Biogeochemistry of organic matter in Lake Geneva: I ? particulate hydrocarbons as biogenic and anthropogenic molecular markers

Abstract

A study of the biogeochemistry of organic matter in Lake Geneva at a central station (SHL2), was carried out at key periods of the biological cycles from November 1985 to September 1986. The seasonal variability of particulate hydrocarbons was studied in the epilimnion and the hypolimnion, focusing on specific periods such as high phytoplankton productivity and rising herbivorous zooplankton activity (May 1986), clearness of waters (June 1986) and intense mixing of waters (February 1986). Analysis of non-aromatic hydrocarbons (NAH) indicated that their major source is the autochtonous phytoplankton. Year 1986 was characterized by a spring bloom of nanoplankton (chlorophyceae and cryptophyceae) which remained predominant during summer and fall. These biological events were correlated with an increase of biogenic NAH, particulary n-alkane and alkene concentrations; the latter increased by one order of magnitude in May. n-Alkane distributions maximized at n-C17 or n-C29, and the n-C17/n-C29 ratio varied in surface water from 2.8 in May to 0.06 in November of the preceding year, reflecting phytoplankton dominant species. Values of NAH/POC, n-alkanes/POC, alkenes/POC and pristane/phytane ratios underwent seasonal and vertical variations which could be related to grazing and/or settling of particles. NAH, n-alkane and alkene enrichment in hypolimnion particles was interpreted to be a result of zooplankton migrations. A series of 37 monoenes and polyenes having from 15 to 31 carbon atoms, originating from planktonic sources, were recognized in the particulate matter by gas chromatography/mass spectrometry (GC/MS). Their distribution was described in 3 sized particles (> 200 µm, 200-60 µm and < 60 µm, identified as adult zooplankton, young zooplankton and nanoplankton respectively) at two different periods of the biological cycle, May and June 1986. Low level inputs originating from terrestrial higher plants were evident in particles; the value of the Carbon Preference Index (CPI) in the carbon range 23–35 was less than 2.8. In all samples analyzed by GC, an unresolved complex mixture of hydrocarbons (UCM) was present and was interpreted, at least in May, as partly originating from the degradation of organic matter by microorganisms. Typical anthropogenic PAH, such as benzofluoranthene and dibenzo (a) anthracene, were found at a low level (9 and 3 ng l−1 respectively). The absence of hopane-type hydrocarbons, except in November 1985 and in September 1986, and typical combustion PAH associated with particles indicated high temperature pyrolytic contaminants rather than petroleum-derived compounds.