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Traces Of Oil Products And Naturally Occurring Hydrocarbons In

The Lake Koumoundourou Of Aspropirgos, Attiki, Greece.


T. Mimides, M. Psychoyou, A. Sgoumpopoulou, S. Rizos
Agricultural University of Athens (AUA). Section of Water Management Resources.
Athens, Greece.

ABSTRACT
At the present work an investigation is made about the existence of petroleum and natural
hydrocarbons in water samples of Lake Koumoundourou.
The samples were collected from different points of the lake, inside the two barriers that were
constructed by ELDA, as well as from the outlet of the lake to the sea.
The analyses were made using gas chromatography. From the results of the analyses and the
estimate of CPI (Carbon Preference Index) in all the samples from first and second barrier,
kerozenes and diesel distillates (C10 – C24, CPI~1) were detected while in water samples from the
lake and the outlet only natural alkanes, chains with odd number of carbon atoms, (CPI>1) were
identified except from a few cases where kerozenes and a small proportion of gasoline distillates
are detected.

Keywords: petroleum and natural hydrocarbons, gas chromatography, FID, CPI (Carbon
Preference Index), unweathered and evaporated gasoline, unweathered and evaporated diesel

Introduction
Lake Koumoundourou is encountered in the southeast exit of the Thriasian plain towards the sea. It
is located in the southwest tailings of the Aigaleo Mountain. Its boundaries are between
Kapsalwnas hill (273m elevation) and Gkika hill (77m elevation. Between the west side of the
Eleusina Gulf and the lake lays a terrestrial zone about 50 m. This zone is at a distance of 15 km
from Athens at a latitude of 38 O 02΄ B and at a longitude of 23O 37΄ A. The surface of the lake is
about 143.000 m2, the total length of its coast is 1300 m, while the maximum length and width is
600 and 400 m similarly. Managerially it comes under the municipality of Aspropirgos (see Figure
1).
Lake Koumoundourou is in the vicinity of the national road, the camp AVEK 871 that supplies with
fuel and oils the majority of the Greek army, the ELDA, as well as with an important amount of fuel
tanks belonging to private companies. This wetland has been disordered and is close to extinction
unless efforts for its protection take place, such as protection from the intense industrial
development in the area, as well as limitation in the licks of the underground fuel reservoirs. Works
of infrastructure shall also be done in order to collect the rainwater that rinses out the national road
ending in the lake, as well as to collect the contaminants from the use of detergents, dissolves and
oil at the AVEK camp.
In order to identify the oil hydrocarbons that are encountered in the lake, analyses were done both
in water samples in several points of it and mainly in samples taken from the two barriers that have
been constructed by ELDA in front of the karstic spring that supplies the lake. These two barriers
were constructed in order to sustain the oil products that either sprout or exist in the outlet of the
lake to the sea.

Identification of oil hydrocarbons and carbon tar


The Environmental Protection Agency of the U.S.A (40CFR Part 136, Federal Register, October
26, 1984) has developed a series of original methods for the analysis of organic chemical
substances dissolvable in water. These methods are known as 600 series and include 15 analytical
techniques numbered 601 – 613, 624 and 625 (see Table 1).
Analysis of hydrocarbons in soil samples may be also done using the TPH (total hydrocarbon
petroleum), (Zemo, Bruya and Graf, 1995). This is a chromatographic analysis that separates
organic mixtures and depends on boiling points. The assumption is based on the fact that all the
picks that fall in the reach of a boiling point come from oil hydrocarbons. Their masses combine
and the sum is determined from the special mixtures. Typically, all the picks, which exist in the
scale with carbon atoms from C4 – C10, are assumed to come from gasoline, while all from C10 –
C24 come from fuel oil. However, this method presents several problems.
Figure 1. Geological Map of Koumoundourou lake
LEGEND

Quarteriat
Sand, gravel and good quality loams

Talus slope screes and recent alluvial


fans

Sand and loams (marsh formations)

Gravel,loam and sand (poorly sorted)

Pelagic Zone

Limestones, dolomatic limestones and


dolomites (Mid Triassic – Lower
jurassic)

Limestones and dolomites like the


previous ones but with fractures

Geological formation contact surface

Fault

Possible fault

Springs of Lake Koumoundourou

Coastal springs

Borehole of Research Project (AUA)

Geological section

Water Divide

Figure 1. (Continued)
Table 1. The analytical methods for organic combinations of series 600 of EPA.
Number of method Analytical Technique Combination targets
601 GC Clear halogen hydrocarbons
602 GC Clear scented hydrocarbons
603 GC Acrolines and Acronitriles
604 FIDGC Phenols
605 HPLC Benzidines
606 GC Phthalic ether
607 GC Nitrosamines
Organo-chlorianated
608 GC
Pesticides and PCB
Nitro-aromatic compounds
609 GC
and Isophines
Polycyclic scented
610 GC and HPLC
hydrocarbons
611 GC Halogen ether
612 GC Chloride hydrocarbons
613 GC/MS 2,3,7,8 – TCDD (dioxin)
624 GC/MS Clear organic combinations
625 GC/MS
Key: GC = gas chromatography
FIDGC = gas chromatography with ionization flame detector
HPLC = liquid chromatography of high performance
GC/MS = gas chromatography/mass spectrography

A more accurate identification of hydrocarbons can be done by using the gas chromatograph with a
flame ionisation detector (GC/FID) (Zemo, Bruya and Graf, 1995) can do a more accurate
identification of hydrocarbons in the soil and NAPLs. This analysis creates traces that give picks
that come out from the chromatographic column as time functions. The first ingredients that come
out are these with low boiling point. The traces of GC/FID are like a stamp that can be used for the
identification of special oil distillates and prove whether these distillates are fresh or biodegradable.
Figure 2 shows traces of GC/FID for non-biodegradable gasoline. It seems that there is an
important variety between the different types of benzene and sold benzene in different periods of
time. Non – biodegradable gasoline has picks that come out generally between C4 and C12. Also,
gasoline has a great concentration of self – scented hydrocarbons such as benzene (C6), toluol
(C7), ethylbenzol (C8), xylene (C8) and trimethylbenzene (C9).
Figure 3 shows traces for non-biodegradable mean distillates. Generally, the area for mean
ingredients from fuel distillates is C10 – C24. Even though mineral distillates have a field from C7 –
C12, mean distillates have indeed an ingredient that is exported in the field of gasoline, containing
VTEX combinations. Mean distillates are mainly normal alkalines and naphthalenes that are much
less soluble than VTEX combinations.
The last distillates are shown in Figure 4. These have more of their picks larger than C24 and while
they tend to contain some very soluble mixtures they can contain multi – core scented mixtures.
In Figure 5 the chromatographs of carbon tar from two constructed factories of gas are given.
When the oil hydrocarbons biodegrade, firstly they lose most of their volatile components. This
vitiation is possibly due to the volatility or the biodegradation. The result is a removal of the GC/FID
traces towards the fractions of distillates with greater molecular weight.
The traces of GC/FID at Figures 2 – 6 come from a sample of product or soil. When such
components dissolve in water, they change dramatically. This is due to the different solvability of
each component (Zemo, Bruya and Graf, 1995).
In Table 2 are written the various solvabilities in water of gasoline ingredients that were separated
at 25 0 C. The solvability in water of a mixture that comes in contact with a hydrocarbon can be
found with the help of Raoult’s law. Most of the petroleum distillates show very poor solvability in
water. Gasoline firstly gives VTEX, several other benzenes (such as trimethylobenzene,
methylbenzene etc.) and napthalenes. Fuel oil gives the same mixtures plus phenanthrene and
anthracene. Carbon tar includes all previous plus some multi – core scented mixtures like
acenapthylene and fluorene. The traces of their soluble phase are similar in a way and it is difficult
to identify and study them as it happens with the maternal material.
Table 2 Water solubility of selected hydrocarbons found in petroleum distillates (Fetter, 1999).
Water Solubility Formula weight
@ 25ºC
Benzene 1780 mg/L 78.11
Toluene 500 mg/L 92.14
p-Xylene 200 mg/L 106.17
o-Xylene 170 mg/L 106.17
m-Xylene 170 mg/L 106.17
Ethylbenzene 150 mg/L 106.17
1,2,3-Trimethylbenzene 63 mg/L 120.19
1,2,4-Trimethylbenzene 57 mg/L 120.19
1,3,5-Trimethylbenzene 50 mg/L 120.19
Napthalene 32 mg/L 128.18
2-Methylnaphalene 25 mg/L 142.20
Acenapthene 3.9 mg/L 154.21
Acenaphtylene 3.9 mg/L 152.20
Fluroene 2.0 mg/L 166.22
Phenathrene 1.3 mg/L 178.24
Fluoranthene 0.26 mg/L 202.26
Pyrene 0.13 mg/L 202.26
Anthracene 0.075 mg/L 178.24

CPI index – naturally occurred Hydrocarbons


The naturally occurred hydrocarbons in fresh or salty water that are constantly supplied from
springs of fresh water include:
• saturated aliphatic hydrocarbons
• unsaturated aliphatic hydrocarbons
• saturated cyclic hydrocarbons
• unsaturated cyclic hydrocarbons
• simple diffused rings of scented hydrocarbons (Saliot 1981)
The most usual of the n – alkanes is dekaeptane (n – C17), while other alkanes occur such as n –
C15, n – C21, n – C23 and n – C29.
The alkanes of terrestrial plants have greater chains than n – alkanes of algae, usually varying
between n – C23 to n – C33, but the dominant ones are n – C29 to n – C31 (Kolattukudy 1970).
The alkanes in plants usually have chains with an even number of carbon atoms of the oily acids.
After the escape of CO2 during the process of alternation, the chains dominating the alkanes of
terrestrial plants have an uneven number of carbon atoms (Robinson 1980). An example of a small
chain of alkanes that comes from higher plants is the hydrocarbon n – eptane (n – C7), which is the
main hydrocarbon found in some kinds of pine (Pinus jeffreyi and Pinus sabiniana).
In living organisms and recent sediments the hydrocarbons C3 – C10 are totally absent (see Figure
7).
Primary plants, bacteria and algae show in general a maximum between n C17 – n C21 where
most of the earthy plants show a maximum at n C29. In living organisms and recent sediments
paraffin with an uneven number of carbon atoms occur more than this with even number. A
qualitative suggestion according to the preference concision in even or uneven number of carbon
atoms is the CPI index (Carbon Preference Index):

1  ΣnC17 − nC 31 ΣnC17 − nC 31 
CPI = +
2  ΣnC16 − nC 30 ΣnC18 − nC 32 

If paraffin with even and uneven number of carbon atoms occur at the same way then CPI is
almost 1. If the uneven dominate then CPI is >1, while for living organisms and recent sediments
CPI is 4 or 5 (see Figure 8).
The most important hydrocarbons with a characteristic branch are pristane C19 and phytane C20,
which belong to the iso – prenoid combinations and are called as terpanes (Figure 9). They can be
characterised as precursors of biologic fermentation. These hydrocarbons are present in living
systems, recent or older sediments, in slow oil and their relevant concentration has been used as
comparison indexes in environmental pollution.
The ratios pristane/nC17 and phytane/nC18 are used as environmental indexes (Lijmach, 1975)
(see Figures 10 & 11).

Regular Gasoline Unleaded Gasoline

Super Unleaded Gasoline Summer Gasoline

Winter Gasoline 80/87 Aviation Gasoline

Racing Gasoline, Brand 1 Racing Gasoline, Brand 2


Figure 2. GC/FID traces of unweathered gasoline (Fetter, 1999)
Stoddard Solvent Mineral spirits

Kerosene Fuel oil

Diesel Fuel #1 Diesel Fuel #2

Jet A 2 JP-4

Figure 3. GF/FID traces of unweathered middle distillate petroleum hydrocarbons


(Fetter, 1999)
Mineral Oil Hydraulic Fluid

30 Wt. Motor Oil 10/40 Wt. Moter Oil

Bunker C Bunker C

Figure 4. GC/FID traces of late distillate petroleum hydrocarbons (Fetter, 1999)


Figure 5. GC/FID trace of tar from two manufactured gas plants (Fetter, 1999)
Unweathered Gasoline 60% Evaporated Gasoline

80% Evaporated Gasoline 98% Evaporated Gasoline

Unweathered Diesel 20% Evaporated Diesel

50% Evaporated Diesel

Figure 6. GC/FID traces showing the effects of weathering on gasoline and diesel fuel
(Fetter, 1999)
Isoprenoid alkanes with several branches are hardly biodegraded by viruses. The cyclicalkanes
show great resistance in the attack from viruses. Complex alycyclic combinations like opanes are
some of the most resistant combinations in oil slicks in nature (Atlas 1981). The most important
genes of bacteria that are fed by petroleum hydrocarbons are Pseudomonas, Archomobacter,
Micrococcus, Nocardia, Vibrio, Acinetobacter, Brevibacterium, Corynebacterium, Flavobacterium,
Candida, Rhodotorula and Sporobolomyces (Bartha and Atlas 1977).

Figure 7. Distribution of the chain length for n-parafines of different types of organic compounds
(modified from the one of Lijbach, 1975)

Figure 8. Distribution of n-parafines C19 – C33 on the upper mud layer of the bottom
lagoon, in the Choctawhatchee bay, Florida (Palacas et al., 1972). The supply is almost
exclusively terrestrial.

Isoprenoid unit

Figure 9. Isoprenoid hydrocarbons that present a characteristic branch in every fifth atom of
carbon, in their chains
Figure 10. Gas chromatographers and different compounds that come from C different
types of Canada petrol and demonstrate the progressive changes that are cause due to
biodegradation ( unaltered on the top, more biodegratated towards the base) (Deroo et
al., 1975)

Analyses – Results

Methodology of Analysis
The method that was used for the analysis of the samples from Lake Koumoundourou was that of
the gas chromatography.
The system used was a gas chromatograph GC 5890 Series II made by Hewlett Packard with
sample induction ports split/splitless and SPI (septum temperature programmable injector) and FID
(flame ionization detector). The chromatographic column used was the HP5 30 m with an internal
diameter of 0.32 mm.
The temperature analysis program that was followed is the one below:
Initial temperature of column: T=500 C for 6 minutes and then with an upward pace of 150 C/minute
reaches the final temperature of T=3150 C and stays there for 20 minutes.
Temperature of induction port: T=2800 C
Temperature of the flame ionization detector FID: T=3200 C.

Results
The analysis of the samples using a gas chromatograph led to the conclusion that there is pollution
from oil hydrocarbons mainly at the bottom, a fact that was justified optically by the use of an
ultraviolet fluoride meter, its color and its smell. Water seems to be free or without traces of
pollutants as a result of the detergentation of the lake.
ELDA has constructed barriers in order to restrain the oil around the karstic spring to achieve the
minimization of the oil transferring to the whole body of the lake. So, the analysis of the water
samples from several points showed the existence only of physical alkanes except from the cases
when the weather conditions favored the propagation of the pollutants. As a result of this, fractions
of kerosene and diesel were found. On regular basis, kerosene and diesel were found in all
samples taken from both of the barriers with the concentration reaching values to 100%.
Figure 11. Biodegratation and its results on crude oil from S.E. Saskatchewan, Canada
(Bailey et al., 1973)

The analyses on all mud samples taken from the bottom showed a typical sequence of
hydrocarbons which, according to bibliography, characterizes the pollution from kerosene and
diesel. Light oil fractions were not found due to their high volatility and their escape to the
atmosphere.
All the above are showed by the gas chromatographs and the estimation of CPI.
The water samples analyzed had been taken from the first and second barrier, which were
constructed, as mentioned before, by ELDA for the minimization of oil transferring, and also from
the outlet of the lake.
The values of CPI for the first and second barriers are almost equal to 1 for all the sampling, since
they are rich in oil hydrocarbons, while as long as the samples at the outlet of the lake are in regard
the CPI index is mainly greater than 1. This shows the existence of physical alkanes except from
some values at times that the weather conditions favored the transfer of pollutants into the lake.
Table 3 shows several samplings in different times and points together with the values of CPI.
In Figures 12, 13 and 14 three characteristic gas chromatographs are given. They come from the
main points of sampling, the first barrier, the second and the outlet of the lake.

Table 3. CPI index in different times and points of sampling


Sample Date CPI
st 24/04/1996 1.14
1 Barrier
05/11/1997 1.014
04/11/1995 1.58
02/01/1996 1.36
nd 01/05/1996 1.08
2 Barrier
01/07/1996 1.48
04/11/1996 1.13
04/11/1997 0.41
22/03/1996 3.81
04/11/1996 4.13
Outlet
25/06/1996 2.99
14/11/1997 0.86
Figure 12. Gas chromatographer of an aquatic sample from the first dam in
Koumoundourou Lake

Figure 13. Gas chromatographer of an aquatic sample from the


second dam in Koumoundourou Lake
Figure 14. Gas chromatographer of an aquatic sample from the third dam in
Koumoundourou Lake

References
Atlas R.M 1981: Microbial Degradation of Petroleum Hydrocarbons: an Environmental Perspection
Microbiological Reviews, March 1981 p. 180 – 209.

Bartha R., and Atlas R. M. 1977: The microbiology of aquatic oil spills. Adv. Appl. Microbiol. 2:
255 – 266.

Fetter, C. W. 1999: Contaminant Hydrogeology Second Edition. Editions Prentice Hall, Inc.

Kollattukudy, P. E., 1970: Plant Waxes: Lipids, 5, 259 – 275.

Lijmbach, G. W. M., 1975: On the origin of petroleum: Proc. 9th World Petrol Conf., Applied
Science Publishes, London, v.2, p. 357 – 369.

Robinson, T., 1980: The organic constituents of higher plants, 4th edition, Cords Press, North
Amberst, Massachusetts.

Saliot A., 1981: Natural hydrocarbons in sea water, In: Marine Organic Chemistry, (Duursma, E. K.
and Dawson, R., eds.) pp. 327 – 374, Elsevier, Amsterdam.

Zemo, D. A., Bruya, J.E. and Graf. T.E., 1995: The application of Petroleum Hydrocarbon
Fingerprint Characterisation in Site Investigation and Remediation, Ground Water Monitoring and
Remadiation Vol. 15, No 2 p. 147 – 156.