Chemical fractionation and mass spectral probe distillation reveal the presence in recent marine sediments of a complex assemblage of nitrogen-containing aromatic compounds. These azaarenes range from three- to eight-membered rings, with homologs containing up to eight alkyl carbons. In their composition, and presumably in their origin in natural fires, they resemble the aromatic hydrocarbons found in the same sediments. The analytical, geochemical, and environmental implications of these findings are discussed.
Crude oil spilled from a subsurface pipeline in northcentral Minnesota has dissolved in the groundwater, resulting in the formation of a plume of aliphatic, aromatic, and alicyclic hydrocarbons. Comparison of paired oil and groundwater samples collected along the central axis of the residual oil body shows that the trailing edge of the oil is depleted in the more soluble aromatic hydrocarbons (e.g., benzene, toluene, etc.) when compared with the leading edge. At the same time, concentrations of monoaromatic hydrocarbons in groundwater beneath the oil increase as the water moves toward the leading edge of the oil. Immediately downgradient from the leading edge of the oil body, certain aromatic hydrocarbons (e.g., benzene) are found at concentrations near those expected of a system at equilibrium, and the concentrations exhibit little variation over time (≈8-20%). Other compounds (e.g., toluene) appear to be undersaturated, and their concentrations show considerably more temporal variation (≈20-130%). The former are persistent within the anoxic zone downgradient from the oil, whereas concentrations of the latter decrease rapidly. Together, these observations suggest that the volatile hydrocarbon composition of the anoxic groundwater near the oil body is controlled by a balance between dissolution and removal rates with only the most persistent compounds reaching saturation. Examination of the distributions of homologous series and isomeric assemblages of alkylbenzenes reveals that microbial degradation is the dominant process controlling the fate of these compounds once groundwater moves away from the oil. For all but the most persistent compounds, the distal boundary of the plume at the water table extends no more than 10-15 m downgradient from the oxic/anoxic transition zone. Thus, transport of the monoaromatic hydrocarbons is limited by redox conditions that are tightly coupled to biological degradation processes.
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