Traces of Oil Products

8/8/2019 Traces of Oil Products

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Traces Of Oil Products And Naturally Occurring Hydrocarbons InThe Lake Koumoundourou Of Aspropirgos, Attiki, Greece.

T. Mimides, M. Psychoyou, A. Sgoumpopoulou, S. RizosAgricultural 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 naturalhydrocarbons in water samples of Lake Koumoundourou.The samples were collected from different points of the lake, inside the two barriers that wereconstructed 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 theestimate 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 thelake and the outlet only natural alkanes, chains with odd number of carbon atoms, (CPI>1) wereidentified 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 (CarbonPreference Index), unweathered and evaporated gasoline, unweathered and evaporated diesel

IntroductionLake Koumoundourou is encountered in the southeast exit of the Thriasian plain towards the sea. Itis located in the southwest tailings of the Aigaleo Mountain. Its boundaries are betweenKapsalwnas hill (273m elevation) and Gkika hill (77m elevation. Between the west side of theEleusina Gulf and the lake lays a terrestrial zone about 50 m. This zone is at a distance of 15 kmfrom Athens at a latitude of 38

O02 B and at a longitude of 23

O37 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 Figure1).Lake Koumoundourou is in the vicinity of the national road, the camp AVEK 871 that supplies withfuel and oils the majority of the Greek army, the ELDA, as well as with an important amount of fueltanks belonging to private companies. This wetland has been disordered and is close to extinctionunless efforts for its protection take place, such as protection from the intense industrialdevelopment in the area, as well as limitation in the licks of the underground fuel reservoirs. Worksof infrastructure shall also be done in order to collect the rainwater that rinses out the national roadending in the lake, as well as to collect the contaminants from the use of detergents, dissolves andoil at the AVEK camp.In order to identify the oil hydrocarbons that are encountered in the lake, analyses were done bothin water samples in several points of it and mainly in samples taken from the two barriers that havebeen constructed by ELDA in front of the karstic spring that supplies the lake. These two barrierswere constructed in order to sustain the oil products that either sprout or exist in the outlet of thelake to the sea.

Identification of oil hydrocarbons and carbon tarThe Environmental Protection Agency of the U.S.A (40CFR Part 136, Federal Register, October26, 1984) has developed a series of original methods for the analysis of organic chemicalsubstances dissolvable in water. These methods are known as 600 series and include 15 analyticaltechniques numbered 601 613, 624 and 625 (see Table 1).Analysis of hydrocarbons in soil samples may be also done using the TPH (total hydrocarbonpetroleum), (Zemo, Bruya and Graf, 1995). This is a chromatographic analysis that separatesorganic mixtures and depends on boiling points. The assumption is based on the fact that all thepicks that fall in the reach of a boiling point come from oil hydrocarbons. Their masses combineand 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.


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Figure 1. Geological Map of Koumoundourou lake


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LEGEND

QuarteriatSand, gravel and good quality loams

Talus slope screes and recent alluvialfans

Sand and loams (marsh formations)

Gravel,loam and sand (poorly sorted)

Pelagic Zone

Limestones, dolomatic limestones anddolomites (Mid Triassic Lowerjurassic)

Limestones and dolomites like theprevious 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)


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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 Phenols605 HPLC Benzidines

606 GC Phthalic ether

607 GC Nitrosamines

608 GCOrgano-chlorianatedPesticides and PCB

609 GCNitro-aromatic compounds

and Isophines

610 GC and HPLCPolycyclic scented

hydrocarbons

611 GC Halogen ether

612 GC Chloride hydrocarbons

613 GC/MS 2,3,7,8 TCDD (dioxin)

624 GC/MS Clear organic combinations625 GC/MS

Key: GC = gas chromatographyFIDGC = gas chromatography with ionization flame detectorHPLC = liquid chromatography of high performanceGC/MS = gas chromatography/mass spectrography

A more accurate identification of hydrocarbons can be done by using the gas chromatograph with aflame ionisation detector (GC/FID) (Zemo, Bruya and Graf, 1995) can do a more accurateidentification of hydrocarbons in the soil and NAPLs. This analysis creates traces that give picksthat come out from the chromatographic column as time functions. The first ingredients that comeout are these with low boiling point. The traces of GC/FID are like a stamp that can be used for theidentification 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 animportant variety between the different types of benzene and sold benzene in different periods oftime. 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 meaningredients 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, containingVTEX combinations. Mean distillates are mainly normal alkalines and naphthalenes that are muchless soluble than VTEX combinations.The last distillates are shown in Figure 4. These have more of their picks larger than C24 and whilethey 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. Thisvitiation is possibly due to the volatility or the biodegradation. The result is a removal of the GC/FIDtraces 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 suchcomponents dissolve in water, they change dramatically. This is due to the different solvability ofeach component (Zemo, Bruya and Graf, 1995).In Table 2 are written the various solvabilities in water of gasoline ingredients that were separatedat 25

0C. The solvability in water of a mixture that comes in contact with a hydrocarbon can be

found with the help of Raoults law. Most of the petroleum distillates show very poor solvability inwater. Gasoline firstly gives VTEX, several other benzenes (such as trimethylobenzene,methylbenzene etc.) and napthalenes. Fuel oil gives the same mixtures plus phenanthrene andanthracene. Carbon tar includes all previous plus some multi core scented mixtures likeacenapthylene and fluorene. The traces of their soluble phase are similar in a way and it is difficultto identify and study them as it happens with the maternal material.


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Table 2 Watersolubility of selected hydrocarbons found in petroleum distillates (Fetter, 1999).

Water Solubility@ 25C

Formula weight

BenzeneToluene

p-Xyleneo-Xylenem-XyleneEthylbenzene1,2,3-Trimethylbenzene1,2,4-Trimethylbenzene1,3,5-TrimethylbenzeneNapthalene2-MethylnaphaleneAcenaptheneAcenaphtyleneFluroenePhenathrene

FluoranthenePyreneAnthracene

1780 mg/L500 mg/L

200 mg/L170 mg/L170 mg/L150 mg/L63 mg/L57 mg/L50 mg/L32 mg/L25 mg/L

3.9 mg/L3.9 mg/L2.0 mg/L1.3 mg/L

0.26 mg/L0.13 mg/L0.075 mg/L

78.1192.14

106.17106.17106.17106.17120.19120.19120.19128.18142.20154.21152.20166.22178.24

202.26202.26178.24

CPI index naturally occurred HydrocarbonsThe naturally occurred hydrocarbons in fresh or salty water that are constantly supplied fromsprings 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 varyingbetween 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 ofterrestrial plants have an uneven number of carbon atoms (Robinson 1980). An example of a smallchain of alkanes that comes from higher plants is the hydrocarbon n eptane (n C7), which is themain 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 Figure7).Primary plants, bacteria and algae show in general a maximum between n C17 n C21 wheremost 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. Aqualitative suggestion according to the preference concision in even or uneven number of carbonatoms is the CPI index (Carbon Preference Index):

+

=

3218

3117

3016

3117

2

1

nCnC

nCnC

nCnC

nCnCCPI

If paraffin with even and uneven number of carbon atoms occur at the same way then CPI isalmost 1. If the uneven dominate then CPI is >1, while for living organisms and recent sedimentsCPI 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 becharacterised as precursors of biologic fermentation. These hydrocarbons are present in living


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systems, recent or older sediments, in slow oil and their relevant concentration has been used ascomparison indexes in environmental pollution.The ratios pristane/nC17 and phytane/nC18 are used as environmental indexes (Lijmach, 1975)(see Figures 10 & 11).

Figure 2. GC/FID traces of unweathered gasoline (Fetter, 1999)

Regular Gasoline Unleaded Gasoline

Super Unleaded Gasoline Summer Gasoline

Winter Gasoline 80/87 Aviation Gasoline

Racing Gasoline, Brand 1 Racin Gasoline, Brand 2


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Figure 3. GF/FID traces of unweathered middle distillate petroleum hydrocarbons(Fetter, 1999)

Stoddard Solvent Mineral spirits

Kerosene

Diesel Fuel #1 Diesel Fuel #2

Jet A 2 JP-4

Fuel oil


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

Mineral Oil Hydraulic Fluid

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

Bunker C Bunker C


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Figure 5. GC/FID trace of tar from two manufactured gas plants (Fetter, 1999)


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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)


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Isoprenoid alkanes with several branches are hardly biodegraded by viruses. The cyclicalkanesshow great resistance in the attack from viruses. Complex alycyclic combinations like opanes aresome of the most resistant combinations in oil slicks in nature (Atlas 1981). The most importantgenes 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 bottomlagoon, in the Choctawhatchee bay, Florida (Palacas et al., 1972). The supply is almost

exclusively terrestrial.

Figure 9. Isoprenoid hydrocarbons that present a characteristic branch in every fifth atom ofcarbon, in their chains

Isoprenoid unit


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Analyses Results

Methodology of AnalysisThe method that was used for the analysis of the samples from Lake Koumoundourou was that ofthe gas chromatography.The system used was a gas chromatograph GC 5890 Series II made by Hewlett Packard withsample 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 internaldiameter of 0.32 mm.The temperature analysis program that was followed is the one below:Initial temperature of column: T=50

0C for 6 minutes and then with an upward pace of 15

0C/minute

reaches the final temperature of T=3150

C and stays there for 20 minutes.

Temperature of induction port: T=2800

CTemperature of the flame ionization detector FID: T=320

0C.

ResultsThe analysis of the samples using a gas chromatograph led to the conclusion that there is pollutionfrom oil hydrocarbons mainly at the bottom, a fact that was justified optically by the use of anultraviolet fluoride meter, its color and its smell. Water seems to be free or without traces ofpollutants 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 theminimization of the oil transferring to the whole body of the lake. So, the analysis of the watersamples from several points showed the existence only of physical alkanes except from the caseswhen the weather conditions favored the propagation of the pollutants. As a result of this, fractionsof 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 10. Gas chromatographers and different compounds that come from C differenttypes of Canada petrol and demonstrate the progressive changes that are cause due tobiodegradation ( unaltered on the top, more biodegratated towards the base) (Deroo et

al., 1975)


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The analyses on all mud samples taken from the bottom showed a typical sequence ofhydrocarbons 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 theatmosphere.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 wereconstructed, as mentioned before, by ELDA for the minimization of oil transferring, and also fromthe outlet of the lake.The values of CPI for the first and second barriers are almost equal to 1 for all the sampling, sincethey are rich in oil hydrocarbons, while as long as the samples at the outlet of the lake are in regardthe CPI index is mainly greater than 1. This shows the existence of physical alkanes except fromsome 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 themain 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

24/04/1996 1.141

stBarrier

05/11/1997 1.014

04/11/1995 1.58

02/01/1996 1.36

01/05/1996 1.08

01/07/1996 1.48

04/11/1996 1.13

2nd

Barrier

04/11/1997 0.41

22/03/1996 3.81

04/11/1996 4.13

25/06/1996 2.99Outlet

14/11/1997 0.86

Figure 11. Biodegratation and its results on crude oil from S.E. Saskatchewan, Canada(Bailey et al., 1973)


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Figure 12. Gas chromatographer of an aquatic sample from the first dam inKoumoundourou Lake

Figure 13. Gas chromatographer of an aquatic sample from thesecond dam in Koumoundourou Lake


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ReferencesAtlas R.M 1981: Microbial Degradation of Petroleum Hydrocarbons: an Environmental PerspectionMicrobiological 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., AppliedScience Publishes, London, v.2, p. 357 369.

Robinson, T., 1980: The organic constituents of higher plants, 4th

edition, Cords Press, NorthAmberst, 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 HydrocarbonFingerprint Characterisation in Site Investigation and Remediation, Ground Water Monitoring andRemadiation Vol. 15, No 2 p. 147 156.

Figure 14. Gas chromatographer of an aquatic sample from the third dam inKoumoundourou Lake

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