Beschreibung: Pelagic tar has been collected daily on a transsect from off Prtugal to south of the Canary Islands in January/February 1975. A new neuston sampler was used which may be towed at speeds between 7 and 10 knots (DERENBACH & EHRHARDT 1975). A total of 22 samples was taken. Dimensions of tar balls ranged from potatoe-size to small specks approximately 1 mm in diameter. Concentrations were found to vary between 20.5 and 0.007 mg/m2, except for one instance of an extremely high tar concentration of 2270 mg/m2. 49 GC analyses were made. 61% showed bimodal peak distributions characteristic of crude oil sludges. The composition of tar balls was independent of their size suggesting diffusion controlled degradation.

Beschreibung: As part of the NOAA/ROPME/MSRC sponsored assessment of the coast of Saudi Arabia, heavily impacted by the large oil spills of the 1991 Gulf War, we measured benthic community respiration (R) and primary production (P) rates in shallow subtidal basins near heavily oiled coastlines. Study sites were located in zones predicted to be basins of maximum deposition of any oiled sediments likely to wash off the adjacent coast and in reference bays predicted to be clean and unaffected. We measured oxygen exchange using in situ benthic respirometers and analysed petroleum hydrocarbon (PHC) levels in the near surface sediments at five stations. We concentrated our efforts in mud habitats to complement related studies in seagrass habitats. Measured community R rates ranged from a low of 700 μM m2 h−1 in coarse sand sediments with total organic carbon content (TOC) of only 0.16% of dry wt to the highest rate of 2184 μm m−2 h−1 in finer mud-sand habitats with 0.39% TOC. All measured rates were in the range of literature values for shallow marine sediments at temperatures of 17 to 19°C. Sediment oil content was 13–540 μg g−1 dry wt by ultraviolet fluorescence (UVF) analysis and 0.5–103 μg g−1 by gas chromatography (GC). Benthic P rates, calculated as light minus dark changes in dissolved oxygen, ranged from a low of 1162 μm m−2 h−1 at the most heavily oiled site to a high of 5216 μm m−2 h−1 at less oiled sites. While a weak inverse relationship between benthic P and sediment oil content was not significant statistically due to the small number of samples, a significant inverse relationship was found between the ratio of production to respiration (P/R) and the total petroleum content of the sediments by UVF. The effect appears to be driven more by differences in production than an effect on respiration which showed little relationship with either oil content or productivity. We conclude that within 1 year after the oil grounded on the intertidal sands of Saudi Arabia, the levels of oil in subtidal benthic sediments had decreased in most habitats to levels that did not show community stress by our oxygen measurements. Rather, long term damage to benthic subtidal habitats was limited only to enclosed bays adjacent to the most heavily oiled coastlines. Preliminary estimates of yearly P converted to carbon units indicates that the shallow mud sediments of the Gulf are at least as productive as most oligotrophic water columns. Since benthic habitats covered by seagrass, algae beds or coral reefs are likely to have even higher production rates, we conclude that benthic processes contribute significantly to the overall carbon flux in the Gulf ecosystem.

Beschreibung: Gas chromatography-mass spectrometry (GC-MS) analyses of organic concentrates from eastern Mediterranean surface water show that dissolved fossil fuel residues are dominated by unsubstituted aromatic hydrocarbons and heterocyclic aromatics and thus resemble products of incomplete combustion. Deviating from this interpretation, preferential photochemical oxidation of alkyl-substituted aromatics is suggested as the principal causative mechanism, although, especially near land-based sources. the influence of combustion-derived unsubstituted aromatics is not defined. Total concentrations of dissolved aromatics as determined by GC-FID (flame ionization detection) and GC-MS from a limited data subset were in reasonable agreement with UV fluorescence measurements of dissolved/dispersed oil residues. The same preponderance of unsubstituted aromatics over their alkyl derivatives was found in extracts of the particulate phase, but concentrations were small relative to alkanes and/or alkenes of recent marine biosynthetic origin. CPI (carbon preference index) values of higher molecular weight n-alkanes indicated varying contributions of plant waxes to the particulate hydrocarbon pool. CPI values of corresponding dissolved n-alkanes were found to be near unity, indicating fossil fuel origin. Despite differences in higher molecular weight n-alkane CPI values and the predominance of recent biosynthetic aliphatics, the similarity of dissolved and particulate aromatic fractions suggests limited adsorption by particles of fossil fuel derived hydrocarbons and heterocyclics.

Beschreibung: Saudi Arabian coastal waters near sandy beaches, severely contaminated with crude oil released in Kuwait during the 1991 Gulf War, as well as underlying sediments and a few bivalves, were analysed to assess concentrations and composition of petrogenic hydrocarbon mixtures and structurally related oxidation products. Concentrations of dissolved oil residues determined by UV spectrofluorometry (UVF) near oil deposits on beaches did not exceed 3.5 μg l−1; concentrations dropped to approximately 1/10th of this value a few miles offshore. Gravimetric concentrations of unfractionated lipophilic material extracted from large volumes of seawater at the same stations were up to 10 times those determined by UVF. After chromatography on silica gel, individual petroleum hydrocarbons in the low polarity fractions and oxidation products in the polar fractions were characterized by their spectra (GC/MS) and quantitated by Selected Ion Monitoring (SIM) GC/MS. Concentrations of oxidation products (ketones, aldehydes, alcohols) of aromatic hydrocarbons exceeded those of their parent compounds by more than an order of magnitude. Significant concentrations were also found of the presumably pyrogenic triplett sensitizer anthraquinone. Contributions to polar fractions of water extracts by biosynthesized lipids were negligible. UVF determinations appear to underestimate concentrations of dissolved oil residues, because many oxidation products have lower fluorescence quantum yields than the respective parent hydrocarbons. Their ecotoxicological properties are unknown. Concentrations measured in sediments by UVF ranged from 13 to 540 μg g−1 dry wt and 0.5 to 103 μg g−1 as measured by gas chromatography with flame ionization detection (FID GC). Bivalves ranged from 0.8 to 1.5 μg mg−1 extractable organic matter (EOM) by UVF, and 0.1 to 0.3 μg mg−1 EOM by GC analysis. PAHs were identified in sediment and bivalve extracts by GC/MS and quantitated by SIM GC/MS. None of the relatively water soluble alkylbenzene photo-oxidation products found in water samples nor any higher molecular weight quinones could be detected in sediment extracts. However, ion chromatograms strongly suggest the presence of numerous high molecular weight aromatics in that matrix.

Beschreibung: Oil released into the sea undergoes immediate compositional changes as a result of processes of volatilization, dissolution, particle adsorption, and microbial and photochemical decomposition. Based on our observation of the molecular composition of oil residues dissolved in subtropical ocean waters, we hypothesized photo-oxidation of alkyl-substituted polycyclic aromatic hydrocarbons (PAH) and heterocyclic aromatics in preference to their unsubstituted parent compounds. As the ratios of alkyl to parent PAH are used to assign sources to contaminant residues in environmental samples, we tested the hypothesis in a controlled experiment: membrane-filtered seawater collected near the island of Bermuda was saturated with a Nigerian crude oil and exposed to natural sunlight in a quartz flask. Comparison with a dark control under otherwise identical conditions served to differentiate between sunlight-induced and microbially mediated decreases in concentration and changes in composition. We conclude on the basis of UV fluorescence, GC-MS, and microbiological data that sunlight-induced oxidation is responsible for the rapid loss of the UV fluorescence signal for total aromatic hydrocarbons and for the preferential depletion of the alkyl-substituted PAH and heterocyclic aromatics. Structure-dependent selectivity in the photo-oxidation of dissolved oil residues may thus result in residual hydrocarbon blends which could be mistaken as originating from incomplete combustion processes.

Beschreibung: Methylcyclohexane dissolved in and forming a thin film on purified seawater with traces of anthraquinone added as triplet sensitizer was exposed to natural sunlight in a quartz flask. The water was circulated through a glass cartridge filled with Amberlite XAD-2 for the concentration of reaction products which were identified by GC/MS after elution and silica gel chromatography. They included isomeric methylcyclohexanols as the principal components, primary hydroperoxides, a tentatively identified secondary peroxide, methylcyclohexanones, and acyclic ketones. Mass spectra and mechanisms are discussed as well as possible biological consequences of the formation of these compounds.

Beschreibung: Along three sections and al a one day permanent station chemical parameters (P04, Si04, N02, N03, NH3, and 02) were determined from NANSEN bottle samples. Significant fluctuations of some of these parameters were observed. From a moored current meter array the current field was determined. It was coupled to the concentrations observed at the permanent station. The horizontal gradients of chemical components showed values up to 50% in less than 500 m distance. By use of the diffusion theory some estimates on the time scale of biochemical processes are presented. From the entire set of about 400 observations the mean relation between phosphate and silicate was found to be linear. Nitrate seemed to be the growth limiting factor. The mean relations between phosphate and nitrate and silicate and nitrate respectively differ considerably from a linear function. The oxidative ratios for nitrate, phosphate and silicate have been calculated and the following combination has been found from these regressions: ΔAOU : ΔP : ΔN : ΔSi = 276 : 1.2 : 14.7 : 7.2

Beschreibung: The distribution of the particulate organic carbon and nitrogen, and of the dissolved organic carbon as a function of depth and of time is investigated. A common pattern of these distributions is found with certain deviations from a mean value. The ratio N/C (particulate) is calculated. The variation of this parameter with depth shows a maximum at 10 m depth indicating increased biological activity. Also calculated are the ratios and the correlation coefficients between the concentrations of dissolved and particulate organic carbon and between the protein content of the particulate organic matter and its organic nitrogen content. Conclusions on the biochemistry of the phytoplankton are drawn from these computations. Die Veränderlichkeit der Konzentration an partikularem organischen Kohlenstoff und Stickstoff und gelöstem organischen Kohlenstoff mit der Tiefe und mit der Zeit werden untersucht. Die Veränderlichkeit dieser Parameter mit der Tiefe hat zu verschiedenen Zeiten ein ähnliches Aussehen mit gewissen Abweichungen von einem Mittelwert. Das Verhältnis N/C der partikulären Substanz wurde berechnet. Die Tiefenverteilung dieses Parameters hat ein Maximum in 10 m Tiefe, das erhöhte biologische Aktivität anzeigt. Ebenfalls berechnet werden die Verhältnisse zwischen den Konzentrationen von partikularem und von gelöstem organischen Kohlenstoff und der Korrelationskoeffizient zwischen beiden Größen. Die gleichen Berechnungen werden angestellt mit dem Proteingehalt der partikulären Substanz und ihrem Gehalt an organisch gebundenen Stickstoff. Aus diesen Berechnungen werden Schlüsse gezogen über die Biochemie des Phytoplanktons.