Characterization of sea surface chemical contamination after shipping accidents.

A contamination survey was conducted after the beaching of the stricken cargo ship MSC Napoli in Lyme Bay on the south coast of Devon (UK). A grid of 22 coastal and offshore stations was sampled to investigate the extent of spilled oil and to screen for chemical contamination, as well as to evaluate the behavior of the oil at the air-sea interface. Samples were collected from the sea surface microlayer (SML) and from subsurface waters (SSW) at each station. The fuel oil spilled (IFO 380) was also analyzed. The determination of oil-related hydrocarbons (aliphatic hydrocarbons, polycyclic aromatic hydrocarbons (PAHs), terpanes, and steranes) and the screening for other harmful chemicals on the inventory of the MSC Napoli in the seawater samples, was performed by PTV-GC/ MS using large volume injection (LVI) techniques. Screening did not reveal the presence of any harmful chemicals other than petroleum-related compounds. Results afforded investigation of oil sources and spatial distributions of total PAH concentrations and enrichments in the sea surface microlayer (SML). Rather than a single source, oil fingerprinting analyses of the samples revealed a mixture of three types of oil: heavy fuel oil, lubricating oil, and a lighter oil (probably diesel oil). Enrichment factors (EF) in the SML (EF = C(SML)/C(SSW)) were calculated and, in the vicinity of the ship, approached 2000, declining with distance away from the wreck. These factors represent approximately a 1000-fold enrichment over typical coastal total PAH enrichments in the SML and reflected a clear petrogenic origin of the contamination (as demonstrated, for example, by a Fl/Pgamma ratio < 1). In addition, the spatial transport and fate (i.e., air-sea exchange processes and water column diffusion) of the oil-related hydrocarbons in the sea surface were investigated. Essentially, near the wreck, the SML was highly enriched in oil forming a visible sheen, both disrupting the normal air-seawater exchange processes and generating a downward diffusion flux of contaminants from the SML to the SSW. This was reflected by a higher occurrence of naphthalene relative to alkyl-naphthalenes in the SSW compared to the SML. The higher concentrations and different sources of oil found in the SML in comparison to those found in the SSW indicate that, if only subsurface water samples are investigated in isolation, the true extent and impact of a spill could be underestimated. It is important to simultaneously evaluate contamination in the sea surface during emergency response.