Download Report of investigation of potential soil contamination in former

Report of investigation of potential soil contamination
in former Zherebkovo military base in Ukraine
Introduction.
As a part of a joint OSCE lead pilot project, Facilitating the Conversion Process of
former Military Bases in Ukraine – The example of Zherebkovo, a test run of an
environmental audit was called for.
Prior to the conversion of former military bases in Ukraine to civilian purposes all
contaminated soils must be identified. This requires that records of former use and
incidents of environmental concern be released. Furthermore, potential contaminated
sites must be screened by an environmental audit in order to disclose the significance
of the contaminated sites. Such contaminated sites need then to be investigated in
more detail in order to determine whether remediation is warranted. It was unclear
whether or not the Ministry of Defence (MoD) will allow for the necessary
transparency. Furthermore, it was uncertain if the State Ecological Inspection, under
the Ministry of Environment and Natural Resources (MD), possessed the scientific
skills and technical equipment required for sampling, handling and analysis of the soil
and water samples needed for a sound environmental audit of the bases. There
appeared to be no harmonized methodology for an environmental audit and there was
no clear delineation of the responsibilities between the various entities dealing with
the issue.
The main purpose of this study was therefore to run through the task of an
environmental investigation in order to identify logistical and practical problems, as
well as shortcomings in the field of science and/or instrumentation. A thorough
environmental investigation was not within the scope of this audit as this was not
feasible neither within the time frame, nor financial funding, available.
Zherebkovo was selected as case study due to this being a typical base. The base is
already transferred from MoD to the Ministry of Emergency. The base was a former
military unit of the Russian 43 military army since 1954. According the base
commander this military base was only used for the storage of empty Intercontinental
ballistic missiles (ICBM) together with their radio-control units until year 1998, i.e.
no warheads or rocket fuel were stored at the base.
Based on this prior usage of the base no major soil contaminations were anticipated.
In the case of Zherebkovo the main environmental concern was therefore limited
contamination by light hydrocarbons (HC) from gas filling stations for vehicles. The
main focus of the audit was therefore on the ability to identify potential contaminated
sites, collect relevant soil and water samples and determine the light HC
contamination in these samples.
Preliminary environmental audit
The scope of the preliminary audit was to:
1. Identify potential soil contamination at the Zhrebkovo base based on interview
with the base commander
2. Sample and measure the highest level of contamination (hot spot) at these
sites.
The 170ha large base is situated on the top of a hill of deep (>10m) soil deposits. Only
grass- and wasteland is found downslope of the base. The base is drained by a small
stream running by in the bottom of the slope and a first order brook originating within
the base. The soil deposits consist of alternating layers of sand, silt and clay. The clay
layers give rise to several artesian wells in the region. The topsoil is an approx. 1.2m
deep Chzernozems soil which is developed above an approx. 50cm thick clay layer
(Picture 1). The clay layer is believed to be an impermeable barrier for the soil
contaminants restricting these to the surface 1.2m layer. Local wells are deeper than
1.2m in order to ensure constant supply of water.
Picture 1
Soil profile visible in a nearby sand-pit.
Two potential sites of soil contamination were pointed out by the base commander
(site A and B). These were former gas filling stations for trucks and lorries. An up to
20cm deep snow cover during the site inspection made the determination of optimum
soil sample spot difficult. The petrol filling stations were paved with concrete. Soil
samples from 0-40 (Ah-horizon) and from 50-70 cm (Ahk-horizon) were collected
just outside the lower end of the pavement from site A (Picture 2). From site B a
sample from 0-40 cm was collected in the bottom of a ditch draining the filling station
(Picture 3). The sample had a distinct smell of petroleum. Deep soil samples above
the clay layer (1.0-1.2m) were not collected due to inadequate sampling equipment.
For reference, soil samples were also collected at a site that was not believed to be
directly contaminated (Picture 4 and 5).
A furnace for central heating of the base buildings was also inspected. The energy
source is a heavy fuel oil (local name: Mazod) with a high viscosity. The tanks and
pipelines were more than 50 years old and need for major maintenance and upgrading
was evident. Faulting equipment had led to several minor oil spills (Picture 6), though
the contamination is likely only superficial as the high viscosity of the crude oil
prevents significant percolation into the ground.
Picture 2
Soil sampling site A, a former petrol
filling station for trucks and lorries.
The sampling location was at the
lower edge of a concrete paving
covering the filling area.
Picture 4
Soil sampling site C, a “background”
site within a deciduous forest where no
known activities have been conducted.
Picture 3
Soil sampling site B, a former petrol
filling station for trucks and lorries.
The sampling location was in a ditch
draining the area.
Picture 5
Soil pit at sampling site C. In the top 40
cm a very dark grayish brown Ah horizon
lying over a dark brown Ahk horizon
with crotovcinas. Soil samples were
collected from the Ah and Ahk horizons
at 0-40 and 50-70cm depth.
Picture 6
The boiler house. Oil spills due to
faulting equipment was evident by
several large dams of oil on the soil
surface.
Picture 7
Surface water sampling site. Sample
1 was collected in the headwater
brook draining directly from the base.
Sample 2 was collected downstream
of the stream passing by the base, just
before converging with the brook
draining the base.
The sewage treatment plant handling the wastewater from the base did not appear to
be adequately maintained technically. The sewage seemed to be flowing through
some primary sedimentation tanks prior to be discharged untreated into the brook
draining the base.
Groundwater above the clay layer at 1.2m downslope from the contaminated site were
not sampled due to lack of existing wells, nor sufficient time for excavation/drilling.
Instead water samples from up- and downstream of the passing stream (sample 1 and
2) as well as the first-order brook draining the base (sample 3) were collected (Picture
4). The latter brook (3) was also the recipient of the waste-water treatment plant.
Incorporated in this study is also the inspection and evaluation of chemical laboratory
personnel and facilities that will be given the task of sampling and analysing of water
and soil parameters identifying soil contamination within an environmental audit. An
expert from the laboratory in Kiev belonging to the State Ecological Inspection
participated in the sampling of soil and water.
Experience from Zherebkovo
The base commander and his deputy were very forthcoming expressing true glasnost
and a sincere desire to give us the information that we required. However, the
commander’s ability to inform us of any incidents of environmental concern was
limited to the period of which he had been stationed at the base. It is therefore
necessary to gain access to previous records of the activities at the base from the
MoD. Furthermore, the base commander appeared to lack the basic understanding
needed to recognize potential contaminated sites. For example, only after a direct
questions regarding petrol filling stations we were informed of the prior existence of
two such stations. The commander failed also in informing us of extensive spillage of
fuel oil at the boiler house and the fouling sewage treatment plant.
The head of department at the chemical laboratory in Kiev was dedicated and
demonstrated meticulous routines during the sampling process. On the downside it
should be commented that ordinary plastic shopping bags, which were provided as
containers for soil samples, are not recommended as light HC will escape and there is
a possibility of phthalate contamination from the bags. Suitable containers for soils
samples that are to be determined for HC content would be glass jars. Furthermore,
far more suitable soil drills are commercially available for soil sampling (e.g. an
Edelman drill) than what was provided by the laboratory. During the interview of the
base commander and the following identification of hot spots for sampling, the
representative from the laboratory did not take any initiative though merely agreed
with our suggestions. Their understanding of the approach and ability to conduct such
a task is therefore still somewhat unclear.
Laboratory survey
Visit to the State Analytical Laboratory
The State Ecological Inspection under the MD is in charge of two major chemical
laboratories, one in Kiev and Eco-Centre 43 in Kharkiv.
We visited the State Chemical Analytical Laboratory in Kiev. Dr. V. Kovba, head of
department of control and methodology, informed us that their main role is to function
as a coordinator of 54 local laboratories. Major tasks are within training, inspection,
standardization and accreditation together with the State committee of standard. The
laboratory consists of three units; 1) Water, 2) Air and 3) Soil and waste.
The laboratory has participated in several international projects; e.g. with US-aid
between 1995-1998, and an EU TACIS project in 1998. The laboratory is accredited
and inspected by state authorities. They apply certified standard water samples from
an institute in Odessa and appear to follow good quality assurance (QA) concept and
routines. The laboratory participated in several international inter-calibrations on
heavy metals and NOx in 1999 with Institute for Inland Water Management and
Waste Water Treatment (RIZA) in the Netherlands with acceptable results.
The Eco-centre 43 in Kharkiv belonging to the State Ecological Inspection is
according to Dr. Kovba a larger and better facilitated chemical laboratory. This
laboratory has a staff of 19.
Hydrocarbon determination
The main concern of soil contamination at the former Zherebkovo base is of light
hydrocarbons (HC) from petrol filling stations. Contaminated soils with HC are
typical for a large number of the former military bases in Ukraine.
In addition to document general HC contamination level the chemical analysis need to
identify the relative composition of key HC compounds in order to verify the source
of contamination. The applied practice at the laboratory in Kiev of extracting the HC
from soil and water using Tri-chloromethane and Hexane and detecting the Non-polar
HC as naphthalene using fluorimetric detection is only useful to document the
presence of HC contamination. Component identification is not adequate due to
difficulties in separating out small HC amounts from the Hexane signal and lack of
sufficient up-concentration. In order to detect and identify the composition of such
contamination in the sampled soils the HC must be separated from the soil matrix by
heat extraction and up concentrated in commercially available “Cold-trap”. HC in
water samples should be separated from the sample matrix by solid phase extraction
using a hydrophobic resin. The various components of the isolated HC sample must
be separated using gas chromatograph (GC) coupled to a Mass spectrometer (MS)
detector (i.e. a GC-MS) for adequate qualitative and quantitative detection.
The laboratory in Kiev had recently acquired a new Hewlett-Packard GC-MS, though
this instrument lacked cold-trap and was still not operational. We were informed that
one of the two GC-MS instruments in the Eco-Centre 43 in Kharkiv had the necessary
equipment (i.e. possibilities for heat extraction and cold-trap injection port). Soil and
water samples where therefore sent to this laboratory for HC
Inorganic analysis
Determinations of major anions were conducted colorimetrically using autoanalyzer
while major cations are determined on a Flame Atomic adsorption spectrophotometer.
(Flame AAS). These are acceptable though somewhat outdated methodologies.
Commonly in up-dated laboratories major anions are determined using Ion
chromatograph (IC) and major cations are determined using Inductive Coupled
Plasma (ICP) AAS or IC.
Soil analysis
Soil pH was measured in a 1M KCl electrolyte extract of the soil. Soil organic matter
was determined by chemical oxidation with dichromate. Content of heavy metals in
soil was determined by first extracting the metals from the soil using both nitric acid
and ammonium acetate and measuring the content of lead (Pb), zink (Zn) and copper
(Cu) in both extract solutions by means of graphite furnace AES. Non-polar HCs
were extracted using tri-chloromethane and hexane and measured fluorimetrically.
Light HC determination
The State Ecological Inspection was requested to conduct a GC-MS determination of
light HC (60-300Da), e.g. BTX analysis (i.e. Light HC determination of Butol,
Etylbenzen, Toluen, Naftalen, Xylol) on the soil and water samples. Sample
preparation was to be performed by means of thermic warming and cold trap
upconcentration prior to injection into GC-MS. A BTX analysis (i.e. benzene, toluene,
xylene) is a standard analytical package for aromatic HC used for environmental
Hazard Identification and Precursor Studies. The BTX compounds are added to the
into petrol to produce high octane fuel.
The determination of key light HC components in water and soil samples was
conducted at Eco-Centre 43 be means of cold-trap extraction and up-concentration
(PURGE & Trap; Hewlett-Packard (HP), USA) followed by chromatographic
separation (HP-6890) using a 25m capillary column (HP-624) and massspectrophotometric detection (HP-5972).
Experience from visiting the State Laboratory in Kiev
The laboratory appeared to be well run with tidy and clean facilities and somewhat
competent staff. The instrumentation ranged from outdated Russian analogue meters
to western state of the art instruments (e.g. Hewlett-Packard GC-MS).
Interpretation of chemical analysis of soil and water samples
Results from water analysis
Result on inorganic and organic components in water samples reported by the
laboratories belonging to the State Ecological Inspection under the MD are given in
Appendix A. Information on detection limit and precision is lacking.
In order to give the laboratories our corroboration we needed to check their ability to
conduct chemical analysis producing reasonably sound data.
A method of assessing the quality of a laboratory is to determine all major anions and
cations, i.e. ions contributing significantly to the charge balance. If the accuracy is
good, the discrepancy from charge balance should be less then 10%. Two of the four
samples had discrepancies less than 10%. The other samples had discrepancies of -20
and +34% in the Upstream sample and in the Tapwater sample, respectively. Another
way of assessing the quality of the data is to compare calculated theoretical
conductivity with measured conductivity. This study revealed a 40% and 20%
deviation in the Upstream sample and in the Tapwater sample, respectively. Based on
this it is clear that the data for the Upstream and Tapwater samples are not
satisfactory. Reservations in the laboratory report regarding possible error in the
alkalinity determinations do not bear any significance relevance relative to the large
discrepancy found in the ion balance. It is also unlikely to be any non-determined ions
that are contributing to the ion balance, except for phosphate in the Wastewater
recipient.
ueq/L
Inorganic w ater chemistry
18000
18000
16000
16000
NH4+ -N
14000
14000
K+
12000
12000
10000
10000
8000
8000
6000
6000
4000
4000
2000
2000
Na+
Mg2+
Ca2+
A lkalinity
ClNO3--N
SO42--S
0
0
Wastew ater Dow nstream Upstream
Tapw ater
Sam pling s ite s
Figure 1
Stacked bars of anions (narrow bars) and cations (wide bars) contributing significantly
to the charge balance.
The recipient of the wastewater appears to be able to cope with the influx of organic
matter as the chemical oxygen demand approx 100m. downstream had reached below
the state limit value (27mg O dm-3) and there was no apparent saprofication in the
streambed. On the other hand, all nutrients are not assimilated causing ammonia
concentrations in the recipient to exceed the national limit by more than threefold.
The ammonia limit was also exceeded in the two samples of the stream passing by the
base, likely due to similar sources in the adjacent village. For further examination of
the issue phosphate data are needed. No elevated levels of heavy metals (Cu, Cd, Pb,
Zn) were detected neither in the recipient of the wastewater, nor in the Tapwater.
The chemical data of the water samples show that the water has a high ionic strength
with calcium, magnesium, sulphate and chloride as the dominating ions.
Results from the soil analysis
The results on inorganic and organic analysis of soil samples reported by the
laboratories belonging to the State Ecological Inspection under the MD are given in
Appendix B. Information on detection limit and precision is lacking.
Sample 1 and 1amare from the Ah and Ahk horizons in site A. Sample 2 is from site
B. Sample 3 and 3a are from the Ah and Ahk horizons of site C.
The soil pH was circum neutral which was as expected for this type of soil. More
surpricing was the rather low organic content. Typically the organic matter in these
soil types decreases from 12% in the Ah horizon to 5% in the Ahk horizon. The
measured values in the background samples were 3,6 and 3,2 in the Ah and Ahk
horizons, respectively.
The content of non-polar HC was between 130 and 98 mg kg-1 in the background
samples. This is likely due to the content of natural organic matter (i.e. 3,2 – 3,6%) of
which non-polar compounds may comprise a substantial fraction. Relative to these
presumed natural levels the soil samples from the petrol stations (site A and B) are
clearly contaminated by HC. A decrease in HC from 417mg L-1 in the top soil layer to
close to background levels (159mg L-1) at 50-70cm depth at site A indicates that the
contamination does not reach this depth to a great extent. The sample collected in the
ditch draining the other petrol station was heavily contaminated with non-polar HC
levels, 26 times above the background level. This warrants a more thorough
inspection in order to determine the extent of this contamination. The examination of
the heavy metal content of the soils show somewhat elevated levels of lead and sink in
the same samples that are contaminated with non-polar HC. The high lead content is
presumably caused by the lead added to the petrol. The content of heavy metals is
within the range that is commonly found in regionally polluted regions as e.g.
southern Poland (see Andersen et al., 1994). Nevertheless, the levels are way above
the national limits and soil remediation should therefore be conducted before this land
can be used for agricultural purposes.
Results of light HC determination
The results on organic analysis of water- and soil samples reported by the Eco-Centre
43 belonging to the State Ecological Inspection under the MD are given in Appendix
C. Information on detection limit and precision is lacking.
The crude COD determination on the water samples (see above) showed that only the
water sample from the recipient of the wastewater effluent (sample 1) had elevated
levels of reduced matter, which in this case likely is large molecular size organic
residuals. Furthermore, no elevated levels of lead were found. This indicates that the
water samples were not contaminated by petroleum. This finding was confirmed by
the GC-MS determination as none of the examined organic compounds were found to
exist at levels above the state limit. Only the water sample (3) collected upstream of
the passing brook (i.e. contaminated from sources other than the former base) gave the
noticeable signals for 4 of the 5 key compounds, followed by the sample (1) from the
wastewater recipient (3 of 5) and tap water sample (4) (only Toluen).
The determination of Non-polar HC using the crude organic extraction and
fluorimetric detection method soil (see above) gave 3.2 and 26.4 times higher levels in
the Ah horizon in plot A and in the sample from plot B, respectively, relative to an
assumed background sample from the base. High petrol contamination in these
samples was also confirmed by high lead concentrations as well as a distinct
petroleum odour in the sample from plot B. It was therefore expected that the GC-MS
data would show similar elevated levels of the BTX compounds and especially
Naftalen in these two samples. On the contrary the results show no contamination. A
comparison of the contaminated soils with the background soil show that the values in
the Ah sample from plot A are 1 – 2.7 times higher, while the levels in the apparent
contaminated soil in plot B are only 1.2 – 1.7 times higher. This is clearly incorrect. A
possible cause for these erroneous data may be mix up of samples. This could explain
how the Visual examination (see chapt. 2.2. in Appendix C) of the samples can
conclude that none of the samples hade any smell
Conclusions
•
•
•
•
•
Access to historical records of base activities are necessary in order to identify
possible contaminated sites
The Zherebkovo base does not appear to have heavily contaminated soils,
though the extent of soil contamination of HC at site B must be further
investigated.
The recipient of the waste water appears to be able to assimilate the sewage
loading from the base.
The technical facilities of the boiler house need major maintenance.
The chemical laboratory of the Ministry of the Environment in Kiev and
Kharkiv need to improve their accuracy on the determination of major anions
and cations in water samples.
APPENDIX A
The results of analysis of water samples which were taken within a
military basis at Gerebkovo, Odesas oblast,
12 March, 2003
Sample №1 – waste water after treatment plant;
Sample №2 – water from a spring before mixing with waste water
Sample №3 – low pound at a border of mil. base
Sample №4 – drink water from a tape in militiry neadquarters room
№
з/п
Parametrs
Unit
№1
Sample
№2
№3
№4
Limit
conc.
(ГДК за
СанПиН
№ 4630-88)
1
2
3
4
5
6
7
8
9
10
11
12
Conductivity
рН
SO4
Cl
NO3
COD
NH4
Ca
Mg
Na
К
Alkalinity*
13
14
Cu
К
15
16
17
Pd
Zn
Aqute
toxisity, 48 h
µS/см
Unit рН
mg/dm3
mg/dm3
mg/dm3
mgO/dm3
mg/dm3
mg/dm3
mg/dm3
mg/dm3
mg/dm3
1383
8,10
80
119,2
<0,5
27
7,24
72
72,1
1,5
2,19
6,37*
1230
8,04
88
116,8
<0,5
3,83
88
53,5
0,33
1,92
6,1*
1396
8,41
175
153,6
1,25
3,42
44
93,6
1,06
4,03
6,9*
718
7,87
48
30,9
<0,5
0,93
72
53,6
<0,2
2,15
4,4*
mg/dm3
mg/dm3
<0,005
<0,0005
-
-
mg/dm3
mg/dm3
-
<0,015
0,022
absent
absent
absent
<0,005
<0,000
5
<0,015
0,018
absent
mgequivalent
/
dm3
6,5-8,5
500
350
45
30
2,0
200
-
1,0
0,001
0,03
1,0
absent
In some samples were found exceeded concentrations of NH4+ ions
sample №1 – in 3,6 one;
sample №2 – in 1,9 one;
sample №3 – in 1,7 one.
*Maybe the results are not correct because the time when the samples have
been taken and brought in a laboratory was also exeeded.
Head of Departmet
V. Kovba
APPENDIX B
Examination of soil samples of military base
Table 1 Results of analyses
Parameter
PH, unit pH
(KCl, 1M, pH=7,0)
Organic contents, C, %
(K2Cr2O7-titrationmethod)
Pb, mg/kg
(HNO3, 50% v/v)
Pb, mg/kg
("NH4 -HAc" - bufer,
pH=4,8)
Zn, mg/kg
(HNO3, 50% v/v)
Zn, mg/kg
("NH4 -HAc" - bufer,
pH=4,8)
Cu, mg/kg
(HNO3, 50% v/v)
Cu, mg/kg
("NH4 -HAc" - bufer,
pH=4,8)
Non-polar
hydrocarbons,
mg/kg
(solvent: CHCL3
→C6H6; fluorimetric
method
NO3 , mg/kg
(alum, 1% w/w)
Sample- Sample- Sample-2 Sample-3 Sample-3a
1
1a
7,6
7,1
7,7
6,4
6,4
Limit
-
4,08
2,66
7,40
3,63
3,22
-
55,7
24,4
130,9
16,8
15,4
32
12,1
5,7
37,8
2,3
3,2
6
124,6
65,1
239,5
53,4
75,3
100
25,7
3,5
75,4
< 0,5
< 0,5
23
15,2
15,7
23,8
15,5
15,6
55
< 0,5
< 0,5
0,65
< 0,5
< 0,5
3
416,8
159,2
3431,7
130,0
98,2
45,2
19,1
32,6
53,2
58,5
to
compare
with
samples
3, 3a
like a
backgrou
nd
130
Results were compared with limit or background.
Conclusion: The petrol-stations for transport are source of contamination of military
base soil with non-polar hydrocarbons, Pb, Zn.
APPENDIX C
JSC "KHARKIV RESEARCH CENTER OF MILITARY
ECOLOGY"
The Results of analyses of Samples From Gerebkovo
1. Introduction
19.03.03 to KRC laboratory were dilivered 4 water samples to determinate next
chemicals: Butol, Etilbenzen, Toluen, Naftalen, Xylol and 5 samples of soil to
determinate total concentration of Butol, Etilbenzen, Toluen, Naftalen, Xylol .
The samples have been collected at Gerebkovo object.
2. Experemental part.
2.1 Visual examination of water samples.
Delivered samples are transparent liquids.
2.2 Visual examination of soil samples.
Delivered samples are common soil without of any smells.
2.3. Determination of the Light HC.
The determination of light HC have been done by the chromato-massspectrofotometric metod. For determinations were used HP-6890 gass
chromatograf
including
HP-5972
mass
selective
detector
and
concentration prefix PURGE & Trap (Hewlet Packard, USA). Separation
the components of a mix was done in capillar column HP-624 (lenht of a
column –25 m, diametr – 0.2 mm with
1.12mkm).
thickness
of active film
2.4. The results of water samples analyses is represented in table 1.
Table 1. Total concentration of light HC in water samples
Butol
# of
sample
mg/kg
Sample 1

Sample 2
Part of
limit
Concetration
Etylbenzen
Part
Part of
mg/kg
of
limit
limit
Toluen
mg/kg
0,00009 0,00018


0,0003

0,0002
5
0,0005 0,00014 0,00028 0,00158
Sample 4

0,00008 0,00016
0,5
0,5
mg/kg
Naftalen
Part
of
limit
0,00015 0,003

Sample 3
Limit
conc.
(Ukraine)
0,03
Xylol
0,16



0,00244 0,049

0,01
mg/kg


0,05
0,01
2.5. The results of soil samples analyses is represented in table
2.
Table 1. Total concentration of light HC in soil samples
# of
sample
Sample 1
Sample 1а
Sample 2
Sample 3
Sample 3а
Limit
conc.
(Ukraine)
Concentration
Butol
Toluen
Etylbenzen
Xylol
Part of
Part of
Part of
mg/kg
mg/kg
mg/kg
mg/kg
limit
limit
limit
0,07
0,23
0,08
0,27
0,06
0,12
0,40
0,10
0,33
0,01
0,03
0,06
0,23
0,77
0,06
0,20
0,05
0,17
0,07
0,10
0,33
0,05
0,17
0,03
0,10
0,06
0,06
0,20
0,14
0,47
0,06
0,20
0,02
0,28
0,93
0,3
0,3
0,3
Naftalen
mg/kg





0,3
Concetrations of Butol, Toluen, Etylbenzen, Naftalen and Xylol in all water
and soil samples were not upper then the limit level.
Chef director of KRC of ME
Michalskaya
L.