chemical partioning of trace and major elements in soil of mining area
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Chemical partitioning of trace and major elements in soilscontaminated by mining and smelting activities
Xiangdong Li a,b,*, Iain Thornton b
aDepartment of Civil and Structural Engineering, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong KongbEnvironmental Geochemistry Research, Centre for Environmental Technology, T. H. Huxley School of Environment,
Earth Science and Engineering, Imperial College, London SW7 2BP, UK
Received 23 May 2000; accepted 18 March 2001
Editorial handling by R. Fuge
Abstract
Soils from historical Pb mining and smelting areas in Derbyshire, England have been analysed by a 5-step sequential
extraction procedure, with multielement determination on extraction solutions at each step by ICP-AES. Each of the
chemical fractions is operationally defined as: (i) exchangeable; (ii) bound to carbonates or specifically adsorbed; (iii)
bound to Fe–Mn oxides; (iv) bound to organic matter and sulphides; (v) residual. The precision was estimated to be
about 5%, and the overall recovery rates were between 85 and 110%. The carbonate/specifically adsorbed and Fe–Mn
oxide phases are the largest fractions for Pb in soils contaminated by both mining and smelting. Most of the Zn is
associated with Fe–Mn oxide and the residual fractions. Cadmium is concentrated in the first 3 extraction steps, par-
ticularly in the exchangeable phase. The most marked difference found between soils from the mining and smelting sites
is the much higher concentrations and proportions of metals in the exchangeable fraction at the latter sites. This indi-
cates greater mobility and potential bioavailability of Pb, Zn and Cd in soils at the smelting sites than in those in the
mining area. The most important fraction for Fe and Al is the residual phase, followed by the Fe–Mn oxide forms. In
contrast, the Fe–Mn oxide fraction is the dominant phase for Mn in these soils. In the mining area, most of the Ca is in
the carbonate fraction (CaCO3), while the exchangeable and residual phases are the main fractions for Ca at the
smelting sites. Phosphorus is mainly in the residual and organic fractions in both areas. The exchangeable fractions of
Pb, Zn and Cd in soils were found to be significantly related to the concentrations of these metals in pasture herbage.
# 2001 Elsevier Science Ltd. All rights reserved.
1. Introduction
Base metal mining and smelting activities are impor-
tant sources of heavy metals in the environment, result-
ing in considerable soil contamination (Davies, 1983;
Alloway, 1990). The historical Pb–Zn mining and
smelting region of Derbyshire in central England is one
such example (Colbourn and Thornton, 1978; Li and
Thornton, 1993a). A number of elements associated
with Pb mineralisation have been found to be highly
elevated in soils contaminated by mining and smeltingoperations in this area (Li and Thornton, 1993a; Mas-
kall and Thornton, 1993a).
Many studies dealing with particular metals in soil sys-
tems are concerned with ’total’ (strong acid extractable)
metal concentrations; this is a valid approach when
studying the degree and extent of contamination and the
mass balance of metals in the soil system. However, the
total contents in soils provide, in most cases, limited
information on the mobility and bioavailability of heavy
metals (Leschber et al., 1985; Kramer and Allen, 1988).
Metals in soils may be present in several different phy-
sicochemical phases that act as reservoirs or sinks of
0883-2927/01/$ - see front matter # 2001 Elsevier Science Ltd. All rights reserved.
P I I : S 0 8 8 3 - 2 9 2 7 ( 0 1 ) 0 0 0 6 5 - 8
Applied Geochemistry 16 (2001) 1693–1706
www.elsevier.com/locate/apgeochem
* Corresponding author. Tel.: +852-2766-6041; fax: +852-
2334-6389.
E-mail address: cexdli@polyu.edu.hk (X.D. Li).
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trace elements in the environment (Jenne, 1977; Sposito,
1983; Beckett, 1988). These phases include the following
broad categories: exchangeable; specifically adsorbed;
carbonate; secondary Fe and Mn oxides; organic mat-
ter; sulphides and silicates, etc., and all of these may
occur in a variety of structural forms. Understanding
the mode of occurrence of elements in soils is essentialfor the environmental assessment of soil contamination.
One approach to the analytical determination of the
distribution of metals among these physicochemical
phases has been made by phase-selective chemical
extractions involving multiple extracting reagents (Tes-
sier et al., 1979; Shuman, 1985; Ure et al., 1993). The
reagents utilised in sequential extractions have been
chosen on the basis of their selectivity and specificity
towards particular physicochemical forms.
Many different sequential extraction procedures have
been developed for partitioning trace elements in sedi-
ments, soils and sludges (Lake et al., 1984; Pickering,1986; Beckett, 1988; Ure et al., 1993). In particular, the
protocol of Tessier et al. (1979) has been thoroughly
researched and rigorously tested (Valin and Morse, 1982;
Rapin and Fo ¨ rstner, 1983; Martin et al., 1987; Kim and
Fergusson, 1991; Howard and Vandenbrink, 1999). This
method has been applied in sediment and soil studies by
many investigators (i.e. Harrison et al., 1981; Hickey
and Kittrick, 1984; Xian, 1989; Ramos et al., 1994,
1999). However, the limitations of this procedure have
also been addressed by several researchers (Jouanneau
et al., 1983; Khebonian and Bauer, 1987; Rauret et al.,
1989). The limitations include technical difficulties asso-
ciated with achieving selective dissolution and complete
recovery of trace metals from geochemical phases in soils
and sediments. Despite these limitations, the sequential
extraction scheme can be a very useful method for char-
acterising solid phase associated trace metals in soils and
sediments (Rapin and Fo ¨ rstner, 1983; Belzile et al.,
1989; Kim and Fergusson, 1991; Adamo et al., 1996;
Ma and Rao, 1997).
Although the procedure of Tessier et al. (1979) has
been widely used, most of the studies have been limited
to one or two elements analysed by atomic absorption
spectrophotometry (AAS). The investigation of soil
contamination often requires the analysis of elementalassociations. This study aims to investigate the chemical
partitioning of heavy metals (Pb, Zn and Cd) and some
major elements (Mn, Fe, Al, Ca and P) in soils con-
taminated by past mining and smelting activities. Soil
samples have been examined by the sequential extraction
method of Tessier, and the extraction solutions have been
analysed by inductively coupled plasma-atomic emission
spectrometry (ICP-AES) for a number of trace and
major elements to enable studies of multielement geo-
chemical associations in the soil system. Pasture herbage
samples from the study sites were also analysed to assess
the bioavailability of these metals in the soils.
2. Materials and methods
2.1. Study area – Derbyshire
The geological structure of Derbyshire (southern
Pennines) comprises a central Carboniferous Limestone
‘dome’ flanked successively by the Millstone Grit withalternating, sandstones and shales of the Lower Coal
Measures (Fig. 1) (Smith et al., 1967; Ford, 1976). Lead
mineralisation is present mainly within the Carbonifer-
ous Limestone, concentrated particularly in the east.
Ore minerals are chiefly sulphides, including galena
(PbS), sphalerite (ZnS) and pyrite (FeS2), with minor
quantities of other minerals including cerussite (PbCO3),
smithsonite (ZnCO3) and pyromorphite (Pb5(PO4)3Cl)
(Ford, 1976; Cotter-Howells, 1991). The most common
ore is galena; the major gangue minerals are calcite,
fluorite and barite.
Lead had been mined in Derbyshire for many hun-dreds of years, dating probably from pre-Roman times
until the beginning of the 20th century (Ford and Rieu-
werts, 1968). The Pb ore was usually transported away
from the limestone mining area to forested hills to the
east overlying Millstone Grit where it was smelted
(Willies, 1990). The most extensive activities occurred
during the 18th and 19th centuries. The relics of this
historical industry can be seen as hillocks surrounding
old surface and subsurface mine workings, and slag
heaps from cupola and bolehill smelters. The early
mining and smelting operations were often grossly inef-
ficient and large quantities of heavy metal were released
to the environment (Davies, 1983). Some 250 km2 of
land in Derbyshire is estimated to be contaminated by
Pb (Colbourn and Thornton, 1978). A recent study
shows that in addition to Pb, other associated elements,
namely Zn, Cd, Ag, As, Sb and Hg, are present as sig-
nificant contaminants (Li and Thornton, 1993a,b).
Two old Pb mining sites were sampled in this study.
Winster is a typical mining village with mine shafts and
waste within and around the dwellings. Tideslow Farm
overlies an open Pb rake which had been intensively
mined in the past (Fig. 1). Three smelting sites were
sampled in this research. Ashover and Ramsley are
Medieval wind-blown lead smelters, while Stone Edge isa cupola furnace which was operated during the 18th
and 19th centuries (Fig. 1). The soils overlying the Car-
boniferous Limestone are mainly well drained brown
earths. Soils at the smelting sites are mainly gleys with a
clay texture, with sandy loam at Ashover.
2.2. Sampling and analysis
Topsoil (0–15 cm) and subsoil (15–30 and 30–45 cm)
were sampled using a hand screw auger of diameter 2.5
cm. At each site, a composite topsoil sample was made
up of 9 auger borings taken within a 22 m square,
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while the 2 subsoil samples each consisted of 3 sub-
samples. Soils were dried at 25C in a filtered air drying
cabinet for 3 days. All the samples were then sieved
through a 2 mm sieve and milled in an agate pot to a
fine powder (<170 mm), which was used in the chemical
analysis. The mixed grass samples from the Derbyshire
study areas consisted of several common pasture species
which were taken within the soil sampling plot by clip-
ping the plant 2.5 cm above the soil surface using sharp
stainless steel scissors.
The details of the sequential chemical extraction pro-
cedure and the ICP-AES analysis have been given by Li
et al. (1995a,b). The extraction was carried out progres-sively on an initial weight of 1.0 g of test material. The
extractants and operationally defined chemical fractions
were as follows:
1. Fraction 1: exchangeable — soil extracted with 8
ml of 0.5 M MgCl2 at pH 7.0 for 20 min, with
continuous agitation at room temperature.
2. Fraction 2: bound to carbonate and specifically
adsorbed — residue from Step 1 leached for 5 h
with 8 ml of 1 M NaOAc (adjusted to pH 5.0 with
HOAc) at room temperature. Continuous agita-
tion was maintained during the extraction.
3. Fraction 3: bound to Fe–Mn oxides — the residue
from Step 2 was extracted with 20 ml of 0.04 M
NH2.OH.HCl in 25% (v/v) HOAc for 6 h. The
extraction was performed at 96C with occasional
agitation. After extraction, the extract solutions
were diluted to 20 ml with DIW and subjected to
continuous agitation for 10 min.
4. Fraction 4: bound to organic matter and sulphide —
3 ml of 0.02 M HNO3 and 5 ml of 30% H2O2
(adjusted to pH 2.0 with HNO3) were added to the
residue from Step 3. The sample was heated pro-
gressively to 85C, and maintained at this tempera-
ture for 2 h with occasional agitation. A second 3 mlaliquot of 30% H2O2 (adjusted to pH 2.0 with
HNO3) was then added, and the mixture was heated
again at 85oC for 3 h with intermittent agitation.
After cooling, 5 ml of 3.2 M NH4OAc in 20% (v/v)
HNO3 were added, followed by dilution to a final
volume of 20 ml with DIW. The tubes were then
continuously agitated for 30 min.
5. Fraction 5: residual phase — the residue from
Step 4 was digested with 4 ml concentrated HNO3
(70%), 2 ml acid HClO4 (60%) and 15 ml HF
(40%) to dryness using the following heating
regime: 90C for 6 h; 120C for 10 h; 190C for 6
Fig. 1. The location and simplified geological map of the study area in Derbyshire (from Ford, 1976).
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h. The remaining material was then taken up in 5
ml of 4 M HCl at 70C for 1 h, and diluted to 25
ml with 0.3 M HCl.
The independent total concentrations of these soil
samples were also determined in this study to assess the
recovery of the sequential extraction. The samples weredigested in concentrated HNO3 and HClO4 (in a ratio of
4:1) and taken to dryness on a heating block. The resi-
due was then leached with 5 M HCl and diluted to 10 ml
with DIW (Li and Thornton, 1993a).
The mixed grass samples were washed in deionised water
3 times, dried at 25C, milled, digested in fuming HNO3
followed by concentrated HClO4, leached with HCl, and
analysed by ICPAES (Thompson and Walsh, 1988).
Multi-element analysis was performanced by ICP-AES
using an ARL34000C model (Ramsey and Thompson,
1987). The accuracy and precision were assessed by use of
international reference materials and analysis of duplicatesamples (Li et al., 1995a,b). The precisions were around
5% for most of elements determined. The overall recovery
rates (the sum of 5 fractions/the independent total con-
centration) ranged from 85 to 110%.
3. Results and discussion
The concentrations of Pb, Zn, Cd, Mn, Fe, Al, Ca
and P within individual fractions of the sequential
extraction analysis are given in Table 1a–h. The mean
partitioning patterns of elements in soils between mining
and smelting areas are presented in Fig. 2a–h. The geo-
chemical phases at each extraction step are largely
operationally defined by the method and reagents used,
and they can be considered as relative rather than
absolute chemical speciation. For example, the carbonate
fraction, as defined by 1 M NaOAc extraction at pH 5,
may not be strong enough to dissolve total carbonate
minerals in calcareous soils and sediments (Tessier et al.,
1979; Jouanneau et al., 1983; Span and Gaillard, 1986).
The 4th extraction step (H2O2 extraction) is operationally
defined as the organic and sulphide fraction (Tessier et al.,
1979), but it has been shown that the primary sulphide
minerals (e.g. PbS) could not be totally leached out in thisstep (Rapin and Fo ¨ rstner, 1983; Khebonian and Bauer,
1987). The possible geochemical fractions or phases are
discussed below on an element by element basis. How-
ever, it should be stated that the main interpretation is
centred on the solubility, possible chemical associations
and potential bioavailability of the metals rather than
the specific mineralogy.
3.1. Pb
Lead in the soils at the old mining sites is shown to be
strongly associated with the carbonate phase (the second
extraction step, c. 24–55%) (Table 1a and Fig. 2a). This
is in keeping with the thermodynamic prediction (Gar-
rels and Christ, 1965; Brookins, 1988) that cerussite
(PbCO3) would be the dominant Pb mineral at the Eh–
pH conditions in these soils. The XRD results in mine
waste soils in Derbyshire also showed that cerussite is
one of the major Pb minerals (Cotter-Howells, 1991).The next most abundant fraction of Pb in these soils is
the Fe–Mn oxide phase, with c. 30% extracted by this
step (Table 1a). Fe–Mn oxides are important scavengers
of heavy metals in soils, particularly at high pH range
(pH>7.0) (McKenzie, 1980; Tipping et al., 1986).
The organic/sulphide fraction accounts for 6–15% of
the total Pb in these soils (Table 1a), while the residual
fraction accounts for 12–33%. This fraction may repre-
sent the Pb held in the primary minerals, galena (PbS)
and possibly pyromorphite [Pb5(PO4)3Cl] (Cotter-
Howells and Thornton, 1991). A very small amount of
Pb is in the exchangeable phase (<
1.0%) at the miningsites (Fig. 2a).
At the historical smelting sites, the largest fraction for
Pb is the carbonate/specifically adsorbed phase, which
accounts for 10–50% of the total soil Pb content (Table 1a
and Fig. 2a). Although the lead carbonate mineral (cer-
ussite, PbCO3) has been identified as a weathering product
in old smelting slag samples in Derbyshire (Murphy,
1992), lead emissions from smelters have been shown to
consist of lead sulphate (PbSO4), lead monoxide (PbO)
and lead oxysulphate (PbO.PbSO4) (Foster and Lott,
1980). Clevenger et al. (1991) showed that 0.5 M
NH4OAc could dissolve 81% of PbO in the soil. The
reagent used here (1 M NaOAC) has a similar strength.
Therefore, it can be assumed that Pb extracted in this
step may represent PbO as well as carbonate. This
represents an important difference to the forms recov-
ered by the same extraction step in mining contaminated
soils.
The second most abundant fraction for Pb is the Fe–
Mn oxide phase (Fig. 2a). There are significant correla-
tions (P<0.01) between Pb, Fe and Al extracted in this
step, which may indicate that Fe and Al oxides are of
major importance in binding Pb in these soils. In con-
trast, the organic/sulphide fraction is of minor impor-
tance accounting for only c. 13% of the total Pb. Theresidual fraction is important in soils overlying slag
heaps, and accounts for over 37% of the total soil Pb
(Table 1a). This could reflect the large amount of Pb
remaining in the form of unsmelted primary minerals,
such as galena (PbS), and/or the Pb in silicate glasses in
the slag. The actual concentration of Pb in the
exchangeable fraction is in the range 230–2570 mg/kg
(1–30% of the total Pb in the soils), which is much
higher than that of the mining area. The first extraction
step (the exchangeable fraction) has been shown to be
the most important fraction for Pb in anglesite (PbSO4)
(Harrison et al., 1981; Clevenger et al., 1991). XRD
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Table 1
The results (mg/kg) of sequential extraction of metals in soils at old Pb mining and smelting sites, Derbyshire
(a) Pba
Site I.D. Pb (1) Pb (2) Pb (3) Pb (4) Pb (5) Pb (S)
Mining area DM001 91 6210 6650 2040 6480 21 470DM005 41 3200 4100 1630 4520 13 490
DM006 16 4680 3940 1040 1990 11 660
DM007 10 4760 2940 1060 2100 10 870
DM037 401 27 200 16 100 5240 6690 55 630
DM038 278 34 100 12 400 4540 10 400 61 720
DM039 109 18 500 7200 2290 6520 34 620
DM041 46 11 100 9600 1650 6910 29 300
DM049 57 2070 1900 975 1650 6650
DM050 34 1380 1610 696 918 4640
Smelting area DS001 1780 3620 3140 1333 2720 12 600
DS006 2570 2540 2680 506 361 8660
DS008 354 18 400 8420 4140 4860 36 200
DS010 547 1060 738 398 293 3040DS011 230 562 412 170 71 1450
DS014 2000 45 400 12 100 7660 38 700 106 000
DS015 1880 23 400 11 300 6410 38 700 81 700
DS016 1510 41 200 10 400 6170 38 700 98 000
DS020 1970 21 500 10 700 8400 17 200 59800
(b) Zn
Site I.D. Zn (1) Zn (2) Zn (3) Zn (4) Zn (5) Zn (S)
Mining area DM001 32 406 2140 98 561 3240
DM005 31 499 1370 101 757 2760
DM006 8 387 1630 68 686 2780
DM007 6 541 2230 58 470 3310
DM037 2 40 168 17 500 728DM038 1 26 112 7 493 639
DM039 1 13 58 11 256 338
DM041 9 231 1140 261 1500 3140
DM049 1 20 110 63 239 434
DM050 1 10 76 41 190 317
Smelting area DS001 31 12 49 14 75 182
DS006 3 1 8 4 21 38
DS008 28 238 734 163 329 1490
DS010 23 10 33 28 101 195
DS011 24 14 34 17 68 157
DS014 65 214 497 437 1090 2300
DS015 119 182 234 106 591 1230
DS016 107 1360 960 362 1290 4080DS020 10 69 318 68 416 882
(c) Cd
I.D. Cd (1) Cd (2) Cd (3) Cd (4) Cd (5) Cd (S)
Mining area DM001 6.7 8.8 14.7 0.9 2.9 34.0
DM005 5.8 6.6 6.9 0.6 3.3 23.2
DM006 2.8 6.8 9.8 0.5 2.9 22.8
DM007 1.8 11.4 19.0 0.4 2.1 34.7
DM037 4.1 6.8 8.2 0.7 2.6 22.4
DM038 1.7 7.6 6.6 0.7 2.8 19.4
DM039 2.1 3.8 2.2 0.3 2.1 10.5
(continued on next page)
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Table 1 (continued )
(c) Cd
I.D. Cd (1) Cd (2) Cd (3) Cd (4) Cd (5) Cd (S)
DM041 6.8 19.2 17.7 1.3 3.1 48.1
DM049 2.3 2.2 1.8 0.3 1.5 8.1
DM050 1.7 1.4 1.6 0.2 1.5 6.4
Smelting area DS001 <0.1 <0.4 <0.1 <0.1 0.3 0.5
DS006 0.2 <0.4 0.1 <0.1 0.6 1.0
DS008 6.5 8.8 9.3 1.4 3.6 29.6
DS010 1.3 <0.4 0.3 0.2 0.9 2.9
DS011 1.6 0.4 0.3 0.1 0.6 3.1
DS014 6.5 6.2 3.9 4.3 25.1 46.0
DS015 11.5 7.6 5.1 1.9 11.8 37.9
DS016 9.1 24.2 7.4 2.9 9.2 52.7
DS020 0.3 0.4 0.4 0.1 2.2 3.4
(d) Fe
I.D. Fe (1) Fe (2) Fe (3) Fe (4) Fe (5) Fe (S)
Mining area DM001 13 13 2630 417 12 200 15 300
DM005 10 22 1970 509 16 500 19 000
DM006 3 18 2240 81 15 900 18 200
DM007 1 26 2320 39 10 400 12 800
DM037 13 26 3610 821 13 400 17 900
DM038 5 18 3490 571 15 500 19 600
DM039 3 42 6170 533 19 700 26 400
DM041 8 20 2820 293 20 000 23 100
DM049 20 74 4460 1950 15 000 21 500
DM050 7 59 7050 1740 17 700 26 600
Smelting area DS001 18 131 2570 696 5790 9200
DS006 4 216 4980 215 5420 10 800
DS008 17 48 2830 980 10 600 14 500DS010 14 232 2620 1080 10 600 14 600
DS011 4 70 2330 495 9180 12 100
DS014 38 182 6810 1480 26 100 34 600
DS015 28 219 8280 4430 31 700 44 700
DS016 18 466 9070 1730 29 200 40 500
DS020 33 418 8470 513 31 300 40 700
(e) Mn
I.D. Mn (1) Mn (2) Mn (3) Mn (4) Mn (5) Mn (S)
Mining area DM001 11 118 2630 66 126 2950
DM005 16 142 2640 89 157 3040
DM006 3 198 3010 26 108 3350
DM007 2 221 2160 16 49 2450
DM037 9 218 3460 84 131 3900
DM038 6 185 2020 55 140 2410
DM039 7 157 1180 44 179 1570
DM041 7 284 3460 82 55 3890
DM049 12 85 556 37 107 798
DM050 12 58 587 29 136 822
Smelting area DS001 34 40 248 8 45 376
DS006 75 36 1380 17 40 1550
DS008 4 41 152 11 54 260
(continued on next page)
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Table 1 (continued )
(e) Mn
I.D. Mn (1) Mn (2) Mn (3) Mn (4) Mn (5) Mn (S)
DS010 15 13 25 3 30 85
DS011 9 10 32 1 35 88
DS014 1 8 18 5 85 117
DS015 3 4 16 4 71 97
DS016 2 23 25 5 98 154
DS020 24 129 501 48 247 948
(f) Al
I.D. A1 (1) A1 (2) A1 (3) A1 (4) A1 (5) A1 (S)
Mining area DM001 4 32 776 496 11 100 12 400
DM005 6 46 420 446 15 800 16 700
DM006 4 58 509 108 13 500 14 200
DM007 3 54 403 76 7610 8150
DM037 8 32 697 848 15 600 17 200
DM038 4 58 918 947 20 000 21 900
DM039 4 122 2030 1670 31 900 35 700
DM041 5 12 546 506 28 900 30 000
DM049 19 86 1290 1590 23 700 26 700
DM050 8 130 2160 1730 27 400 31 400
Smelting area DS001 68 80 650 700 23 200 24 700
DS006 27 66 545 428 23 300 24 400
DS008 13 124 1520 1230 21 000 23 900
DS010 78 178 839 981 28 600 30 700
DS011 40 134 564 684 29 600 31 000
DS014 34 894 3550 1480 25 600 31 600
DS015 70 784 2760 1130 26 700 31 400
DS016 24 952 3060 1330 15 500 20 900
DS020 17 144 1170 979 35 400 37 700
(g) Ca
I.D. Ca (1) Ca (2) Ca (3) Ca (4) Ca (5) Ca (S)
Mining area DM001 3070 10 600 11 600 3030 67 300 95 600
DM005 3330 9700 9410 3410 72 000 97 800
DM006 1690 38 700 13 200 3710 94 000 151 000
DM007 1060 48 900 14 100 2500 105 000 172 000
DM037 4580 24 600 60 600 2530 21 700 114 000
DM038 4080 33 900 55 500 3040 18 400 115 000
DM039 3640 24 300 8020 2140 5940 44 000
DM041 3640 49 200 76 600 3000 27 700 160 000
DM049 4290 6070 2420 1720 11 900 26 400
DM050 3510 1830 1950 1810 5260 14 400
Smelting area DS001 269 78 140 79 338 903
DS006 68 10 55 52 376 561
DS008 3920 8880 3980 1560 10 500 28 800
DS010 1170 271 742 502 201 2790
DS011 1070 206 175 69 683 2200
DS014 1600 1400 3770 1910 18 300 27 000
DS015 3320 1370 3310 1970 8880 18 900
DS016 1800 1750 4380 2330 16 400 26 700
DS020 452 398 1220 1780 12 300 16 200
(continued on next page)
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analysis of the soils from Stone Edge showed that
anglesite (PbSO4) was present in the soils (Cotter-
Howells, 1991). Therefore, the Pb in the exchangeable
fraction may represent the Pb in the sulphate phase in
the smelting area. The higher Pb contents and propor-
tions in the exchangeable fraction clearly illustrate that
Pb in smelting waste soils is potentially more soluble
and bioavailable than that present in soils contaminated
by mine waste.
3.2. Zn
In the old mining area, the majority of Zn is asso-
ciated with the Fe–Mn oxide and residual fractions
(Table 1b and Fig. 2b), which agrees with the observa-
tions of Kuo et al. (1983) and Hickey and Kittrick
(1984) in other contaminated soils. The Zn in the car-bonate/specifically adsorbed phases accounts for 2–18%
of the total Zn, which is much less than that for Pb. The
organic/sulphide fraction is of minor importance,
accounting for less than 10% of the total Zn in the soils.
The exchangeable fraction of Zn is also very low
(<1.0%).
In the historical Pb smelting area, a large amount of
Zn is in the residual fraction, accounting for about 40%
of the total Zn content. The next most abundant phase
is the Fe–Mn oxide fraction (c. 25%). The organic/sul-
phide fraction accounts for less than 2%. The second
extraction step (carbonate/specifically adsorbed phase)
is important for the high Zn soils, and accounts for up
to 33% of the total Zn. A possible explanation for this
could be the presence of Zn oxysulphates [ZnO.ZnSO4
or Zn(OH)2.ZnSO4] in the smelting waste, as observed
previously by Foster and Lott (1980). The proportions
of Zn in the exchangeable fraction varies from 1 to
15%, which is generally much higher in the smelting
area than that of the mining area.
3.3. Cd
Cadmium in the soils at the mining sites is con-
centrated in the first 3 extraction steps (Table 1c and
Fig. 2c). About 5–29% of the total Cd is associated
with the exchangeable fraction. This contrasts strongly
with Pb and Zn (less than 1%). These results agree
with many previous observations, for example, Kuo etal. (1983), Hickey and Kittrick (1984) and Xian
(1989). As commonly reported, the organic/sulphide
phase has only a minor role in binding Cd (c. 3%). The
residual phase accounts for only 15% of total Cd in the
soils.
At the smelting sites, the exchangeable Cd in the soils
is also high, accounting for 7–52% of the total Cd con-
centration (Fig. 2c). The carbonate/specifically adsorbed
phase and Fe–Mn oxide fraction are also important
phases for Cd in these soils. Therefore, as with soils
from the mining area, the first 3 extraction fractions
account for more than 70% of the total Cd content
Table 1 (continued )
(h) P
I.D. P (1) P (2) P (3) P (4) P (5) P (S)
Mining area DM001 5 35 187 373 1830 2430
DM005 6 59 215 442 1910 2630
DM006 1 8 70 203 1290 1570
DM007 1 8 64 119 933 1120
DM037 8 19 74 218 3050 3370
DM038 2 8 53 249 2960 3270
DM039 1 6 30 132 1690 1910
DM041 2 5 33 177 1690 1910
DM049 2 19 26 118 893 1060
DM050 2 10 16 68 763 859
Smelting area DS001 4 16 91 115 337 563
DS006 1 13 56 75 295 440
DS008 3 19 79 207 782 1090
DS010 5 21 47 261 329 663
DS011 1 6 17 88 215 328
DS014 2 10 47 50 818 927
DS015 2 6 24 27 715 774
DS016 2 10 37 32 638 719
DS020 5 30 70 40 1760 1910
a Following the sequential extraction steps described in the text: Pb (1), the exchangeable fraction; Pb (2), the fraction bound to
carbonate and specifically adsorbed; etc. and Pb (S), represents the sum of the 5 fractions.
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(Table 1c). As in the mining area, the organic/sulphide
fraction is small, while the residual fraction normally
accounts for about 30% of the total soil Cd concentration.
3.4. Fe
Iron oxides play a major role in binding many trace
metals in soils (Jenne, 1977; Alloway, 1990). The parti-
tioning patterns of Fe in soils at both mining and
smelting sites are very similar. The first 2 steps extract
very little Fe from these soils (Table 1d and Fig. 2d).
However, the Fe–Mn oxide fraction accounts c. 20% of
the total Fe content in soils in both mining and smelting
areas. This may represent the amorphous Fe oxides or
hydroxides as suggested by Tipping et al. (1986), Tessier
et al. (1985) and Kim and Fergusson (1991). The most
abundant Fe fraction, however, is the residual phase
(Fig. 2d), with the proportion of Fe in this fraction
accounting for approximately 70–80% of the total soil
Fe. This may represent crystalline Fe oxides and the Fe
in primary silicate minerals. The organic/sulphide frac-
tion is of minor importance for Fe in these soils.
Fig. 2 (a–d). The mean chemical partitioning of trace and major elements in soils between the mining and smelting areas, Derbyshire.
(a) Pb, (b) Zn, (c) Cd, (d) Fe.
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3.5. Mn
In contrast to Fe, the majority of Mn is associated
with the Fe–Mn oxide fraction, which accounts for c.
80% of the total soil concentration (see Table 1e and
Fig. 2e). This result indicates that most of Mn is in the
form of relatively soluble oxides. The Mn concentration
in this phase in the old mining sites varies from 556 to
3460 mg/kg (Table 1e), which is similar to concentra-
tions of Fe in this phase. It is indicated that Mn could
have an important role in binding trace metals in these
mining soils. A small amount of Mn is in the carbonate
fraction (c. 7%), which may result from the dissolution
of divalent salts, such as Mn carbonate [MnCO3 or
(Ca,Mn)CO3] (Tessier et al., 1984). The residual fraction
accounts for only 1.4–18%, while the exchangeable and
organic/sulphide fraction is of little importance (Fig. 2e),
as is the case for Fe.
The total concentrations of Mn in the soils at the old
Pb smelting sites are much lower than those of the old
mining area because of the different soil parent materials.
However, as with the mining area, the largest fraction is
Fig. 2(e–h). The mean chemical partitioning of trace and major elements in soils between the mining and smelting areas, Derbyshire.
(e) Mn, (f) A1, (g) Ca and (h) P.
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the Fe–Mn oxide phase (Table 1e and Fig. 2e). The
exchangeable fraction and specifically adsorbed/carbon-
ate fraction accounts for about 20% of the total Mn. The
Mn in the organic/sulphide phase is less than 5%.
3.6. Al
The partitioning pattern of Al in the soils at both
mining and smelting sites is very similar to that of Fe
(see Table 1f and Fig. 2f). The vast majority of Al (90%)
is in the residual fraction (Fig. 2f). This reflects the fact
that Al is present in the soils mainly in the form of pri-
mary and secondary silicate minerals (Tessier et al.,
1979; Karlsson et al., 1988). The second most abundant
fraction for Al is the Fe–Mn oxide phase (<10%)
(Table 2f). This phase may represent the Al in the oxide
form, in particular as hydroxides, which are also
important for the absorption of heavy metals (Tessier et
al., 1985; Karlsson et al., 1988). The organic/sulphidephase accounts for about 3–4% of the total Al content
in the soils.
3.7. Ca
Most Ca in the soils at the mining sites is present in
the carbonate, Fe–Mn oxide and residual phases
(Table 1g and Fig. 2g). These fractions accounts for up
to 85% of the total Ca. Calcium is mainly in the form of
carbonate (calcite CaCO3) in soils derived from lime-
stone. As the sequential procedure used in this study
was initially designed for partitioning low to medium Ca
content sediments (Tessier et al., 1979), complete dis-
solution of the carbonate phase in calcareous soils
requires a pH adjustment and more extractant solution
(Span and Gaillard, 1986; Rauret et al., 1989). There-
fore, the Ca in the carbonate fraction may not be com-
pletely dissolved at step 2 (1 M NaOAc, pH=5.0) due
to the high calcite content of these soils. The next
extraction step (the Fe–Mn oxide fraction) probably
contains a proportion of Ca belonging to the carbonate
phase. The organic/sulphide phase does not account for
very much of the total soil Ca (c. 5%). The residual
fraction could represent the Ca within many primary
and secondary silicates and phosphates such as feldspar,clay minerals and apatite (Kilmer, 1979; Sposito, 1983).
At the smelting sites, the most abundant fraction for
Ca in the soils overlying the slag heaps is the residual
fraction, accounting for 60% of the total Ca (Fig. 2g).
This probably indicates the amounts of Ca incorporated
in silicate glass and minerals such as wollastonite (CaSiO3)
during the smelting process. At the other sampling sites in
the smelting area, the exchangeable fraction is the domi-
nant phase (c. 55%), with the residual fraction being of
secondary importance (c. 25%). These results reflect the
influence of low soil pH and the possible presence of
CaSO4
in the smelter surrounding area. The contributions
from the remaining 3 fractions are relatively low. In
contrast to that in the mining area, the carbonate phase
accounts for only 6% of the total Ca in these soils, while
the Ca in the Fe–Mn oxide fraction accounts for 11%.
3.8. P
The partitioning patterns of P in the mining and
smelting areas are very similar, with the first 3 steps
extracting very little P (Table 1h and Fig. 2h). However,
the organic fraction accounts for about 11% of the total
P in these soils. The residual fraction is the largest (c.
85%) (Fig. 2h), which could represent the P in various
mineral phases in these soils, particularly minerals such
as Ca and Pb phosphates. There is a significant correlation
between Pb and P in the residual fraction in soils at the old
mining sites (Fig. 3), probably reflecting the presence of Pb
phosphate mineral, pyromorphite [Pb5(PO4)3Cl] in these
soils as reported in a previously study using SEM by Cot-ter-Howells and Thornton (1991).
Harrison et al. (1981) have suggested that the mobi-
lity and bioavailability of metals decrease approximately
in the order of the extraction sequence, from readily
available to unavailable, because the strength of extrac-
tion reagents used increases in this order. The
exchangeable fraction may indicate the form in which
metals are most available for plant uptake. The second
step extracts metals bound to carbonate and specifically
adsorbed phases, which can become easily mobile and
available under conditions of lower soil pH. Metals
Fig. 3. Relationship between the Pb and P concentrations in the
residual fraction in soils at the old Pb mining sites, Derbyshire.
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bound to the oxide and organic/sulphide fractions are
generally more strongly held within the soil constituents
than the first two fractions. The residual phase usually
represents metals incorporated in the lattice of minerals,
which are unavailable to plants and animals.
The results of sequential extraction, particularly those
of the exchangeable fraction of metals, have been com-pared with the plant metal contents from the same
sampling sites to assess the influence of metal speciation
on plant uptake. There is a significant relationship
between the exchangeable Pb in soils and the plant Pb
concentrations (Fig. 4). Plant uptake of Pb increases as
the exchangeable Pb in soils increases. Thus the Pb in
the exchangeable fraction can be used to assess the bia-
vailablity of Pb in the contaminated soils. There are also
significant relationships between the exchangeable Zn
and Cd in soils and the Zn and Cd concentration in the
pasture herbage.
The most marked difference between the oper-ationally defined metal speciation in the soils of the
mining and smelting areas is the varying proportions of
these elements in the exchangeable fraction. The average
Pb in the exchangeable form in the smelting area
accounts for 7.7% of the total soil concentration, in
comparison to only 0.5% of the total Pb in the soils at
the old mining sites. The exchangeable Zn is also much
higher in the smelting area (c. 7.6% compared with c.
0.4%). The Cd in the exchangeable form is also higher
at the smelting sites than in the mining area, although
the difference is much smaller.
In general, the higher proportions of Pb, Zn and Cd
in the exchangeable fraction at the smelting sites com-
pared with the mining sites indicate the greater mobility
and availability of these metals at the former. Therefore,
soils contaminated by smelting operations contain
metals in a more mobile and bioavailable form and are
more likely to cause environmental problems than those
in the mining area.
4. Conclusions
The sequential extraction procedure of Tessier et al.
(1979) has been used for partitioning trace and majorelements in soils using ICP-AES with good precision
and accuracy. This modified method can thus be applied
to studies of multielement geochemical associations in
the soil system.
In the old mining area in Derbyshire, the main che-
mical phases hosting Pb are carbonates (PbCO3) and
Fe–Mn oxides. Lead is mainly in the sulphate (PbSO4),
oxide (PbO) and carbonate (PbCO3) forms at the former
smelting sites. The major fractions for Zn in the soils are
the carbonate/specifically adsorbed phase and the Fe–
Mn oxide form. Most of Cd is concentrated in the first 3
extraction steps, especially in the exchangeable fraction,
indicating the different chemical binding and higher
solubility of this element compared to Zn and Pb. The
most important differences in the partitioning patterns
between the mining and smelting areas are the higher
Fig. 4. Relationship between the plant Pb content and the
exchangeable Pb in soils.
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proportions of the exchangeable fraction of Pb and Zn
at the smelting sites. This probably reflects the different
chemical forms of these metals from the two contamina-
tion sources. These results indicate the greater mobility
and potential bioavailability of Pb and Zn in the soils at
the smelting sites compared to those in the mining area.
The Pb, Zn and Cd concentrations in pasture herbageshow significant relationships with the exchangeable metal
contents in these soils. Therefore, soils contaminated by
smelting operations are more likely to cause environ-
mental problems than those in the mining area.
The most important fraction for Mn is the Fe–Mn
oxide phase whilst only small proportions of Fe and Al are
extracted from this phase. In the old Pb mining area
overlying the limestone, most of Ca is in the carbonate and
the overlapping (carry-through) Fe–Mn oxide fractions. A
large amount of Ca is in the exchangeable fraction of the
acidic soils from the historical smelting sites. Phosphorus
is mainly in the residual and organic phases. The sig-nificant correlation between Pb and P in the residual
fraction at the old mining sites probably reflects the
presence of Pb phosphate minerals in these soils.
Acknowledgements
The authors gratefully acknowledge Dr. M. Ramsey,
B. Coles and A. Doyle for their advice and help in the
analytical aspects of this study. We wish to thank Dr. J.
Maskall, Ms. G. Sawbridge and Dr. J. Kelly for helpful
comments on earlier versions of the manuscript. Dr. R.
Fuge and the reviewer’s thorough and helpful commentshave improved the quality of the paper.
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