SUBSURFACE PERSISTENCE OF CRUDE OIL SPILLED ON LAND AND ITS TRANSPORT IN GROUNDWATER

J. J. Duffy and M. F. Mohtadi University of Calgary Calgary, Alberta, T2N 1N4 E. Peake Hudson s Bay Oil and Gas Calgary, Alberta T2P OX5

ABSTRACT
The persistence of water-soluble hydrocarbons from crude oil spills on land was investigated as a source ofgroundwater contamination by means of theoretical models, percolation experiments, and the analysis of core samples from spill sites. Examination of a one-dimensional flow model of convection, dispersion, biodgradation, and adsorption of an oil-water solution beneath a water table revealed that under certain conditions adsorption has no effect on the maximum oil concentration reached at any given distance from a spill. Chemical analysis of water percolated through an oil spill zone in a sand trough and also through soil cores taken at spill sites revealed that it may take the equivalent of much more than 100 times the average annual rainfall of Calgary to diminish the water-soluble components in the leachate to a level acceptable in drinking water. Measurements of the amount of alkanes and isoprenoids as functions of depth infield cores at spill sites of various ages and locations indicated that biodgradation rates are much lower in the anaerobic zone than above. Theoretical predictions indicate that contaminated groundwater may extend in the direction of flow from less than one meter to several thousand meters from a spill depending primarily on biodgradation rates and pore velocities. It is concluded that oil in the subsoil resulting from spills on land has the potential to pose very long-term threats to groundwater quality and, by the mechanism of resurfacing, to vegetation.

table under a spill area, and is based on previous work on models in soil of soluble hydrocarbons13 and of chemicals in general.3

i^9
8t

<LS = A( D iWQ
8t 8x \ 3x / 9x

+ 0

(1)

where C = concentration of hydrocarbons in water, = water content of soil (volume of water per volume of soil), S = concentration of adsorbed oil in soil, D = dispersion-diffusion coefficient, v = flux of solution (pore velocity), = source of sink term, and x = space coordinate in direction of solution flow. The following additional assumptions seem reasonable. Equilibrium is reached between the adsorbed and solution phases23 (see the next section of this paper), which can be described by the Freundlich equation with the exponent equal to one:25 S = KC, where K is an adsorption coefficient. The concentration of oil in water (C) is small. Therefore, the sink term can be approximated by a first order reaction: = kC, where k is a rate constant. The pore velocity in the saturated soil zone is relatively constant. The soil is homogeneous, and thus water content () is constant. The diffusion-dispersion coefficient is constant. With the above assumptions, Equation (1) becomes:
( e + K )

INTRODUCTION
The threat of ground and surface water contamination caused by oil spills on land often is overlooked in favor of the more obvious and immediate effects to surface vegetation and soil. The subsurface effects appear to have the potential for being more long-lasting and difficult to remedy. Although subsurface contamination from oil spills is recognized in Europe, 2,8 ' 9 ' 1314 ' 19 ' 20,22 23 probably because of greater dependence on ground water, relatively little attention appears to have been given the problem in North America until recently when many contamination cases came to light.4'7'12'15-17'18'24 This paper summarizes a recent study10 the objective of which was to investigate the persistence in the subsoil of spilled oil, particularly the water-soluble components. Three approaches were used: development of conceptual and mathematical models, soil column percolation laboratory experiments, and collection and analysis of soil cores from various oil spill sites.

=D^.vi_kC

9x2

ax

or i=Iyif -v-^-k'C at ax ax2 (2)

" +K G+K

Models
The following model is proposed to predict the concentration of oil in water as a function of time and distance along a flow line below the water

If the additional assumptions are made that at time = 0 the concentration in the water-saturated zone is zero and that the concentration entering the

475

476

1977 OIL SPILL CONFERENCE Field sampling

In order to study the behavior and persistence of spilled oil under natural conditions, soil core samples were taken at the sites of several known oil spills in Alberta. Instead of extensive samples at one site, a few samples were taken at each of several oil spill sites with varying soil types, locations, ages, etc., to see if any trends or relationships would become apparent. The oil from core samples at three spill sites was separated to obtain the aliphatic compounds, aromatic compounds, and the polar compounds. Although in general the total concentration of oil declined with depth, in several cores the aromatic fraction at a particular depth appeared to increase relative to the other two fractions. These accumulations at depths from 30 to 60 cm could result from end products of microbial degradation, or from Chromatographie processes in the soil. The degree of microbial degradation of paraffinic crude oils can be determined by measuring changes in the ratio of isoprenoid to n-alkane hydrocarbons. The normal alkanes are preferentially utilized by the microorganisms, and the relative amounts of isoprenoids increase.6 The isoprenoid to alkane ratios of cores at four locations are determined by gas chromatography are summarized in Table 1. These results indicate that in the deeper, more anaerobic zones, the degradation is very slow compared to the aerobic zones and, in fact, is non-detectable even at the 10% significance level at the 13-year-old spill site. During field sampling, some free oil was noted "floating" on the water table at two locations. In fact, resurfacing of spilled oil because of high water tables had occurred at these locations with resulting damage to crops.

water table is constant (C0), as in the next section, the solution to Equation 2 is 5: C(x,t) = C n P(x,t) where P(x,t) = l / 2 J e x p [ ^ j j , (v - V(v')2 + 4D'k' )J

Xerfc

rx-tN/(v/)2 +

wi

4Dy

exp

[('
(3)

+ V(v') 2 + 4D'k' ) X erfc

x + tV(v)2 + 4DV 4D't

where erfc (y) is the complementary error function of y and is defined as 2 f . ,v2 , erfc(y) = j=-\ e~ dt This solution is the typical breakthrough curve with center at v't. 21 A close inspection of Equation (3) shows that adsorption (K) affects merely the velocity (') of the breakthrough point and not the maximum concentration reached.

Model calculations Laboratory percolation experiments

In order to estimate the magnitude, composition, and persistence of water-soluble oil leached from a soil zone contaminated by a spill or leak (i.e., C0 as above), percolation experiments were performed. Basically, one experiment consisted of spilling three Imperial gallons of an Alberta crude oil (55 API) on a large trough (89 x 89 x 106 cm) containing sand, allowing the contaminated soil to weather for 40 days, irrigating with 100,000 liters of water over a four-month period, and sampling the effluent water and analyzing its hydrocarbon content by ultraviolet spectrophotometry and gas chromatography. Related experiments have been reported in the literature.1113-18'19'20'23 Gas Chromatographie analyses revealed that low molecular weight aromatic compounds, benzene and alkylated benzenes, together with low molecular weight paraffinic hydrocarbons were preferentially leached from the contaminated soil. As the lower molecular weight hydrocarbons became depleted, the alkylated naphthalene compounds increased in both relative and absolute abundance. Initial hydrocarbon concentrations measured greater than 1,500 /ug/1, and even after 5,300 cm of leachate (the equivalent of 120 times the average annual precipitation of 46 cm at Calgary) the water contained more than 400 g/l hydrocarbons. It is estimated that 39 g of dissolved hydrocarbons were leached from the soil during the course of the experiment. Some oil components can be detected by humans at a concentration of l/xg/l,14 and the leachate after 5,300 cm of simulated precipitation gave a threshold odor number greater than one as determined by the American Public Health Association method with 10 people. The 39 g of dissolved hydrocarbons leached from the simulated spill of 10 liters of oil was sufficient to impart an unpleasant odor and taste at the 400 ^g/1 level to a theoretical maximum of approximately 100,000 liters of ground water, or 10,000 times the volume of oil spilled. Ultraviolet spectroscopy analysis of a time series of samples of both the trough leachate and the water taken from beneath "weathering" Viking crude oil floating in a large open beaker revealed a close similarity. This result suggests similar chemical compositions over time, equilibrium concentrations of oil in water percolating through the trough, and the possibility of predicting oil concentrations in contaminated water entering the natural water table by means of simple laboratory experiments (i.e., C(0, t) as above). Water also was percolated through undisturbed cores taken from various depths at three spill sites. Volumes ranging from 13 to 130 cm percolated through seven cores resulted in concentrations varying from 0.4 to 12.6 mg/1. Some of the information obtained from laboratory and field experiments described above can be used along with the previously described theoretical model to make predictions on the extent of contamination of groundwater from oil spill sites in the direction of groundwater flow. Although based on simplifying assumptions, these estimates would be useful in planning groundwater monitoring and/or cleanup programs. The following steady-state solution to Equation 2 will be used: C(x, oo)

:oexp

(- A 7 ?)*]
2D ln(C/C 0 ) 4kD

(4)

Equation 4 can be easily solved for distance x:

(5)

- ^

For a particular spill the parameters in Equation 5 would have to be estimated. For example, C0 could be estimated on the basis of a simple oilweathering-on-water experiment, as discussed above. Table 2 contains some estimates of distance in the direction of groundwater flow from a crude oil spill site needed to reduce the concentration of water-soluble oil components by a factor of one-tenth, for an estimated range of parameter values for Alberta. Reduction factors of 1/100 to 1/1000 could be necessary to get the concentrations below that detectable in drinking water and would increase the distance by factors of 2 to 3, respectively, from those in Table 2. The corresponding time for the breakthrough curve to reach the 5,000 m indicated in Table 2 is 13.6 years. Thus, it appears that in certain situations, groundwater polluted as a result of an oil spill could appear many years after the spill at a considerable distance from the original spill site and persist for decades.

CONCLUSIONS
Based on the results of field sampling, laboratory experiments, and theoretical analysis summarized in this paper, as well as related literature, the following conclusions can be drawn.

OIL SPILL BEHAVIOR AND EFFECTS

Table 1. Relative isoprenoid/alkane weights for various spills Spill No Soil tion (y r s ) Average of five isoprenoid-alkane ratios Above estimated average water table (Number of samples) 11 Silty clay loam, cultivated Muskeg Greywooded Grey, hay meadow 2 0.70 (1) Below est. average water table (Number of samples) 0.56 (5) Crude similar to that spilled

477

75 108 100

4 7 13

1.25 (2) 3.65 (1) Alkanes absent

0.61 ! (3) 1.35 (2)

0.56

0.56 2 (5)

0.52

1. No significant difference at the 5% level between the crude oil ratios and two out of the three samples, on the basis of paired-t statistics 2. No significant difference at the 10% level between the crude and all of the samples, based on paired-t statistics

Table 2. Distances (m) for oil concentrations to be reduced by a factor of 0.1 for extremes of parameter values, based on equation 5 k = 3.2 X 10~ 8 sec. 1 v = 10" 5 cm/sec. = 0.25 300 0.72 1.1 v = 7 X 10 500 500
3

k = 3.2 X 10~9sec." sec. v = 10" 5 cm/sec. 7.2 v = 7 X 10~ 3 sec. 1400 5000

The water soluble components of crude oil spilled on land are very persistent and represent long-term environmental threats to ground water. More than the equivalent of 120 times the average yearly rainfall in Calgary (46 cm/yr) was required to reduce the oil concentration in the leachate to below 0.4 mg/1. Oil product spills pose an even more serious situation. Dietz9 estimated that 750 years of rainfall at 40 cm/year would be needed to reduce the concentration of hydrocarbons in leachate to below one mg/1 in an experiment by van der Waarden et al.23 involving benzene spills. These "rainfall" estimates are intended to indicate mainly the quantities of water needed, not necessarily lengths of time, since biodgradation of the oil in both water and soil and the vapotranspiration effects are neglected. The actual lengths of time could vary considerably depending on vapotranspiration and biodgradation rates. It appears that the types and concentrations of water-soluble components that would enter the water table over a period of time from a spill zone could be readily simulated in a laboratory by a simple oil-weathering-on-water experiment. Comparison of UV analysis of leachate from the trough experiment and of water in an oil-weathering experiment indicates that equilibrium concentrations are reached as water percolates through a spill zone in soil. Analysis of an idealized model of the concentration of oil in groundwater as a function of time and distance from a spill zone with a constant input reveals that adsorption may not have an effect on the maximum concentration reached at any given distance from a spill zone. From the experimental results, it appears that the persistence of oil in water entering the water table is sufficiently long (on the order of 100 years) as to approach a constant input, even when compared to some slow groundwater travel speeds (sometimes measured in scores of years) and low biodgradation rates in ground water.9'16

In summary, it appears that the damage to water resources from crude oil spills on land (to say nothing of oil product spills) can be very long-lived even if not very widespread. In addition, experience elsewhere 4'9 indicates that contamination of groundwater by oil may not appear until several decades after a spill. Today's spills may become tomorrow's problems.

ACKNOWLEDGMENTS
The authors are grateful for the support of this work by the Alberta Environmental Research Trust and the National Research Council. Acknowledgment is also due to the following for their valuable assistance in laboratory analysis: Karen Black, Bob Fitch, Karen Larsen, David Smith, and Bernadette Chan. The assistance of Vince Kraus and the technicians of the Chemical Engineering Department in constructing experiment apparatus also is gratefully acknowledged.

REFERENCES
1. American Public Health Association, 1971. Standard Methods for the Examination of Water and Wastewater, 13th Edition. American Public Health Association, Washington, D.C. 2. Blokker, P.C., 1971. Migration of oil in soil. Stichting CONCAWE Report No. 9/71. Presented at International Conference Antinquinamento 71 at Milan Fair of Anti-Pollution Equipment, November 15-19, 1971

478

1977 OIL SPILL CONFERENCE

15. Kerr, H.A., L.C. Topp, and M.D. Magas, 1973. Hydrocarbon contamination of shallow water table aquifers. Presented at CSAE Annual Meeting, August 1973. Victoria, British Columbia 16. Litchfield, J.H., and L.C. Clark, 1973. Bacterial activity in groundwater containing petroleum products. API Publication 4211. American Petroleum Institute, Washington, D.C. 17. Manitoba Clean Environment Commission, 1976. Preliminary report on contamination of underground water sources by refined petroleum products, Ground Water vl4, nl, pp36-44 18. McKee, J.E., F.B. Laverty, and R.M. Hertel, 1972. Gasoline in groundwater, Journal of the Water Pollution Control Federation, v44, n2, pp293-302 19. Mull, R., 1971. The migration of oil products in the subsoil with regard to groundwater pollution by oil. in S.J. Jenkins (ed.), Advances in Water Pollution Research, Proceedings 5th Intl. Conference, 1970. Pergamon, Oxford 20. Schwle, F., 1967. Petroleum contamination of the subsoila hydrological problem, in P. Hepple (ed.), Joint Problems of Oil and Water Industries. Institute of Petroleum, London 21. Thomann, R. V., 1972. Systems Analysis and Water Quality Management. Environment Research and Applications, New York 22. Van Dam, J., 1967. The migration of hydrocarbons in a water bearing stratum, in P. Hepple (ed.), Joint Problems of the Oil and Water Industries. Institute of Petroleum, London 23. Van der Waarden, M., A.L.A.M. Bridie, and W.M. Groenwoud, 1971. Transport of mineral oil components to groundwater. Water Research, v5, pp213-226 24. Vonhof, J.A., 1976. Contamination of shallow aquifers by refined petroleum products. Proceedings of Third Annual Engineering Institute of Canada Western Regional Conference, May 1976, Calgary, Alberta 25. Wood, A.L., and J.M. Davidson, 1975. Fluometuron and water content distributions during infiltration: measures and calculated. Soil Sei. Soc. Amer. Proceedings, v39, 820-285

3. Boast, C.W., 1973. Modeling the movement of chemicals in soils by water. Soil Sei. 115, pp224-230 4. Burnham, A.K., G. V. Calder, J.S. Fritz, G.A. Junk, H.J. Svec, andR. Vick, 1973. Trace organics in water: their isolation and identification. Journal of American Water Works Association. November 1973, pp722-725 5. Cho, C M . 1971. Convective transport of ammonium with nitrification in soil. Can. J. Soil Sei. 51, pp339-350 6. Cook, F.D., and D.W.S. Westlake, 1973. Biodegradability of northern crude oils. Northern development report 73-20, Information Canada Catalog R72-8373 7. Davis, J.B., V.E. Farmer, R.E. Kreider, A.E. Staub, and K.M. Reese, 1972. The migration of petroleum products in soil and ground water. API Publication 4149, American Petroleum Institute, Washington, D.C. 8. Dietz, D.N., 1971. Pollution of permeable strata by oil components. In Water Pollution by Oil. Institute of Petroleum, London 9. Dietz, D.N., 1972. Behavior of components from spilled oil on their way through the soil. AIME-Society of Petroleum Engineers Annual Fall Meeting SPE, October 1972. Paper SPE 4077 10. Duffy, J.J., E. Peake, and M.F. Mohtadi, 1976. Subsurface biophysiochemical transformations of spilled crude. Report to Alberta Environment Research Trust, April 11. Guard, H.E. and A.B. Cobet, 1973. The fate of bunker fuel in beach sand. Proceedings 1973 Conference on Prevention and Control of Oil Spills. American Petroleum Institute, Washington, D.C. 12. Hall, P.L., and H. Quam, 1976. Countermeasures to control oil spills in western Canada. Ground Water. 14:3 13. Hoffman, B. 1971. Dispersion of soluble hydrocarbons in ground water streams, in S.J. Jenkins (ed).), Advances in Water Pollution Research, Proceedings 5th Intl. Conference, 1970, Intl. Assn. Water Pollution Research. Pergamon, Oxford 14. Ineson, J., and R.F. Packham, 1967. Contamination of water by petroleum products, in P. Hepple (ed.), Joint Problems of Oil and Water Industries. Institute of Petroleum, London