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Journal of Environmental Management 95 (2012) S42eS49

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Journal of Environmental Management


journal homepage: www.elsevier.com/locate/jenvman

Heavy metals, salts and organic residues in old solid urban waste landlls and
surface waters in their discharge areas: Determinants for restoring their impact
J. Pastor a, *, A.J. Hernndez b
a
b

MNCN, CSIC, c/Serrano 115 dupl, 28006 Madrid, Spain


Dept. of Ecology, University of Alcal, 28871 Alcal de Henares, Madrid, Spain

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 30 September 2009
Received in revised form
16 June 2011
Accepted 24 June 2011
Available online 20 July 2011

This study was designed to determine the state of polluted soils in the main landlls of the Community of
Madrid (central Spain), as part of a continuous assessment of the impacts of urban solid waste (USW)
landlls that were capped with a layer of soil 20 years ago. Our analysis of this problem has been highly
conditioned by the constant re-use of many of the USW landlls, since they have never been the target of
any specic restoration plan. Our periodical analysis of cover soils and soils from discharge areas of the
landlls indicates soil pollution has worsened over the years. Here, we examined heavy metal, salts, and
organic compounds in soil and surface water samples taken from 15 landlls in the Madrid region.
Impacts of the landll soil covers on nematode and plant diversity were also evaluated. These analyses
continue to reveal the presence of heavy metals (Zn, Cu, Cr, Ni, Pb, Cd) in soils, and salts (sulphates,
chlorides and nitrates) in soils and surface waters. In addition, non-agricultural organic compounds,
mainly aromatic and aliphatic hydrocarbons, often appeared in very high concentrations, and high levels
of insecticides such as gamma-HCH (lindane) were also detected in soils. Around 50% of the water
samples collected showed chemical demand of oxygen (CDO) values in excess of 150 mg/l. Traces of
phenolic compounds were detected in some landlls, some of which exhibited high levels of 2chlorophenol and pentachlorophenol. All these factors are conditioning both the revegetation of the
landll systems and the remediation of their slopes and terrestrial ecosystems arising in their discharge
areas.
This work updates the current situation and discusses risks for the health of the ecosystems, humans,
domestic animals and wildlife living close to these landlls.
2011 Elsevier Ltd. All rights reserved.

Keywords:
Anthrosols
Soil pollution
Water pollution
Salinity
Heavy metals
Anions
Organic pollutants
Plants biodiversity
Nematodes

1. Introduction
Municipal solid waste landlls often represent a major environmental problem due to their proximity to inhabited areas.
According to Chiemchaisri et al. (2007) for example, in 2004 there
were 425 disposal sites (95 landlls; 330 open dumps) in Thailand
such that for many years over 60% of solid waste disposal in
Thailand involved open dumping. Recent literature in this area has
been abundant, with emphasis on publications from Asian countries (Esakku et al., 2005; Fan et al., 2006; Nagendran et al., 2006;
Xiaoli et al., 2007); eastern and southern Europe (Eitminaviit
and Matuseviit, 2005; Zupancic et al., 2009; Businelli et al.,
2009; Mari et al., 2009) but also with signicant contributions
from other regions (ygard et al., 2004; Slack et al., 2004;

* Corresponding author.
E-mail address: jpastor@ccma.csic.es (J. Pastor).
0301-4797/$ e see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jenvman.2011.06.048

Herwijnen et al. 2007; stman et al., 2006; MacDonald et al.,


2008; Schenato et al., 2008). In contrast, few research efforts
have been devoted to landlls in arid or semi-arid environments
(Illera et al., 2000; Al-Yaqout and Hamoda, 2003).
The risks of soil pollution for ecosystems in periurban areas are
especially linked to the pollution effects of old mixed solid waste
landlls (industrial and urban solids). It is possible that a signicant
role may be attributed to effects arising from these waste materials
such as the physical medium, the movement of contaminants due
to ow forces, and new interactions occurring in the system due
mainly to salinity, heavy metal toxicity and organic contaminants.
Around 20 years ago, a large number of the Madrid regions urban
solid waste landlls were sealed. At different times over these past
twenty years, the landll soils and the discharge areas of the sealed
tips have been analyzed. Since then, we have constantly been
assessing the presence of contaminating residues both in landll
soils and in affected surrounding ecosystems. Hernndez et al.
(1998a, b), Pastor et al. (1993b) and Pastor and Hernndez (2002)

J. Pastor, A.J. Hernndez / Journal of Environmental Management 95 (2012) S42eS49

S43

Table 1
Current uses (2008) of the 15 landlls.
Landlls
Gneiss & granite
Colmenar Viejo
S. Lorenzo
El Escorial
Arkoses
Mstoles
Villaviciosa
Navalcarnero
El lamo
Limestone
Pinto 1
Pinto 2
Pinto 3
La Poveda
Arganda del Rey
Mejorada de campo
Alcal de Henares
Gypsum
Aranjuez

Lat.

Long.

Discharge areas

Current use of the landll

No. slopes

40 390 N
40 350 N
40 35 0 N

3 450 W
4 80 W
4 70 W

Creek & wet grassland


Creek & ash-trees
Creek & wet grassland

Cattle grazing
Nomad shepherding; Reforestation
Cattle grazing

3
3
4

40
40
40
40

200 N
210 N
170 N
130 N

3
3
4
3

520 W
540 W
170 W
590 W

Creek & wetland


Wetland
Cereal crops
Wetland

Cereal crops and shepherding


Leisure
Sheep grazing; Housing
Restoration with herbaceous covers

3
1
e
2

40
40
40
40
40
40
40

140 N
140 N
140 N
170 N
180 N
230 N
290 N

3
3
3
3
3
3
3

410 W
420 W
420 W
260 W
260 W
290 W
220 W

Cereal crops
Cereal crops
Road
Creek
Creek
River
River

Reforestation
In disuse
Re-used; Use controlled at present.
Re-used for rubble disposal
Uncontrolled; new spillages of rubble
Nomad shepherding. Reforestation
Reforestation

5
4
4
2
2
1
1

Creek

Crumbling observed after sealing

40 10 N

3 380 W

have described the physical and chemical condition of these soils,


taking into account the substrate underlying the landlls that were
capped with soils from their respective surroundings. These past
reports have also described the main plant species growing during
the process of revegetation of the tips in the rst few years. The aim
of the present paper was to describe some of the most signicant
chemical determinants for the design of measures to restore the
impacts of these landlls. The goal of the road-map we propose is
to identify the heavy metals, salinity and organic compounds
responsible for the main detrimental effects produced, mainly on
soils and surface waters, but also on plants and soil organisms.
2. Materials and methods
We examined 15 old urban (and industrial) solid waste landlls
near the major cities and towns of the province of Madrid. These
landlls were sealed around twenty years ago, simply by capping
with soil. The main characteristics of the waste landlls can be
found in Pastor and Hernndez (2002 and 2007).
At each of these 15 landll sites, 4 to 6 soil samples (0e10 cm)
were collected depending on their size to give a total of 75 samples.
Control samples were taken from the topsoil layer (0e15 cm) of
surrounding grazing lands (reference ecosystems).
A spade was used to obtain an average sample of topsoil in each
zone that was subsequently used for physical-chemical determinations (MAPA, 1982; Hernndez and Pastor, 1989; Pastor and
Hernndez, 2007). Determination was made of pseudototal
contents of Al, heavy metals and trace elements (Cr, Ni, Pb, Cd, Cu,
Zn, Fe, Mn), as well as pH, soil anions and EC. Metals in the soil were
determined by inductively coupled plasma-optical emission spectroscopy (ICP-OES). For these determinations, the soil samples were
ground in an agate mortar and acid digested using a 4:1 mixture of
Table 2
Heavy metal contents (mg/kg) recorded for the soil covers (mean values and standard deviation) of landlls overlying the main representative substrates of the
Madrid area ve years after capping.
Soil heavy metals

Granites and gneiss

Zn
Cu
Pb
Ni
Cr
Cd
Co

125.5
8.7
7.7
22.2
0.0
0.0
0.0









69.8
19.4
5.6
3.6
0.0
0.0
0.0

Arkoses
83.5
150.9
72.8
15.7
4.4
0.3
1. 5









HNO3 and HClO4. Soil anions were analyzed by ion


chromatography.
The organic pollutants determined were: total hydrocarbons by
infrared spectrophotometry (UNE 77307); chlorinated insecticides
and polychlorinated biphenyls by gas chromatography (ISO 10382),
PAHs by gas chromatography (ISO 18287), and phenols by gas
chromatography (U.S. E.P.A 3550B, U.S. E.P.A 3650B and U.S. E.P.A
8401).
Water samples were also collected from the main discharge
zones of the landlls. These samples were obtained at random
points across the wetland and stored in dark glass containers to
determine organic and inorganic compounds.
For the determination of organic pollutants in water, organic
compounds (lipophilic) were extracted from the water sample by
retention on a cartridge or a disk containing the organic phase
octadecylsilyl chemically bound to a solid matrix. Retained
compounds were subsequently eluted using a small amount of
dichloromethane, separated by gas chromatography and identied
by mass spectrometry.
In a separate study conducted only on the arkosic landlls,
a further 91 soil samples were obtained in spring from 1 m2
-quadrants set up in semi-natural grasslands and agricultural lands
abandoned in the last 20 years (55 sites) and in 36 urban waste
landll sites sealed with a 30 cm layer of soil. After inventoring the
plant species present in these plots, the soil samples (maximum
depth 10 cm) were subjected to nematode counts using previously
described methods (Hernndez and Pastor, 1989). Samples were
kept at 4  C until processing. Nematodes were extracted from
100 ml by the sugar centrifugation method as described in
Hernandez and Pastor (1989). After counting the total number of
nematodes, 100 nematodes per sample were randomly selected
and identied to the genus level if possible with the help of an
inverted compound microscope. Identied taxa were classied into
fungivore, bacteriovore, omnivore, predator or plant feeding
trophic groups on the basis of either reported feeding habits or
stoma and oesophageal morphology (Yeates et al., 1993; Urcelai
et al., 2000).

Limestones
146.0
730.2
297.0
8.1
4.5
2.1
2.3

57.5
13.0
28.5
22.5
0.0
0.0
0.0









10.5
11.0
3.5
3.5
0.0
0.0
0.0

3. Results and discussion


3.1. Main characteristics of the landlls
Table 1 shows the geographical coordinates of each of the 15
landlls and their current uses. Mean soil heavy metal contents and

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J. Pastor, A.J. Hernndez / Journal of Environmental Management 95 (2012) S42eS49

Table 3
pH and heavy metal contents (mg/kg) recorded for the soil covers of landlls in the Madrid area 18e20 years after capping (2007e08).
Landlls

pH

Al

Fe

Mn

Zn

Cu

Cr

Ni

Pb

Cd

Colmenar Viejo
San Lorenzo
El Escorial
Mstoles
Villaviciosa
Navalcarnero
El lamo
Pinto 1
Pinto 2
Pinto 3
La Poveda
Arganda
Mejorada del campo
Alcal
Aranjuez
Reference levels

6.3
7.3
7.2
5.7
7.5
6.5
7.2
7.3
7.6
7.9
7.6
8.0
7.7
7.6
7.7

33588
29819
29067
23886
26751
8744
8711
27366
31327
42483
28985
29684
70090
51800
71420

22598
21304
77315
12188
15479
5019
4149
16794
20261
25938
19731
15488
39706
32384
37512

293
218
446
241
213
202
93
217
204
631
225
193
366
288
256

68
185
693
38
93.3
12.4
26
39
39
144
50
110
148
130
86
140

14
40
139
8.8
36.1
4.3
8.0
8.5
8.2
55
28
27
29
23
69
36

3.7
12
23
2.7
1.3
1.6
1.9
0.3
0.4
40
2.8
5.9
8.1
12
2.2
100

5.6
6.0
13
3.1
2.9
1.1
1.5
3.4
3.4
5.0
9.1
7.4
15
15
15
35

13.9
223
182
9.4
24.8
2.7
4.4
7.0
4.7
51
13.4
60
20
13.4
11.6
50

0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1

their corresponding standard deviations are provided by geological


substrate in Table 2. The plant cover characteristics of the waste
landlls can be found in Pastor and Hernndez (2002).
The residues deposited in the landlls examined here are of
a heterogeneous nature (urban, industrial and inert solids) and
have undergone no previous treatment. The edaphic landll
material has never exceeded 40 cm. The scant layer of landll soil
and the steep slopes have meant that much soil has been lost over
the years through erosion, leaving many un-decomposed residues
in the cracks produced by surface run-off. The characteristics of the
slopes do not only affect plant colonization in these systems but
also the ecosystems of the discharge areas. Even where there is only
one slope, its run-off sometimes fans out, and thus differently
affects the biodiversity of the damp ground in different zones of the
discharge area. Also, considerable variation in soil variables exists
on a given slope (Pastor and Hernndez, 2002, 2007). Since our rst
analyses, differences have also arisen in relation to the landll
material originating from the different substrates. Research into
this problem is strongly conditioned by the constant re-use of many
of the landlls, given that no particular recovery plan was envisaged for any of them. This has led to the deposition, after the rst
sealing, not only of inert residues but also residues of manifest
chemical composition. This aggravates the problems of many tips
and poses great difculty when trying to restore their impacts. In
the following sections we describe some of the ndings on which
these assertions are based.

Table 4
Anion contents (mg/kg) and electrical conductivity (mS/cm) recorded for the soil
covers of the landlls 18e20 years after capping (2008).
Landlls

Cl

NO2

NO3

PO4

SO4

EC

Colmenar Viejo
San Lorenzo
El Escorial
Mstoles
Villaviciosa
Navalcarnero
El Alamo
Pinto 1
Pinto 2
Pinto 3
La Poveda
Arganda
Mejorada del Campo
Alcal
Aranjuez
Reference levels

0.7
0.4
0.4
0.8
0.3
0.7
0.3
3.6
4.6
1.6
2.9
1.4
4.9
0.9
1.3
>12

53.8
9.7
15.1
65.3
9.6
4.9
10.8
9.8
5.8
30.9
10.8
64.4
55.0
43.9
20.3
>55

1.4
2.6
3.7
1.0
6.1
1.3
2.7
5.3
8.2
3.0
4.4
5.6
2.3
8.4
2.7
e

51.7
544.3
783.1
64.9
74.5
167.5
13.6
9.3
7.3
409.1
70.8
19795
298.5
443.3
189.4
>100

22.1
16.7
13.4
30.7
45.8
9.8
34.9
5.1
0.0
8.3
5.3
2.5
6.3
28.3
3.8
>45

64.3
46.1
73.3
852
19.3
17.7
14.8
17.2
17.2
676.9
774
3164
1195
102
4065
>150

244
669
606
160
392
101
106
190
184
759
645
1947
1248
650
2440
>350

3.2. Identifying pollutants in the topsoil layer


The landll soils and the soils from the discharge areas have
been periodically assessed over the last 20 years, with attention
mainly paid to inorganic chemical compounds. Tables 3 and 4 show
the maximum levels of heavy metals recorded for each landll.
These factors compromise the biotic components of the affected
ecosystems. Tables 2 and 3 show the soil variables indicating
contamination produced by residues from the tips; in 5 of the
landlls these exceed the benchmark levels for heavy metals.
Johansen and Carlson (1976) found that among the heavy metals, Fe
were high in all soils examined followed by Zn. We also detected Zn
in highest quantities in our landlls. Concentrations of Cr, Ni, Cu, Cd
and Pb were low. Xiaoli et al. (2007) studied the characteristics,
distribution, and mobility of heavy metals in a landll. The refuse
was characterized as containing high concentrations of heavy
metals and a relatively high pH. Zn demonstrated the greatest
mobility compared to other heavy metals, whereas Cd was well
retained in the landll. Zn was also found at higher concentrations
than the remaining heavy metals. In the dumpsite examined by
Esakku et al. (2005), total metal contents in descending order were
Fe, Cu, Zn, Cr, Mn, Pb, Ni and Cd.
In a semi-arid environment, Illera et al. (2000) observed
considerably increased levels of Cd, Cu, Pb and Zn as a consequence
of the high contents and/or high availability of these metals in
mixed solid waste (MSW) landlls. According to these authors Zn,
followed at some distance by Cu, was the most abundant heavy
metal. In arid regions, the generation of leachate from MSW landlls has long been neglected on the assumption that only minimal
leachate could be formed in the absence of precipitation (Al-Yaqout
and Hamoda, 2003). The latter authors found that leachates
collected from both active and old (closed) landlls were severely
contaminated with organic compounds, heavy metals and salts.
The metals we found in our 15 landlls mainly in semi-arid environments in descending order were Fe, Al, Zn, Mn, Cu, Pb, Cr, Ni and
Cd. Leachate Zn contents in the study by Al-Yaqout and Hamoda
were similar to those detected here while Cu levels were higher.
Heavy metals absorbed by plants can be harmful to the animals
that consume them, both domestic and wild. Snchez-Chardi and
Nadal (2007) quantied the bioaccumulation of metals (Pb, Hg,
Cd, Fe, Mg, Zn, Cu, Mn, Mo, and Cr) from the landll of Garraf
(Barcelona, Spain) in the greater white-toothed shrew, Crocidura
russula (Insectivora, Mammalia). These authors observed substantial amounts of potentially toxic metals (Pb and Cd concentrations
of up to 59.71 and 56.57 mg g1 DW respectively in the kidneys). The
genotoxic actions of these metals suggested detrimental effects also

J. Pastor, A.J. Hernndez / Journal of Environmental Management 95 (2012) S42eS49

S45

Table 5
Organic pollutants (mg/kg) recorded in the old urban landlls in 2008.
Landll

Phenolic compounds

Chlorinated Insecticides

Colmenar Viejo
San Lorenzo
El Escorial

Phenol

Lindane, Hexachlorebencene

Mostoles
Villaviciosa
Navalcarnero
El Alamo
Pinto 1a
Pinto 2
Pinto 3

La Poveda
Arganda
Mejorada

Alcala de H.
Aranjuez
Refer. Levels

Hydrocarbons

PCBs

PAHs

58.21

0.054
0.027

Benzo(a)pyrene
Dibenzo(a,h)anthracene

Lindane
Lindane
Lindane
Phenol (0.033)
2-chlorophenol
2,4,5-trichlorophenol,
2,4,6-trichlorophenol,
2,4-dichlorophenol,
Pentachlorophenol
Phenol, Cresols
2-chlorophenol,
Pentachlorophenol,
Phenol, Cresols
Pentachlorophenol, Cresols
Phenol

p,p-DDD
Hexachlorebencene

Benzo(a)pyrene
Benzo(a)pyrene

Lindane;
Hexachlorebencene
Lindane
Lindane (gamma-HCH)

62.34
Benzo(a)pyrene

0.01 (Lindane)

59.7

0.038
0.01

50.0

0.027
0.01

Higher contents are represented in bold.


a
Chlorinated hydrocarbons: 1,4-dichlorobencene, 1,2,4-trichlorobencene, 1,4-dichlorobencene.

on biota. In general, the heavy metal contents of the huge landll


investigated by these authors were higher than those observed
here. This may be explained by the industrial importance of
Barcelona.
Soil salinity in the landlls emerged as a factor that was more
detrimental than soil heavy metal concentrations (Hernndez et al.,
1998b), although the landlls showed intensely varying concentrations of the different anions examined, as may be seen in Table 4,
which is provided as an example. Soil EC was high in 9 of the
landlls, NO3 in 8 and SO4 in six.
To assess the impact of pollutants from the main landll of the
city of Zagreb (Croatia) on the underlying soil, Ahel et al. (1998)
determined a broad spectrum of inorganic and organic constituents in samples of solid waste, soil and aquifer sediments. The
compounds identied in the landll could be classied into the
two main categories: markers of biological waste and of its
microbial transformation (ammonia, dissolved organic carbon,
short-chain aliphatic acids, phenols and derivatives of abiotic
acid) and markers of anthropogenic waste (toxic metals, hydrocarbons chlorinated hydrocarbons, surfactant-derived compounds, phthalates and pharmaceutical chemicals). These authors
noted that, besides the vertical inltration of leachate from the
solid waste, the hydrological groundwater regime also had

a strong impact on contaminant distributions in soils beneath the


landll.
We also observed considerable differences in the organic
pollutants appearing on our landll slopes. The hydrocarbons
analyzed often occurred at exceedingly high values. Some chlorinated insecticides (of the 13 studied) such as lindane also exist at
harmful levels in the soils, according to the indicator values recommended for terrestrial organisms. In discharge areas, other
organic pollutants detected were phenolic compounds, polychlorinated biphenyls (PCBs) and polyaromatic hydrocarbons
(PAHs). Slack et al. (2004) examined pollutants in leachates from
household hazardous waste (HHW) in municipal landlls. Their
results indicate that the risks associated with the disposal of HHW
have not been fully elucidated. This review revealed that a broad
range of xenobiotic compounds occurring in leachates could be
linked to HHW. Mari et al. (2009) analysed the exposure to heavy
metals and polychlorinated dibenzo-p-dioxins and polychlorinated
dibenzofurans (PCDD/Fs) of people living in the vicinity of
a hazardous waste landll (HWL) in Castellol (Barcelona, Spain).
The metals most often detected were again Zn and Cu, while Pb, Ni
and Cd were lower and Cr higher than the values we recorded.
Health risks were evaluated according to the distance from the
sampling locations to the HWL (near and far-sites). Concentrations

Table 6
Differences in soil variables (Students t-test) between landll covers (n 59) and reference ecosystems (92 pasture soils) in arkosic substrates.
Soil variable

Landll covers
X  s.d.

pH
OM
Fe
Mn
Zn
Cu
Pb
Cd
Cr
Ni
Co
Al
B

7.1 
0.7 
15291 
223 
89 
187 
89.8 
1.9 
4.6 
14.0 
1.9 
37404 
5.5 

0.3
0.4
6455
113
157
741
313
3.4
4.7
9.2
2.6
13696
11.8

Reference ecosystems
Range

X  s.d.

6.3e7.6
0.2e1.6
5047e28453
46e552
13.8e960
2.5e3680
0e797
0e10
0e17
0e32
0e9
15250e65790
0e50.0

6.2 
3.5 
9057 
112 
32 
19.6 
8
0.1 
2.7 
7.4 
0.0 
24783 
2.6 

Signicance level
Range

0.5
2.7
4029
88
11
32.1
22.8
1.6
2.8
6.3
0.0
11062
5.5

5.1e7.1
0.2e12.2
2315e21945
40e269
9.7e5.8
0e63
0e11.3
0e6.1
0e6.0
1.6e21
0e1.9
5700e54300
0e20.0

99.9
99.9
99.9
99.9
99.0

90.0
95.0
99.0
99.9

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J. Pastor, A.J. Hernndez / Journal of Environmental Management 95 (2012) S42eS49

Table 7
Mean and s.d. of electrical conductivity (EC) and soil anions in discharge areas of
several landlls (L) located in different substrata versus soils from nearby reference
ecosystems (R.E.).
Soil variable

Arganda del Rey


L.

EC (mS/cm)
Chlorides
(mg/100 g)
Sulphates
(mg/100 g)
Nitrates
(mg/100 g)

M
s.d.
M
s.d.
M
s.d.
M
s.d.

1430
156
33.5
7.8
68.5
3.5
4.2
0.5

Alcal de Henares

Pinto 1

R.E.

L.

R.E.

L.

R.E

530

3890
735
22.0
2.8
155.5
3.5
3.9
0.9

1200

11045
6583
76.5
10.6
4544.0
5883.1
31.3
19.1

3940

5.0
1.0
2.0

5.0
4.0
0.5

18.0
412.0

3.3. Impacts of landll covers on the diversity of plants and


nematodes

19.8

Table 8
Statistically signicant differences recorded in 36 soil samples taken from landlls
and 55 samples from a reference ecosystems in arkosic terrain.
Biological parameters

Landll
covers

Plants
Plant cover (%)
Average height of plant cover (cm)
Plant diversity (No sp/m2.)
Nematodes
Total Density (No/100 cm3)
Ectoparasites
Endoparasites
Omnivores
Bacterial feeders
Fungal feeders

34.9  17.1
14.9  9.1
15.5  7.3
45.6
10.1
0.1
10.6
71.3
8.0








38.3
13.2
0.4
11.3
18.7
9.3

Reference
ecosystem
soils

Signicance
level

60.6  25.0
22.7  10.2
29.5  11.4
122.1
30.5
0.9
12.6
37.7
17.0








95
95

50.7
15.7
4.0
10.2
17.5
13.3

Table 6 shows differences in soil variables between the arkosic


landlls and their reference ecosystems. It may be observed that
the differences recorded for most of these variables are highly
signicant. Heavy metal contents were higher in the landll covers
than the control soil samples. Table 7 shows differences in the
electrical conductivity and soil anion levels in discharge areas of
several landlls located in different substrates compared to soils
from nearby reference ecosystems.

99.9
99.9

99.9
95

of PCDD/Fs, as well as those of some metals, were found to be


relatively higher in the HWL and Castellol (the nearest village)
than in samples collected far away, resulting in slightly increased
exposure to those pollutants.
Open landll dumping areas for municipal wastes in developing
countries have received particular attention with regard to environmental pollution problems. Because of the uncontrolled burning
of solid wastes, elevated contamination by several toxic chemicals
including dioxins and related compounds in these dumping sites
has been anticipated. Hung Minh et al. (2003) analyzed concentrations of PCDD/Fs and coplanar PCBs in soils from dumping sites
in the Philippines, Cambodia, India, and Vietnam. Residue
concentrations of PCDD/Fs and coplanar PCBs in dumping site soils
were apparently greater than those in soils collected in agricultural
or urban areas far from dumping sites, suggesting that dumping
sites are potential sources of PCDD/Fs and related compounds.
Observed PCDD/F concentrations in soils from dumping sites in the
Philippines and Cambodia were comparable or higher than those
reported for dioxin-contaminated locations in the world. Table 5
indicates the current values of organic variables recorded in our
study. The contents of these pollutants were at times quite high.
Values exceeding permissible levels according to Spanish legislation appear in bold.

The topsoil layer of the landlls is inhabited by soil populations such as microorganisms or nematodes, and is also the
main source of mineral nutrients for plant species growing in the
soil (Hernndez et al., 1998a; Urcelai et al., 2000; Pastor and
Hernndez, 2002). Our phytoecological and soil studies performed in the past years both on the capping soils and soils of the
discharge zones of urban waste landlls have revealed certain
features that may be of help when planning to ecologically
restore this type of environmental setting. Table 8 shows the
reduced diversity of plants and nematodes detected in the
capping layer of the landlls, which is probably the result of
adverse conditions in general, and toxicity due to heavy metals,
high contents of salts or organic pollutants. This diversity is even
lower than that reported for other highly degraded ecosystems of
the area (Urcelai et al., 2000). Biederman et al. (2008) also
investigated nematode community early development in ecological restoration.
Contrary to expectations, surface amendment treatments
signicantly increased bacterivorous, plant parasitic, omnivorous
and predator nematode densities, but had no inuence on fungi/
root-tip feeding nematodes. In agreement with these authors,
bacterial feeders were the predominant group detected at our
landlls. Numbers of ectoparasites, endoparasites, fungal feeders
and omnivores were signicantly lower than in our reference
ecosystems. Other observations in soil fauna were made by
Eitminaviit and Matuseviit (2005) who summarized data on
the domestic waste landlls of Vilnius (Lithuania). These authors
focused on the inuence of landlls on the soils of their environment. The structure of microarthropod complexes was monodominant, species composition was poor, and herbaceous plants
intensively accumulated heavy metals. Even after fteen years, the
landlls remained polluted with high concentrations of Cd, Ni, Pb,
and Zn.
Taking into account these ndings together with those of
Pastor et al. (1993a, b) and Hernndez et al. (1998a, b), who also
observed increased levels of salts in landlls, the difculty in
securing an environment of available nutrients for plants
becomes clear, despite the appropriate pH of the soil (means of
7.1 were detected for landlls and 6.2 for control soil samples).
Such high salt contents indicate a need for bioassays aimed at
evaluating the suitability of native plant species as plant covers
for landlls.

Table 9
Current pH, macroelement and boron contents (mg/l) of water samples obtained from the discharge areas of the landlls.
Landlls

pH

Ca

Mg

Na

Al

Fe

Mn

Colmenar Viejo
San Lorenzo
Mstoles
El Alamo
Getafe
Aranjuez

6.9
7.8
8.8
8.4
8.1
8.6

22.3
18.4
110.3
55.4
530.0
410.8

8.6
3.9
24.4
7.9
244.4
583.6

103.3
2.2
61.4
7.1
4.1
33.6

126.0
6.2
210.9
30.7
71.3
2736.5

0.0
0.0
2.19
0.56
0.0
0.0

43.6
8.7
20.3
26.1
567
2780

0.12
0.0
0.05
0.04
0.06
0.0

0.04
0.00
0.36
0.06
0.06
0.11

0.10
0.0
1.97
0.03
0.08
0.06

0.19
0.03
0.22
0.06
0.18
0.75

J. Pastor, A.J. Hernndez / Journal of Environmental Management 95 (2012) S42eS49


Table 10
Heavy metal (mg/l) contents of water samples collected from damp ground and
streams at the foot of the landlls in early spring.

S47

Table 12
List of organic compounds detected in 2008 in water samples affected by the
presence of a landll.

Landlls

Zn

Cu

Mstoles

El lamo

Colmenar Viejo
San Lorenzo
Mstoles
El Alamo
Aranjuez

0.06
n.d
0.034
n.d
n.d

n.d
n.d
0.011
0.025
0.023

Tetradecane
4-tert-butyl benzoic acid
Dietiltoluamide
Diethyl phthalate
Heptadecane
Tetradecanoic acid

Undecane
Octanoic acid
Tetradecane
Terbucarb
Diethyl phthalate
2-methyl-, 1-(1,1-dimethylethyl)-2-methyl-1,
3-propanodyl, propionate
Diisobutyl phthalate
Butyl isobutyl phthalate
Dibutyl phthalate
Hexadecanoic acid
Pentadecane
Tricosane
Di 2-ethylhexyl adipate
Tetracosane
Eicosane
Di 2-ethylhexyl phthalate

Pb, Cd, Cr, Ni, As: not detected.

3.4. Composition of waters in discharge areas


In a study in Denmark by Kjeldsen et al. (1998), an old municipal
landll emerged as a groundwater pollution source based on
landll history and leachate composition. Table 9 shows the current
pH and composition of water obtained from damp ground and
streams at the foot of the present landlls. Table 10 provides the
heavy metal contents (mg/l) of these samples. Elevated values were
recorded of pH, Na and S. High Ca and Mg contents were also
detected in the waters close to the landlls of Getafe and Aranjuez.
Table 11 shows the electrical conductivity (mS/cm), chemical
demand of oxygen (CDO) and anion contents (mg/l) of water
samples collected from damp ground and streams in the discharge
areas. Around 50% of the water samples collected showed CDO
values greater than 150 mg/l. In contrast, nitrates and uorides
have undergone a considerable rise over the years. These trends
differ according to the aquatic ecosystem affected by the landlls,
although salinity also seems to be declining in the landlls on
a granite substrate (Pastor et al., 1993c). Similar studies to ours
reporting comparable ndings include those by Mikac et al. (1998),
who assessed groundwater contamination in the vicinity of
a municipal solid waste landll in Zagreb (Croatia), Paxus (2000),
who examined organic compounds in municipal landll leachates,
and Slack et al. (2004), who analyzed the hazardous components of
household waste.
Table 12 shows the relationship between the organic
compounds in the waters and their proximity to the landlls.
Harmsen (1983) and Albaiges et al. (1986) identied organic indicators of groundwater pollution close to a biohazardous waste
landll. We observed a tendency towards higher carboxylic acid
levels in some of our landlls, but more intense effects have been
attributed to biohazardous waste in the landlls of Barcelona than
those examined here. Albaiges et al. detected around double the
concentration of phthalates, a group of colourless, odourless liquid
chemical compounds mainly used as laminates, to that observed in
our landlls. In Oman and Rosqvists (1999) study of the transport
fate of organic compounds in water owing through landlls, the
maximum concentration of diethyl phthalate (DEP) detected was
346 ml.
According to Jobling et al. (1995), a variety of environmentally
persistent chemicals, including some phthalate plasticizers, are
weakly estrogenic. Bauer and Herrman (1997) estimated the environmental impacts of phthalic acid esters leaching from household
wastes. These authors recorded maximal concentrations of 2.6%

Diisobutyl phthalate
Dibutyl phthalate
Hexadecanoic acid
Oleic acid
Octadecanoic acid
Tricosane
Di-2-ethylhexyl adipate
Tetracosane
Eicosane
di-2-ethylhexyl phthalate
Squalene
San Lorenzo

Colmenar Viejo

Octanoic acid
3-hydroxy-2,2,4-trimethylpentyl
isobutanoate
Tetradecane

Butyric acid
Undecane
3-Hydroxy-2,2-dimethyl
hexyl butyrate
Tetradecane
Diethyl phthalate

Diethyl phthalate
1,3-pentanediol, 2,2,4-trimethyl
diisobutyrate
Tetradecanoic acid

1,3-Pentanediol,
2,2,4-trimethyl diisobutyrate
Diisobutyl phthalate
Pentadecanoic acid
Dibutyl phthalate
Hexadecanoic acid
Octadecanoic acid
Pentadecane
Tricosane
Bis 2-ethylhexyl adipate
Tetracosane
Eicosane
Di-2-ethylhexyl phthalate
Squalene

Diisobutyl phthalate
Butyl isobutyl phthalate
Dibutyl phthalate
Hexadecanoic acid
Pentadecane
Tricosane
Di 2-ethylhexyl adipate
Tetracosane
Eicosane
Di-2-ethylhexyl phthalate
Dotriacontane
Squalene
Aranjuez
Undecane
Octanoic acid
Tetradecane
Diethyl phthalate
Tetradecanoic acid
Diisobutyl phthalate
Pentadecanoic acid
Butyl isobutyl phthalate
Dibutyl phthalate
Hexadecanoic acid

Oleic acid
Octadecanoic acid
Pentadecane
Tricosane
2-etilhexil adipate
Tetracosane
Eicosane
Bis 2-ethylhexyl phthalate
Squalene

Most dangerous pollutant are represented in bold.

di-(2-ethylhexil)phtalate and calculated this gure to translate to


around 1 kg of phthalate esters per ton of dry waste and the
leaching of some 1 g of phthalic acid esters per ton of dry waste.
Staples et al. (1997) reviewed the global environmental fate of

Table 11
Electrical conductivity (mS/cm), chemical demand of oxygen and anion contents (mg/l) of water samples collected from damp ground and streams close to the landlls.
Landlls

EC

CDO

Cl

NO2

NO3

PO4

SO4

CO3

HCO3

Colmenar Viejo
San Lorenzo
Mstoles
El Alamo
Aranjuez

1281
265
2490
523
13420

261.0
168.0
207.8
91.4
111.8

0.12
0.17
0.28
0.24
0.12

269
4.46
568.3
41.5
770

n.d
n.d
0.10
0.49
n.d

67.7
5.2
4.5
5.4
20.3

n.d
n.d
3.0
2.3
n.d

130.9
26.2
60.9
69.3
8341.0

0.0
0.0
60.0
30.0
48.0

0.0
48.8
201.3
97.6
207.4

S48

J. Pastor, A.J. Hernndez / Journal of Environmental Management 95 (2012) S42eS49

phthalate esters determining that traces of these compounds are


common in waters despite their relatively low solubility in water,
high solubility in oils and low volatility. The most employed
phthalate is the one used for PVC; others are used as solvents to
elaborate perfumes, pesticides, enamels, adhesives, putties and
paint pigments. The high quantities found in our water samples,
despite their low solubility, is worthy of note, although there is
much controversy regarding their effects on health. Several
experiments have shown that the bioaccumulation of phthalate
esters in the aquatic and terrestrial food chain is limited by
biotransformations, which occur more frequently with increasing
trophic level. Thus, they are usually considered to be low- or
medium-level pollutants although high doses of some of them may
cause abnormal hormone behaviour in rodents, as well as damage
to the liver, kidneys, lungs and testicles. Fukuoka et al. (1997)
suggested phthalic acid esters as a cause of testicular damage. In
contrast, studies conducted in primates have not been able to
conrm this theory. Diisobutyl phthalate (DIBP) is used as a plasticizer in coatings (e.g. in antislip coatings and epoxy repair mortars)
and toxic effects of DIBP on reproduction and development have
been described. Diisobutyl phthalate has also been described to
have comparable anti-androgenic effects to di-n-butyl phthalate in
foetal rat testis (Borch et al., 2006; Saillenfait et al., 2008).
It therefore seems evident that diisobutyl phthalate fulls the
criteria for its classication as a CMR (carcinogenic, mutagenic and
reprotoxic) substance according to article 57a) of the REACH
regulation.
The European Union, however, has not yet established any
guidelines for the control of phthalic acid esters. We also detected
large quantities of the resin 4-(1-pyrrolydinyl)-2(1H)-pyrimydinone, detergent components and the herbicide Terbucarb at
our landll sites.
4. Conclusions
Chemical analyses conducted on the soils and waters around
landlls sealed 20 years ago continue to reveal the presence of
heavy metals (Zn, Cu, Cr, Ni, Pb, Cd) in soils, and salts (sulphates,
chlorides and nitrates) and high levels of organic pollutants in both
soils and waters. The events and/or ever-changing uses given to the
landlls after their initial sealing, together with their particular
characteristics pose difculties both for the revegetation and
remediation of these soils that show great variation and heterogeneity in terms of the pollutants found, the density of nematodes
(trophic groups) in the soil, and plant cover.
The existence of intense differences between the landlls and
the surrounding reference ecosystems was identied in terms of
the diversity of plants and nematodes, as well as differences in soil
variables among the different landlls themselves.
Our ndings reveal the real risks posed by these mixed industrial/household landlls in periurban areas and also illustrate how
different concentrations of salts and ions can affect the biotic
components of the surrounding ecosystems.
Acknowledgements
This study was funded by grants from the Spanish Ministry of
Science and Innovation (Project CTM2008-04827) and Madrids
Regional Government (EIADES, Programme P2009/AMB-1478A).
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