In recent decades. an exponential increase in the concentration of anthropogenic Polycyclic Aromatic Hydrocarbons (PAHs; see Table I for a li st of PAH abbreviations) has been observed worldwide. Regulators need to know the sources if concentrations are to be reduced and appropriate remediation measures taken. "Source characterization of PAHs" involves linking these contaminants to their sources. Scientists place PAH sources into three classes: pyrogenic, petrogenic. and natural. In this review. we investigate the possibility of using PAH molecular ratios individually or in combination for the purpose of deducing the petrogenic or pyrogenic origin of the contamination in sediments. We do this by reviewing the characteristic PAH patterns of the sources and by taking into account the fate of PAHs in the aquatic environment. Many PAH indicators have been developed for the purpose of discriminating different PAH sources. In Table 4 we summarize the applicability of different PAH ratios and threshold values. The analysis of two- to four-ringed alkylated PAH soilers the possibility to distinguish two or more single sources or categories of pollution in greater detail. For example. the FLO/PYO. the PPI. and PO/AO ratios can be used to discriminate between pyrogenic and petrogcnic sources of contamination. When petrogenic contamination is suspected. chrysenes. PAHs lighter than CO. and in particular. alkylated PAHs can usually be of use. For unburned coal PAHs. The methylphenanthrenic ratios (MP!s). the 1-D I/4- DI. and BbF/BkF are promising, since they are sometimes correlated with vitrinite rellectance (coal ranks). Alkylphenanthrenes can be used to detect biomass combustion. Higher molecular weight parent and alkylated PAHs are appropriate for pyrogenic discriminations. When PAH indices are coupled with discriminant analysis techniques such as PMF (positive matrix factorization),the origin of multiple sources in even the most complex environments can be traced and measured. Even so. the most stable isomer pairs degrade differentially. depending on their thermodynamic stability, the environmental conditions, and the type of degradation. If PAH ratios are to be used, it is usually necessary to have pri or knowledge of the degradation state of the matrices examined (air, sediment, etc.) and of how the PAH ratio behaves under such conditions. PAH ind ices (e.g ., NO/CO or LPAH/HPAH ) can be app lied for distinguishing differential degradation gradients (photodegradation, biodegradation, etc.). Degradation does not significantly affect the ratio of parent to alkylated PAHs and the PI. The degradation arrow in Table 4 and Figs. 9. I 0. II . 12. 13, 14. 15. 17. 18. 19, 20, 2 1, 22. 23. and 24 shows how the ratio usually changes with degradation. Merely detecting the six PAHs of Borneff6 is not enough to establish petrogenic contamination, because Borneff6 includes main ly HMW PAHs. The LPAH 16 appears to be the most suitable for identify ing pyrogenic and petrogenic sources. For more specific information on sources and their...

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Abstract. This paper presents new results from high temporal resolution observations over two years (2007 and 2008) from instrumented moorings deployed in the central North Sea, at the Oyster Grounds and on the northern slope of Dogger Bank (North Dogger). The water column was stratified in the summer at both sites, leading to limited exchange of the water in the bottom mixed layer. Data from these moorings revealed the variable nature of summer oxygen depletion at the Oyster Grounds. The combination of in situ and ship-based measurements allowed the physical and biological conditions leading to decreasing dissolved oxygen concentrations in bottom water to be examined. In 2007 and 2008, the concentration of dissolved oxygen in the bottom water at both sites was observed to decrease throughout the summer period after the onset of stratification. Depleted dissolved oxygen concentration (6.5 mg l −1 , 71% saturation) was measured at the North Dogger, a site which is not significantly influenced by anthropogenic nutrient inputs. Lower oxygen saturation (5.2 mg l −1 , 60% saturation) was measured for short durations at the Oyster Grounds. The seasonal increase in bottom water temperature accounted for 55% of the decrease in dissolved oxygen concentration at the Oyster Grounds compared to 10% at North Dogger.Dissolved oxygen concentration in bottom water at the Oyster Grounds was shown to be strongly influenced by short term events including storms and pulses of particulate organic matter input. In contrast, dissolved oxygen concentration in bottom water at the North Dogger reflected longer seaCorrespondence to: N. Greenwood (naomi.greenwood@cefas.co.uk) sonal processes such as a gradual temperature increase over the summer and a more steady supply of particulate organic matter to the bottom mixed layer. The differences between the study sites shows the need for an improved understanding of the mechanisms driving these processes if the use of oxygen in marine management and ensuring ecosystem health is to be meaningful and successful in the future. These high frequency observations provide greater understanding of the nature of the depletion in bottom oxygen concentration in the North Sea.

Abstract. Recent observations and modelling studies suggest that biogeochemical changes can mask atmospheric CO 2 -induced pH decreases. Data collected by the Dutch monitoring authorities in different coastal systems (North Sea, Wadden Sea, Ems-Dollard, Eastern Scheldt and Scheldt estuary) since 1975 provide an excellent opportunity to test whether this is the case in the Dutch coastal zone. The time-series were analysed using Multi-Resolution Analysis (MRA) which resulted in the identification of systemdependent patterns on both seasonal and intra-annual time scales. The observed rates of pH change greatly exceed those expected from enhanced CO 2 uptake, thus suggesting that other biogeochemical processes, possibly related to changes in nutrient loading, can play a dominant role in ocean acidification.

Population fluctuations are often driven by an interplay between intrinsic population processes and extrinsic environmental forcing. To investigate this interplay, we analyzed fluctuations in coastal phytoplankton concentration in relation to the tidal cycle. Time series of chlorophyll fluorescence, suspended particulate matter (SPM), salinity and temperature were obtained from an automated measuring platform in the southern North Sea, covering 9 years of data at a resolution of 12 to 30 minutes. Wavelet analysis showed that chlorophyll fluctuations were dominated by periodicities of 6 hours 12 min, 12 hours 25 min, 24 hours and 15 days, which correspond to the typical periodicities of tidal current speeds, the semidiurnal tidal cycle, the day-night cycle, and the spring-neap tidal cycle, respectively. During most of the year, chlorophyll and SPM fluctuated in phase with tidal current speed, indicative of alternating periods of sinking and vertical mixing of algal cells and SPM driven by the tidal cycle. Spring blooms slowly built up over several spring-neap tidal cycles, and subsequently expanded in late spring when a strong decline of the SPM concentration during neap tide enabled a temporary “escape” of the chlorophyll concentration from the tidal mixing regime. Our results demonstrate that the tidal cycle is a major determinant of phytoplankton fluctuations at several different time scales. These findings imply that high-resolution monitoring programs are essential to capture the natural variability of phytoplankton in coastal waters.