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: [email protected] (X.D. Li).



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,

1694 X. Li, I. Thornton / Applied Geochemistry 16 (2001) 1693–1706



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).

X. Li, I. Thornton / Applied Geochemistry 16 (2001) 1693–1706 1695



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




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)




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






(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





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


(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.




(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.




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.




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.




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.




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.

References

Adamo, P., Dudka, S., Wilson, M.J., McHardy, W.J., 1996.

Chemical and mineralogical forms of Cu and Ni in con-

taminated soils from the Sudbury mining and smelting

region, Canada. Environ. Pollut. 91, 11–19.

Alloway, B.J., 1990. Heavy Metals in Soils. Blackie, London.

Beckett, P.H.T., 1988. The use of extractants in studies on the

trace metals in soils, sewage sludges and sludge-treated soils.

Advan. Soil Sci. 9, 144–175.Belzile, N., Lecomte, P., Tessier, A., 1989. Testing reabsorption

of trace elements during partial chemical extractions of bot-

tom sediments. Environ. Sci. Technol. 23, 1015–1020.

Brookins, D.G., 1988. Eh–pH Diagrams for Geochemistry.

Springer, Berlin.

Clevenger, T.E., Saiwan, C., Koirtyoham, S.R., 1991. Lead

speciation of particles on air filters collected in the vicinity of

a lead smelter. Environ. Sci. Technol. 25, 1128–1133.

Colbourn, P., Thornton, I., 1978. Lead pollution in agricultural

soils. J. Soil Sci. 29, 513–526.

Cotter-Howells, J. 1991. Lead Minerals in Soils Contaminated

by Mine-waste: Implications for Human Health. PhD thesis,

Univ. London.

Cotter-Howells, J., Thornton, I., 1991. Sources and pathways

of environmental lead to children in a Derbyshire mining

village. Environ. Geochem. Health 13, 127–135.

Davies, B.E., 1983. Heavy metal contamination from base

metal mining and smelting: implications for man and his

environment. In: Thornton, I. (Ed.), Applied Environmental

Geochemistry. Academic Press, London, pp. 425–460.

Ford, T.D., 1976. The ores of the South Pennines and Mendip

Hills, England: a comparative study. In: Wolf, K.H. (Ed.), The

Handbook of Strata-bound and Stratiform Ore Deposits, Vol.

5, Regional Studies’. Elsevier, Amsterdam, pp. 161–195.

Ford, T.D., Rieuwerts, J.H., 1968. Lead Mining in the Peak

District, 2nd edition. Peak Park Joint Planning Board,

Bakewell, UK.

Foster, R.L., Lott, P.F., 1980. X-ray diffractometry examina-

tion of air filters for compounds emitted by lead smelting

operations. Environ. Sci. Technol. 14, 1240–1244.

Garrels R.M. Christ C.L. Minerals, Solution and Equilibria.

Harper & Row, New York.

Harrison, R.M., Laxen, D.P.H., Wilson, S.J., 1981. Chemical

association of lead, cadmium, copper, and zinc in street dustand roadside soil. Environ. Sci. Technol. 15, 1378–1383.

Hickey, M.G., Kittrick, J.A., 1984. Chemical partitioning of

cadmium, copper, nickel, and zinc in soils and sediments

containing high levels of heavy metals. J. Environ. Qual. 13,

372–376.

Howard, J.L., Vandenbrink, W.J., 1999. Sequential extraction

analysis of heavy metals in sediments of variable composi-

tion using nitrilotriacetic acid to counteract resorption.

Environ. Pollut. 106, 285–292.

Jenne, E.A., 1977. Trace element sorption by sediments and

soils — site and processes. In: Chappell, W., Peterson, S.K.

(Eds.), Proc. Symp. Molybdenum in the Environment. Mar-

cel Dekker, New York, pp. 425–552.

Jouanneau, J.M., Latouche, C., Pautrizel, F., 1983. Critical ana-

lysis of sequential extractions through the study of several

attack constituent residues. Environ. Technol. Lett. 4, 509–514.

Karlsson, S., Allard, B., Ha ˚ kansson, K., 1988. Characteriza-

tion of suspended solids in a stream receiving acid mine

effluents, Bersbo, Sweden. Appl. Geochem. 3, 345–356.

Khebonian, C., Bauer, C., 1987. Accuracy of selective extrac-

tion procedures for metal speciation in model aquatic sedi-

ments. Anal. Chem. 59, 1417–1423.

Kim, N.D., Fergusson, J.E., 1991. Effectiveness of a commonly

used sequential extraction technique in determining the spe-

ciation of cadmium in soils. Sci. Tot. Environ. 105, 191–209.

Kilmer, V.J., 1979. Minerals and agriculture. In: Trudinger,

P.A., Swaine, D.J. (Eds.), Biogeochemical Cycling of Mineral-Forming Elements. Elsevier Scientific Publishing

Company, Amsterdam, pp. 515–558.

Kramer, J.R., Allen, H.E., 1988. Metal Speciation: Theory,

Analysis and Application. Lewis Publishers, MI, USA.

Kuo, S., Heilman, P.E., Baker, A.S., 1983. Distribution and

forms of copper, zinc, cadmium, iron and manganese in soils

near a copper smelter. Soil Sci. 135, 101–109.

Lake, D.L., Kirk, P.W.W., Lester, J.N., 1984. Fractionation,

characterization, and speciation of heavy metals in sewage

sludge and sludge-amended soils: a review. J. Environ. Qual.

13, 175–183.

Leschber R. Davis R.B. L’Hermite P. Chemical Methods for

Assessing Bio-Available Metals in Sludges and Soils.




Li, X.D., Thornton, I., 1993a. Multi-element contamination in

soil and plant in the old mining area. U.K. Appl. Geochem.

S2, 51–56.

Li, X.D., Thornton, I., 1993b. Arsenic, antimony and bismuth

in soil and pasture herbage in some metalliferous old mining

areas in England. Environ. Geochem. Health 15, 135–144.

Li, X.D., Coles, B.J., Ramsey, M.H., Thornton, I., 1995a.

Sequential extraction of soils for multielement analysis by

ICP-AES. Chem. Geol. 124, 109–123.

Li, X.D., Coles, B.J., Ramsey, M.H., Thornton, I., 1995b.

Chemical partitioning of the new NIST SRMS (2709–2711)

by sequential extraction using ICP-AES. Analyst 120, 1415–

1419.

Ma, L.Q., Rao, G.N., 1997. Chemical fractionation of cad-

mium, copper, nickel, and zinc in contaminated soils. J.

Environ. Qual. 26, 259–264.

Martin, J.M., Nirel, P., Thomas, A.J., 1987. Sequential extrac-

tion techniques: promises and problems. Mar. Chem. 22,

313–341.

Maskall, J.E., Thornton, I., 1993. Metal contamination of soils

at historical lead smelting sites. Land Contam. Reclam. 1,92–100.

McKenzie, R.M., 1980. The adsorption of lead and other heavy

metals on oxides of manganese and iron. Aust. J. Soil Res.

18, 61–73.

Murphy, S., 1992. Smelting residues from boles and simple

smeltmills. In: Historical Metallurgy Society: Boles and

Smeltmills Seminar, 15–17 May, 1992, pp. 43–47.

Pickering, W.F., 1986. Metal ion speciation — soils and sedi-

ments (a review). Ore Geology Review 1, 83–146.

Ramos, L., Hernandez, L.M., Gonzalez, M.J., 1994. Sequential

fractionation of copper, lead, cadmium and zinc in soil from

or near Donana National Park. J. Environ. Qual. 23, 50–57.

Ramos, L., Gonzalez, M.J., Hernandez, L.M., 1999. Sequential

extraction of copper, lead, cadmium, and zinc in sediments

from Ebro River (Spain): relationship with levels detected in

earthworms. Bull. Environ. Contam. Toxicol. 62, 301–308.

Ramsey, M.H., Thompson, M., 1987. High-accuracy analysis

by inductively coupled plasma atomic emission spectrometry

using the parameter-related internal standard method. J.

Anal. Atomic Spectrosc. 2, 497–502.

Rapin, F., Fo ¨ rstner, U., 1983. On the selectivity of various

extractants used in sequential leaching techniques for parti-

culate metal speciation. In: Proc. Int. Conf. Heavy Metals in

the Environment Heidelberg, Germany, pp. 1074–1077.

Rauret, G., Rubio, R., Lopez-Sachez, J.F., 1989. Optimization

of Tessier procedure for metal solid speciation in river sedi-

ments. Intern. J. Environ. Anal. Chem. 36, 69–83.

Shuman, L.M., 1985. Fractionation method for soil microele-

ments. Soil Sci. 140, 11–22.

Smith, E.G., Rhys, G.H., Eden, R.A., 1967. Geology of the

Country around Chesterfield, Matlock and Mansfield. Mem.

Geol. Surv. Gt. Br., Brit. Geol. Survey.

Span, D., Gaillard, J.-F., 1986. An investigation of a procedure

for determining carbonate-bound trace metals. Chem. Geol.

56, 135–141.

Sposito, G., 1983. The chemical forms of trace metals in soils.

In: Thornton, I. (Ed.), Applied Environmental Geochem-

istry. Academic Press, London, pp. 123–170.

Tessier, A., Campbell, P.G.C., Bisson, M., 1979. Sequential

extraction procedure for speciation of particulate trace

metals. Anal. Chem. 51, 844–851.

Tessier, A., Campbell, P.G.C., Auclair, J.C., Bisson, M., 1984.

Relationships between the partitioning of trace metals in

sediments and their accumulation in the tissues of the fresh-

water Mollusc Elliptio complanata in a mining area. Can. J.Fish. Aquat. Sci. 41, 1463–1472.

Tessier, A., Rapin, F., Carignan, R., 1985. Trace metals in oxic

lake sediments: possible adsorption onto iron oxyhydroxides.

Geochim. Cosmochim. Acta 49, 183–194.

Thompson, M., Walsh, J.N., 1988. A Handbook of Inductively

Coupled Plasma Spectrometry, 2nd Edition. Blackie, London.

Tipping, E., Thompson, D.W., Ohnstad, M., Hetherington,

N.B., 1986. Effects of pH on the release of metals from

naturally-occurring oxides of Mn and Fe. Environ. Technol.

Lett. 7, 109–114.

Ure, A., Quevaullier, P.H., 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

CEC. Int. J. Environ. Analyt. Chem. 51, 135–151.

Valin, R.V., Morse, J.M., 1982. An investigation of methods

commonly used for the selective removal and characteriza-

tion of trace metals in sediments. Mar. Chem. 11, 535–564.

Willies, L., 1990. Derbyshire lead smelting in the eighteenth

and nineteenth centuries. Bull. Peak. Dist. Min. His. Soc. 11,

1–19.

Xian, X., 1989. Response of Kidney Bean to concentration and

chemical form of cadmium, zinc and lead in polluted soils.

Environ. Pollut. 57, 127–137.


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