ENVIRONMENTAL MONITORING

PROGRAMME OF THE RESTORED

LANDFILL SITE AT SCHISTO, ATTICA.
INTRODUCTION OF A MODERN
LEACHATE TOXICITY ANALYSIS
TECHNIQUE USING BIOASSAYS

T. LOLOS, G. LOLOS, C. TSOBANIDIS, K.OIKONOMOU, C. RAPTIS AND

I. GEORGIOU
Enviroplan S.A., 40, Ag. Konstantinou St., “Aethrio” Business Center 15124,
Athens, Greece

SUMMARY: Environmental monitoring of Solid Waste Management Facilities and especially of

Closed and/or (Un)controlled Solid Disposal Sites is conducted in many countries and has as
target to ensure Public Health as well to avoid any kind of environmental pollution. In the
present work, certain parameters are presented that were examined during the environmental
monitoring of the old restored Solid Waste Disposal Site of Schisto. In particular, the main
components of this work are focused on the following points: i) the chemical composition of
leachates that are produced ii) checking of the degree of pollution in the underground and surface
waters due to leachates iii) analysis of the quality of landfill biogas produced. Also, with the use
of suitable toxicity tests the potential toxicity of both ground /surface waters and leachates has
been evaluated.

1. INTRODUCTION

The subject of environmental monitoring is obligatory in the European Union according to the
Directive 1999/31/EC "Sanitary Landfill of Waste", but also according to the Greek Legislation,
Law 114218/97 "Framework of specifications and programs for general solid waste
management" as well as Law 29407/3508/2002 "Measurements and terms for Sanitary Landfill
of waste".
The environmental monitoring program of the restored landfill site at Schisto includes the
control of all parameters that are likely to cause environmental pollution and endanger Public
Health (mainly leachate and biogas). In addition the programme also checked all environmental
factors that could be influenced from the restored landfill site (mainly surface water, ground
water and atmosphere), as well as other parameters that concern the functional and long-term
safety behavior (meteorological data, settlings, etc.).

Proceedings Sardinia 2007, Eleventh International Waste Management and Landfill Symposium
S. Margherita di Pula, Cagliari, Italy; 1 - 5 October 2007
 2007 by CISA, Environmental Sanitary Engineering Centre, Italy
 Sardinia 2007, Eleventh International Waste Management and Landfill Symposium

Waste disposal from the broad Piraeus Region until 1991 took place in the landfill site of
Schisto. This landfill had operated for almost 25 years covering an area of 416.400 m2, while the
waste deposited amounts to 8.176.000 tones. Until 1978 both municipal and industrial solid
wastes were disposed in Schisto, followed by municipal solid waste only, until its operation was
stopped in 1991. Moreover, Schisto operated without an appropriate impermeable bottom liner
or an effective gas/liquid collection and treatment system for almost 25 years. From 1991
various restoration works have been executed at the site, i.e. final capping of the site, leachate /
biogas management and other infrastructure works (operating facilities, environmental
monitoring works, etc).
In particular, two artificial lagoons for leachate collection were constructed, as well as the
pipeline and the wastewater treatment plant (activated sludge method followed by artificial
wetland). Moreover, biogas management works comprises of the Landfill fuel gas (LFG)
extraction system consisting of 140 vertical wells, an LFG transport network leading to 23 sub-
stations and then to 5 central stations, and a gas flare capable of processing 1.400Nm3/h.
Monitoring works include 9 wells for off-site migration of biogas detection, 3 groundwater-
monitoring wells and 50 marker posts to evaluate waste movements.
The site of Schisto is now in the aftercare –maintenance period according to the requirements
of 99/31 Directive. Regulations governing the disposal of solid waste in landfills specify that
they must be monitored until the emission potential is so low, that do not harm the environment.
The monitoring and aftercare program comprises the analysis of raw/ treated leachate quality,
ground and surface water monitoring, inspection of the final cover and maintenance as required,
and monitoring for any methane off-site migration.

2. MATERIALS AND METHODS

2.1 Chemical analysis

The composition of leachates, surface and ground water was examined with scheduled (monthly)
samplings in representative points in the site, during the period 01/06/2003 - 31/08/2004.
Leachate samples are taken from the artificial lagoons, while samples of ground water were
taken from the existing wells. Finally, 4 sampling points were used for the collection of surface
water. The examined parameters for the determination of chemical composition according to the
environmental terms requirements were:
(a) physical parameters: pH, temperature, conductivity, turbidity, total solids, suspended solids,
dissolved solids
(b) organic parameters: dissolved oxygen, biochemical oxygen demand (BOD5), chemical
oxygen demand (COD), total organic carbon (TOC), organic nitrogen
(c) chemical parameters: ammonium, nitrous, nitric ions, phosphorus, chlorides, fluorine,
phenols, arsenic, cadmium, copper, lead, mercury, nickel, zinc, cobalt.
The methods of analysis were based on the Standard Methods for the Examination of Water and
Wastewater by APHA, AWWA, WEF. Sampling is consistent with ISO 5667-11 and 5667-2
methods.

2.2 Toxicity tests

Leachates arising from waste disposal sites contain toxic substances. Chemical analysis can
detect only a small percentage of the total chemical substances, while it cannot take into account
their synergistic action [2,7]. On the contrary, toxicity tests assess toxicity typically not detected
with chemical analysis, since they take into account all additive effects from the various
 Sardinia 2007, Eleventh International Waste Management and Landfill Symposium

compounds to a living species. Therefore, these tests are considered particularly valuable as far
as environmental samples are concerned.
In most toxicity tests, toxicity is reported as LC50 or EC50, meaning the lethal or effective
concentration that affects 50% of the population. The smaller the indicator LC50 or EC50 is, the
more toxic is the sample, since lower concentration of the toxic sample is required in order to
have a 50% effect to the associated population.
For the evaluation of the relevant samples reported above, Daphnia magna species was used.
The Daphnia magna belongs to shellfishes and is on top of the food chain (consumers). It regards
a widespread species for toxicity tests, and it is certified test according to OECD 202. Toxicity is
determined after counting the number of dead organisms in the sample after keeping the samples
for 24 and 48 hours in constant temperature and absence of light.

2.3 Biogas measurements

Determination of biogas qualitative characteristics was carried out with a gas portable instrument
(GA 94 Geotechnical Instruments) measuring CH4, CO2, O2, N2, H2S, CO, HCN , H2, SO2, NO2,
and Cl2 in biogas collection and control sub and central stations. For evaluating the presence of
air pollutants in the boundary of the site, arising from any biogas losses, gas wells have been
manufactured, in order to sample and analyze the biogas.

3. RESULTS AND DISCUSSION

3.1 Leachate
Leachate characteristics from lagoons A and B is presented in table 1.
The pH values were found to be alkaline (8,80-8,84) which mainly can be considered a
characteristic of the anaerobic phase. Leachate samples had a variable organic load, which
contribute to a high COD value, but with BOD5 values less than 105mg/l, indicating an advance
state of degradation. Moreover, the changes in leachate biodegrability are mainly reflected by
BOD5/ COD. The BOD5/ COD ratio varying from 0,06 to 0,07. This fact suggest that the
biochemical activity in the landfill body is in its final stage and the organic load is biologically
stabilized.
The NH4 concentration reaches the values between 367,1 to 370,6mg/l. Conversely, the
concentration of nitrates was found to be rather low due to the stabilization process [5]. The
relatively high concentrations of chloride remain constant with time, contrary to similar studies
that show increasing chloride concentration with leachate age. This was explained by the fact
that chlorides are not influenced by biochemical actions and accumulate inside the disposal site
[4]. Finally, due to the alkaline pH a reduction of solubility can be observed. This results in low
concentrations of heavy metals, which can be further explained by the formation of non-
dissolvable sulphides from the reduction reactions.

3.2 Groundwater
The uncontrolled disposal site of Schisto is currently under restoration and is located above burst
and karst limestone. Initially, no bottom lining was incorporated, which is necessary in order to
protect from leachate pollution.
In the following tables, the average value of various characteristics is presented per sampling
place. The pH of groundwater is neutral (7,05-7,67). The presence of nitrogen compounds
suggests pollution of organic origin.
 Sardinia 2007, Eleventh International Waste Management and Landfill Symposium

Table 1. Monitoring leachate quality

MEAN VALUE
PARAMETER UNIT
Sample Α Sample B
Temperature °C 19,4 21
pH 8,80 8,84
O.R.P. V 0,04 0,03
Conductivity (250C) µS/cm 10.860 10.434
Turbidity NTU n.d. n.d.
Total Solid mg/l 6.114 5.772
Dissolve Solids mg/l 6.039 5.709
Suspended Solids mg/l 75 63
D.Ο. mg /l 0,75 0,73
BOD5 mg /l 95,73 105,07
COD mg /l 1.603 1.612
TOC mg C/l 297,1 295,8
Kjeldahl-N mg /l 14,73 14,73
ΝΗ4+ mg /l 370,6 367,1
ΝΟ2- mg /l <0,03 <0,03
T.P. mg /l <0,4 <0,4
T.P. mg /l 16,83 17,94
PO43- mg /l 41,44 44,23
Cl- mg /l 2.239 2.421
SO42- mg /l 54,33 54,13
F- mg /l 0,08 0,11
Phenol mg /l 0,28 0,35
CN- mg /l <0,002 <0,002
As µg /l <0,5 <0,5
Cd µg /l 6,04 5,81
Cu mg /l 129,73 141,17
Cr µg /l 557,33 521,87
Pb µg /l 216,9 255,2
Hg µg /l 1,27 1,18
Ni µg /l 144 166,2
Zn mg/l 0,22 0,17
Co µg /l 25,31 27,21
* Not detected

Also, samples from wells have ammonium concentration higher than 0,5 mg/l, which is the
maximum permissible value of potable water in EU.
The BOD5 constitutes an important parameter that can be used to make statements about the
organic load in water, whereas COD determines almost all organic compounds present. BOD5
expresses the quantity of oxygen consumed by bacteria during the first 5 days for the
decomposition of organic pollutants. The concentration of BOD5 for the water samples does not
 Sardinia 2007, Eleventh International Waste Management and Landfill Symposium

exceed 40 mg/l, that is the maximum value for irrigation water according to the Ministry of
Agriculture. COD ranges from 30,8-254,5 mg/l, and W3 having the highest COD value. An oily
supernatant phase was recognized in the W3 samples, the presence of which was not resulted
from the operation of the uncontrolled site (possibly an accidental spill).
Chloride concentration ranges from 36-684,67 mg/l. These relatively high concentrations can
possibly be attributed not only to leachate effects, since the possibility of sea penetration to
groundwater cannot be excluded.

Table 2. Monitoring groundwater quality

UNIT MEAN VALUE
PARAMETER
W1 W2 W3
Temperature °C 18,31 20,7 19,03
pH 7,05 7,27 7,67
O.R.P. V 0,35 -0,043 0,09
Conductivity (250C) µS/cm 3.327 659,2 2.159
Turbidity NTU 17,04 12,98 21,35
Total Solid mg/l 2.531 422 1.531
Dissolve Solids mg/l 2.446 412 1.481
Suspended Solids mg/l 85 10 50
D.Ο. mg /l 1,64 2,46 0,99
BOD5 mg /l 18,51 1,89 9,99
COD mg /l 103,01 30,8 254,5
TOC mg C/l 20,33 3,6 n.d.*
Kjeldahl-N mg /l 0,56 0,1 0,51
ΝΗ4+ mg /l 2,28 0,6 6,31
ΝΟ2- mg /l 2,20 0,12 3,21
ΝΟ3- mg /l 252,27 4,55 12,65
Τ-Ρ mg /l 0,02 0,035 0,03
PO43- mg /l 0,07 0,068 0,06
Cl- mg /l 684 36 340
SO42- mg /l 405 47,2 415,2
F- mg /l <0,025 <0,025 0,05
CN- mg /l <0,002 <0,002 <0,002
As µg /l <0,5 <0,5 <0,5
Cd µg /l 0,43 16 0,52
Cu mg /l 3,34 1,5 1,26
Cr µg /l 13,19 1,54 <0,6
Pb µg /l <0,5 0,54 1,13
Hg µg /l <0,04 <0,04 0,80
Ni µg /l <0,6 1,15 <0,6
Zn mg /l 25,85 0,17 0,07
Co µg /l 0,72 <0,4 <0,4
* Not detected
 Sardinia 2007, Eleventh International Waste Management and Landfill Symposium

3.3 Surface water

Samples from surface water (rain) were taken from four different points collected in suitable
bottles. The surface water pH is slight alkaline (7,86-7,99), whereas the conductivity is
particularly low (725-301 mS / cm). The BOD5 value in the samples ranges from 8,1-65,5 mg O2
per litre.
Also, the content in ammonia and nitric ions ranges between 0,07-1,4 mg / l and 1,2-1,8 mg /
l respectively. The overall concentrations imply that no mixing of rain water with leachate takes
place.

3.4 Biotests
Because of the unknown toxicity of the samples under examination, a preliminary test was done,
so as to find the toxicity level (range finding test), consisting of 5 dilutions with four repetitions
per dilution.
After asserting toxicity levels for the samples, subsequent final testing (definitive test)
followed, from which the EC50 indicator was derived. Statistical processing of results proceeded
with the help of PC statistical program SPSS (probit analysis).
As expected, leachate sample is the most toxic. Leachate toxicity is a function of mainly
ammonia, alkalinity and COD content [8]. In particular, ammonia directly affects Daphnia
species, while alkalinity rises ammonia toxicity [6].
Another author relates toxicity to chloride, ammonia and hardness content [1]. In similar
studies, the important role of zinc and organic compounds to the toxicity of Daphnia species is
documented.
As far as ground water is concerned, the greatest toxicity is posed by W3, while no toxicity
was observed for the W1 and W2 samples, 24h test. Toxicity however was present for the 48 h
tests. Finally, no toxicity was observed in any of the rain water samples, therefore these are
characterized as non toxic.

3.5 Biogas
Production of gas (biogas) is one main phenomenon that takes place in Landfill Sites due to
aerobic or anaerobic processes. During aerobic digestion of organic compounds CO2, water and
energy is produced.
This is promoted mainly by air intrusion to the waste top layer and air already present.
Fermentation in anaerobic conditions takes place in four stages: initially the undissolved
compounds are hydrolysed.
In the second stage organic matter is degraded to intermediate products such as organic acids,
alcohols, CO2, H2 or H2O. In the third stage alcohols and fatty acids are further degraded to
acetic acid, H2 and CO2 and finally CH4, CO2, H2S, H2 is produced.

Table 3. EC50 & NOEC Toxicity Testing 24h & 48h

Test 24h Test 48h
Sample EC50 (ml/l) NOEC (ml/l) EC50 (ml/l) NOEC (ml/l)
leachate 156 60 151 60
W1 - 125 454 <125
W2 - 125 656 <125
W3 264 <125 <125 <125
 Sardinia 2007, Eleventh International Waste Management and Landfill Symposium

60

50

40

30

20

10

0
A B C1 C2 D

CH4 55,0 40,2 32,0 41,8 26,9

CO2 40,1 32,4 34,5 36,8 20,8
O2 1,7 10,8 2,7 4,8 13,5
N2 3,2 16,6 30,8 16,6 38,8

Figure 1. Main components of biogas composition (mean values)

70,0

60,0

50,0

40,0

30,0

20,0

10,0

0,0
A B C1 C2 D

H2S 6,4 4,3 19,7 2,3 0,3

CO 15,7 2,4 4,0 1,1 6,4
H2 65,6 0,3 8,7 11,6 50,1
HCN 51,4 8,1 63,9 4,4 1,3

Figure 2. Secondary components of biogas composition (mean values)

4. CONCLUSIONS

Leachate originating from the restored, uncontrolled disposal site at Schisto contain a high
amount of organic load, mainly not biodegradable. At the same time, the inorganic load
(consisting to a large degree of chloride and ammonium) was also measured to be high.
The accumulative and additive effect of the pollutants was evaluated with the use of biotests.
Leachate presents a high toxicity, as expected. Biogas consists of methane and carbon dioxide in
high concentrations and nitrogen, oxygen, hydrogen sulfide, CO, hydrogen, cyanides to a lesser
extent.
Other gases were not detected. Biogas with fraction of methane higher than 40% could be
pumped from about 60% of the wells. Finally, no biogas escapes could be detected in the
surroundings of the site.
 Sardinia 2007, Eleventh International Waste Management and Landfill Symposium

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