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Received for review December 31,1981. Accepted May 26,1982. This research was supported by the Ecological Research Division, Office of Energy Research, U.S. Department of Energy and the US.Nuclear Regulatory Commission.
I-Alkenes as Potential Indicators of Sediment Shale Oil Contamination Robert G. Riley,” Thomas R. Garland, Martln L. O’Malley, Dale C. Mann, and Raymond E. Wildung
Environmental Chemistry Section, Pacific Northwest Laboratory, Battelle Memorial Institute, Richland, Washington 99352 Hydrocarbon fractions isolated from four shale oils, two petroleum oils, and one solvent-refinedcoal liquid product were analyzed by capillary gas chromatography/mass spectrometry for the presence of a homologous series of 1-alkenes. Of the liquid oil products examined, only the shale oils contained the 1-alkenes. 1-Alkenes were not detected in the hydrocarbon fractions of extracts from a raw oil shale or surface sediments collected in a drainage at locations above, adjacent to, and below the Department of Energy Anvil Points Oil Shale Facility, Rifle, CO. However, 1-alkenes were detected in retorted shale, sediment aggregates formed after oil transport downstream of the facility, and oil discharging from a shale pile. The absence of 1-alkenesin petroleum and a coal liquid product suggests that this class of compounds may be unique to shale oils, perhaps allowing their use as diagnostic indicators of sediments in contact with shale oils or their refined products. Introduction
In the past, the United States has relied extensively on domestic sources of petroleum to supply its energy needs. With domestic supplies limited and the assurance of uninterrupted supplies of foreign crude uncertain, the US. has embarked on a plan to reinitiate development of fuels from oil shale and coal. During production of shale oil, both waste water and retorted shale would be produced. The environmental consequences of ground disposal of these materials are largely unknown (1,2). Recent studies have identified one group of organic compounds (alkylpyridines) that have potential as indicators of impact to surface and ground waters by shale oils and retort waters (3). The alkylpyridines were shown to be mobile through substrata and thus useful for ground-water studies. However, little information is available regarding other chemical species that might be unique to shale oils and aid in the assessment of shale oil spills a t sites of development or during transport (4,5). The need for such analytical approaches was recently exemplified by a spill of solvent-refined coal liquid at a pilot plant at Ft. Lewis, WA (6). The purpose of this study was to examine the distribution and possible use of a homologous series of 1-alkenes as additional, confirmative indicators of shale oil contam-
ination at a site of oil shale development. Experimental Section
1. Substrate Materials, Samples of raw shale, retorted shale, and shale oil were obtained from the Department of Energy Anvil Points Oil Shale Facility, Rifle, CO. Over the period 1976-1977, shale oil was being produced by Development Engineering, Inc., from oil shale mined at the site (mahogany zone, Green River Formation). The shale was retorted by using the Paraho process operating in the direct heating mode, Le., retort gases recycled to the retort and combustion of a portion of the carbonaceous fraction provided the heat for the process. Product shale oil was sampled from the separation tank in a Teflon-lined stainless steel keg. The headspace was purged with N2 and cooled by packing the keg in an ice bath for shipment to the laboratory and storage at 4 “C. Oil samples used in this study for comparative purposes included three other shale oils, a solvent-refined coalblended distillate, and Prudhoe Bay and South Louisiana crude oils. Sampling and storage of the synthetic fuels materials have been previously described (7, 8). In addition, oil, discharging from the bottom of a retorted shale and shale fines pile located adjacent to the facility, was collected and stored at 4 OC in glass bottles. A 24-h composite of raw feed shale yielding 24-26 gallon/ton was obtained from the raw shale sampler installed in the semiworks retort. The sampler system removed a periodic sample from the raw shale conveyor belt running from the crusher to the retort by a timer-controlled flip gate. The composites (20-25 kg) were crushed to
