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Organic Geochemistry


Pyrolysis-GC/MS is advantageous as a tool for rapid sediment contamination assessment because of the small sample size required, minimal sample preparation, and its ability to detect a wide variety of organic pollutants as well as naturally-occurring biological materials. Py-GC/MS was applied, together with determination of organic carbon, and major and minor element concentrations, to evaluate potentially contaminated sediments in the port of Barcelona (Spain) and the adjacent Llobregat River delta. Detected contaminant markers, most evident in the Old Port (Port Vell) area, included hopanes and alkylated PAHs (petroleum), sterenes (sewage), C16-C19 phenylalkanes (detergents) and parent PAHs (combusted fuels).


Waterways in the world’s great port cities have been subject to many decades of environmental degradation, as an unintended consequence of shipping, industrial activity near the water’s edge, and non-point urban discharge within the associated watershed. Harbor and coastal waters provide natural laboratories for the study of the impact of urban runoff, airfall combustion debris, shipping activities and navigational dredging. Organic substances form a significant fraction of the potential pollutants in these urban systems, often originating as fossil fuels (raw or modified) and the combustion products thereof. As such, analytical methods initially developed for petroleum exploration are well suited for organic pollution assessment in sediments.

Enrichment in Corg, S and P was observed at affected sites, as were heavy metal pollutants (Ag, Hg, Pb, Cu, Zn). Evidence for organic pollution included C16-C19 phenylalkanes (detergents), hopanes and alkylated PAHs (petroleum), sterenes and alkylnitriles (suspected sewage pollution), and parent PAHs (combustion products). Modes of contaminant transport are sewer outfall (sewage and urban/industrial runoff), aeolian deposition of combustion particulate matter (industrial, vehicular, maritime), removal of polluted sediments by navigational dredging, and dumping of dredged materials. The restricted basin formed by the breakwater in the Old Port is a significant sink for pollutants and is likely the site of episodic water column hypoxia.

This preliminary study demonstrates that Py-GC/MS is effective for rapid screening for organic contaminants in sediments and is in the spirit of "green chemistry", in that it is a microanalytical technique which requires no hazardous solvents. Full-scan MS is recommended for the initial evaluation of a suite of samples, while selected ion monitoring is best for routine detection of trace contaminants. The semi-quantitative data which result are amenable to interpretation using multivariate methods and, with a larger sample set, geographic information systems (GIS), with the potential to provide valuable information for government, industry and public interest groups.


Published Citation

Kruge M.A. and Permanyer A (2004) Application of pyrolysis-GC/MS for rapid assessment of organic contamination in sediments from Barcelona harbor: Organic Geochemistry 35:1395-1408.