of the plant species most
palatable to livestock showed very low arsenic con-
centrations, except for the leaves of P. lanceolata (9 –
24 mg kg 1 on d.w.; Table 7).
Table 4
Sampling area A. Arsenic content in plant species growing on mineral processing tailing ponds S6 (meanFS.E.; mg kg 1)
Plant species Leaves Shoots Roots Rhizomes Inflorescences
Achillea ageratum 15.29F 3.94 6.89F 1.64 12.27F 2.71 34.58F 7.03Silene vulgaris 82.77F 25.07 73.64F 25.09 52.46F 5.27
Plantago lanceolata 24.00F 7.02 56.06F 21.03
Phragmites australis 3.71F 0.95 1.52F 0.08 688.24F 64.00 5.07F 1.09
Dorycnium hirsutum 33.95F 16.82 54.23F 3.49 16.11F 3.72
Aster squamatus 1.49F 0.07 9.63F 2.19 2.92F 0.81
Atriplex patula 37.63F 14.67 10.44F 3.47 21.91F 7.16
Inula viscosa 47.33F 9.32 5.14F 0.94 5.77F 1.49
Melilotus alba 5.74F 1.07 1.05F 0.05 3.58F 0.85
Table 5
Sampling areas B and C. Arsenic content in plant species (meanFS.E.; mg kg 1)
Sampling area and site Leaves Shoots Leaves and shoots Roots
Area B
Dactylis hispanica 0.06F 0.04 1.74F 0.59
Helichrysum italicum 0.33F 0.18 0.05F 0.04
Plantago lanceolata 0.26F 0.10 0.06F 0.02
Cichorium intybus 0.55F 0.21
Calluna vulgaris 0.38F 0.12
Hypericum perforatum < 0.02
Reichardia picroides 0.77F 0.25
Area C
Quarry slopes
Cytisus scoparius 0.96F 0.17 0.67F 0.22
Euphorbia cyparissias 61.3F 10.62 41.42F 7.31
Medicago sativa 1.14F 0.48 2.21F 0.97
Plantago lanceolata 3.61F 0.83 37.79F 9.18
Pasture
Silene dioica 176.27F 21.31 3.07F 0.73
Medicago sativa 2.23F 0.74 5.51F1.46
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Very low arsenic contents were found in plant
species collect ed in ar ea B (<1 mg kg 1 in almost
all the plants; Table 5) and area C. Exceptions were
Euphorbia cyparissias and P. lanceolata sampled on
the quarry slopes and notably Silene dioica from
pastures, which contained 176 mg kg 1 As in its
leaves.
5.3. Arsenic accumulation and translocation in plants
In general, the ability of the plants to accumulate
arsenic, as expressed by the Biological Accumulation
Coefficients (BACs) and Concentration Factors (CFs),
was independent of the As contents in the soils. These
indices were not correlated with total, soluble or extractable arsenic in soil.
Nevertheless, when the plant part with the highest
As content was considered for each species, there
were significant relationships between arsenic in the
plant tissue and the total, soluble and extractable
arsenic in the soil (r = 0.635, 0.439 and 0.951, respec-
tively; p < 0.001; n = 80).
With the exception of M. aquatica (BAC = 2.03),
the BACs of all the plant species were < 1; in 91% of
them, the BAC was < 10 1 and in 55% < 10 2. The
CFs for extractable arsenic were generally low: < 5 in69% and < 20 in 86% of cases. The highest values
referred to the roots of the two wetland plants M.
aquatica (818) and P. australis (459).
Very high CFsol values were found in M. aquatica
(90,026), P. lanceolata (10,363) and P. australis
(17,206). They were also high in A. stolonifera
(1688), C. myconis (3805), Conyza bonariensis
(1283), D. hirsutum (1356), G. tomentosa (2697),
Holoschoenus vulgaris (1145), I. viscosa (1183) and
S. vulgaris (2069).
Table 6
Arsenic content (mean or range; mg kg 1) in the more common plant species of the main habitats occurring in the sampling area A
Habitats and species Roots Shoots Leaves Shoots and leaves Fruits
Mine dumps and slopes and neighbouring badlands Bromus hordeaceus < 0.02
Bromus madritensis 0.04
Dactylis hispanica < 0.02 0.20
Inula viscosa 0.20 – 6.00 0.06 – 5.00 3.00 – 47.00
Helichrysum italicum 1.00 2.53
Spartium junceum <0.02
Rubus ulmifolius 0.90
Dorycnium hirsutum 3.00 –16.00 3.00 –54.00 3.00 –34.00
Quercus cerris 0.05 < 0.02
Quercus ilex 0.10 3.00
Ulmus minor 0.10 0.20
Lake (ex open mine pit) shores and wet surfaces neighbouring to the tailing ponds
Agrostis stolonifera 10.00 Mentha aquatica 540.16 37.44 216.35
Phragmites australis 688.00 2.00 4.00
Table 7
Sampling area A. Arsenic content (mean or range; mg kg 1) in
leaves and shoots of the most pabular species for livestock
Species Leaves Shoots Shoots and
leaves
Avena fatua 0.40
Bromus hordeaceus < 0.02
Dactylis hispanica 0.20 < 0.02
Hedysarum coronarium 0.50
Lotus corniculatus 0.10
Medicago sativa 3.00
Plantago lanceolata 9.00–24.00
Sanguisorba minor 0.10
Trifolium incarnatum 0.40 0.90
Trifolium pratense 0.50 0.08
Sonchus asper 0.11
Medicago hispida 0.62
Phalaris coerulescens 0.54
Brassica napus 0.19 0.02
Reichardia picroides 1.51 0.72 0.77
Cichorium intybus 0.55
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In most of the sampled species, the roots had the
highest arsenic concentration (Tables 2 – 5). The trans-
location of As to shoots was low or very low, with
translocation coefficients (TC) < 2 in 76% of cases.Three species showed enhanced As transport to shoots:
A. ageratum collected in the old field (TC = 14.8), I.
viscosa from the tailing ponds (TC = 8.2) and dumps
(TC = 12.4) of area A and S. dioica collected in the
pastures of area C (TC = 57.4).
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. Nev-
ertheless, 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 con-
ditions (Vink, 1996).
Our results clearly showed that when the concen-
tration 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 totalsoil 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 experimen-
tal soils (Otte et al., 1990) and for Agrostis species
growing at mining sites (de Koe, 1994). We must
observe, however, that this relationship was not found
in other cases (O’Neill, 1995; Pitten et al., 1999).
Perhaps a parallel change of As contents in plants and
As contents in soils through a gradient can be moreeasily detected when several plant species are sampled
(as in our study).
In contrast, As translocation from the roots to the
above-ground biomass appeared to be under stronger
biological control than As uptake. This could explain
the lack of correlation between As contents of soils
and As concentrations in the epigeal parts. In this
respect, our results strongly agree with the literature
data (Otte and Ernst, 1994; O’Neill, 1995).
When we compared the As contents in our plants
with those sampled at other mining sites by de Koe
(1994), Bech et al. (1997), Jung et al. (2002), Made-
jon et al. (2002) and Visoottiviseth et al. (2002), we
found much lower maximum values (from less than
one-half to less than one-tenth). Since As contents in
our soils were also lower in the most contaminated
situations, a weaker selective pressure can be inferred
or, simply, more effective accumulator plant species
may have escaped our sampling.
Neither the arsenic availability in soils nor its
concentration in plants reflected the differences in
organic matter content, pH and available phosphorus
in soils of the sampling sites. All these factors areknown to affect both bioavailability and plant uptake
of As (Otte et al., 1990; Bhumbla and Keefer, 1994).
Yet in our study, these factors had no apparent
influence.
6.2. Biogeochemical and environmental aspects
Plants contributed very little to the arsenic diffu-
sion, cycling and transfer from soil to biosphere in the
study areas. Both the As concentrations in plant
tissues and the ability of plants to accumulate theelement were low or very low. This was especially so
in the most common crops (corn, lucerne, sunflower,
wheat), in common wild herbs ( Bromus hordeaceus,
Bromus madritensis, D. hispanica, I. viscosa), in the
main chamaephytes ( D. hirsutum and H. italicum) and
shrubby colonizers ( Rubus ulmifolius and Spartium
junceum), as well as in the main components of the
local forest (Quercus cerris and Quercus ilex).
However, species such as M. aquatica, P. lanceo-
lata, P. australis and some others growing on soils
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very rich in arsenic (especially in dumps and tailing
ponds of study area A) appeared to be good pumps for
soil As. Their CFs were high or very high, especially
for soluble soil As.A low As concentration in the above-ground plant
biomass decreases the risk of food chain contamina-
tion through grazing. Indeed, with the exception of P.
lanceolata (9–24 mg kg 1 of As in its leaves), this
was the general case for the species most palatable to
livestock. However, P. lanceolata also had As con-
tents below the maximum level (50 mg kg 1) toler-
ated by cattle, sheep and swine (Chaney, 1989). Thus,
plant contamination by As-rich soil particles (or soil
ingestion) could be the main route of As intake by
wild herbivores and livestock, as found elsewhere
(Thornton and Abrahams, 1983; Li and Thornton,
1993).
The As contents found in the edible parts of crops
and vegetables are not cause for concern, since they
were close to or below the instrumental detection
limit.
6.3. Remarks on some plant species
One of the sampled species, S. vulgaris, is well
known for its tolerance to several trace elements, such
as antimony, cadmium, cobalt, copper, lead, nickeland zinc, which are even accumulated or hyperaccu-
mulated (Harmens et al., 1993; de Knecht et al., 1995;
Wenzel and Jockwer, 1999; Baroni et al., 2000b).
With regard to the ability of S. vulgaris to accumulate
arsenic, our data agree with literature reports. Mean
values such as 261 mg kg 1 (Paliouris and Hutch-
inson, 1991) or 637 mg kg 1 (Sneller et al., 1999)
have been reported for soils with soluble As 25–37
times higher than the highest value (tailing ponds) in
our soils. Moreover, our plants had higher As contents
in the shoots than in the roots; this is an important aspect since a substantial As depletion occurs at the
end of the growing cycle when most of the above-
ground biomass is shed.
Rather high As contents were also found in S.
dioica growing in pastures of study area C. However,
in this case, the levels of soluble and extractable As in
the soil were high: 8.5 and 35.8 mg kg 1, respectively.
M. sativa sampled in area C, as well as in the old
fields and mine dumps of area A, behaved as an
excluder.
P. australis, with a mean As content of 688 mg
kg 1 in the roots, 1.5 mg kg 1 in the shoots and 3.7
mg kg 1 in the leaves, clearly confirmed its low
ability to translocate arsenic from root s t o t h eabove-ground biomass (Otte et al., 1990). Reduced
metal transport from roots to shoots appears to be the
usual behavior of the species (see for instance Ye et
al., 1997).
A. stolonifera has been found to be an As accu-
mulator in other mining areas, with contents up to
1350 mg kg 1 (Porter and Peterson, 1975), but this
was not the case in our study (maximum concentra-
tions of 21 mg kg 1 were found). Nevertheless, it
must be stressed that Porter and Peterson also found
extremely high As contents in the soils they studied
(from 8510 to 26,530 mg kg 1).
The ability of M. aquatica to concentrate As and
translocate it to the leaves is rather interesting. There-
fore, its potential use as a phytoremediator could be
assessed.
7. Conclusions
The soil levels of organic matter, available phos-
phorus, 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 contam-
ination 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 contami-nation 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 geochem-
ical 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.
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Acknowledgements
This paper is a contribution to the research project:
‘‘Dispersion and transfer of metals to the biosphere inmining areas’’, supported by Ministero dell’Universita
e della Ricerca Scientifica e Tecnologica (MURST)
and the University of Siena.
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