Comparison of sampling devices for the determination of polychlorinated biphenyls in the sea surface microlayer

Over 30 sea surface microlayer (SML) samples from two contrasting sites in the North Western Mediterranean -- Barcelona (Spain) and Banyuls-sur-Mer (France) -- were collected using three different sampling devices, namely, glass plate, metal screen (MS) and a surface slick sampler (SS), and compared with the corresponding underlying water (16 samples). The distributions of 41 polychlorinated biphenyl congeners (PCBs) were determined in the different phases: particulate (1.17-10.8 SigmaPCB ng L(-1)), truly dissolved (0.080-16.7 SigmaPCB ng L(-1)) and colloidal matter (1.17-43.0 SigmaPCB ng L(-1)), being the last two estimated from the analysis of the apparently dissolved phase. Concentrations of PCBs in the SML were higher than those in the underlying water (ULW), giving rise to enrichment factors (EF=[C](SML)/[C](ULW)) up to first-order of magnitude. The ANOVA statistical approach was used to assess differences of bulk data (e.g. dissolved organic carbon, DOC; particulate organic carbon, POC; suspended particulate matter, SPM) among sampling devices, whilst p-tailed t paired tests were used in order to compare the enrichments obtained for each sampling date. In this respect, no significantly different enrichment factors were found among sampling devices (p < 0.05), although the surface SS showed lower enrichments, probably due to the dilution of the SML with the ULW during sampling. The MS seemed to be the most suitable device for the determination of PCBs in the SML in terms of sampling efficiency under a variety of meteorological conditions.     

Porphyrin and chlorin distributions in a Late Pliocene lacustrine sediment

The tetrapyrroles in a highly immature Late Pliocene lacustrine sediment (Willershausen, Germany) show a simple distribution of both chlorin and porphyrin components as the free bases. The major components are C32 desoxophylloerythroaetioporphyrin (DPEP), a C33 bicycloalkano porphyrin, the chlorin analogue of the latter, and desoxophylloerythrin and its chlorin counterpart. The structure of the novel bicycloalkano chlorin was determined using a combination of two-dimensional phase-sensitive COSY NMR and nOe studies. Measurements of delta 13C and other data indicate that DPEP and the bicycloalkano porphyrin were derived from the chlorophyll(s) of photosynthetic organisms utilising a common source of CO2, probably diatoms. The occurrence of DPEP and other minor alkyl porphyrins indicates that the chlorophyll defunctionalisation pathway leading to these components can occur at low temperature and was probably biologically mediated, as was the condensation leading to the fused ring components.     

The effect of aromatization on the isotopic compositions of hydrocarbons during early diagenesis

Polycyclic aromatic hydrocarbons with varying degrees of aromatization were isolated from the Eocene Messel Shale (Rheingraben, Germany). The high abundances of these compounds and their structural resemblances to cyclic triterpenoid lipids are consistent with derivation from microbial rather than thermal processes. Compounds structurally related to oleanane contain from five to nine double bonds; those within a series of aromatized hopanoids contain from three to nine. All are products of diagenetic reactions that remove hydrogen or methyl groups, and, in several cases, break carbon-carbon bonds to open rings. Aromatized products are on average depleted in 13C relative to possible precursors by l.2% (range: l.5% enrichment to 4% depletion, n = 9). The dependence of 13C content on the number of double bonds is not, however, statistically significant and it must be concluded that there is no strong evidence for isotopic fractionation accompanying diagenetic aromatization. Isotopic differences between series (structures related to ursane, des-A-ursane, des-A-lupane, des-A-arborane, and possibly, des-A-gammacerane are present) are much greater, indicating that 13C contents are controlled primarily by source effects. Fractionations due to chromatographic isotope effects during HPLC ranged from 0.1 to 2.8%.     

Carbon isotopic fractionation associated with lipid biosynthesis by a cyanobacterium: relevance for interpretation of biomarker records

For the cyanobacterium Synechocystis UTEX 2470, grown photoautotrophically to a logarithmic stage of growth, the total lipid extract is depleted in 13C by 4.8% relative to average biomass. Depletions observed for acetogenic (straight-chain) lipids range from 7.6 (hexadecanoic acid) to 9.9% (a C16 n-alkyl chain bound in a polar-lipid fraction), with a mass-weighted average of 9.1%. Polyisoprenoid lipids fall into two isotopic groups, with phytol, diplopterol, and diploptene depleted by 6.4-6.9% and bishomohopanol (produced from the extracts by the preparative degradation of bacteriohopanepolyol) depleted by 8.4%. Analysis of the pattern of depletions indicates that two carbon positions in each C5 biomonomer leading to polyisoprenoid products are probably depleted in 13C relative to average biomass. The depletion of bacteriohopanepolyol relative to other polyisoprenoids can be ascribed to changes that occur over the life of each cell: (1) the 13C content of carbon flowing to lipid biosynthesis decreases as the cell size increases and (2) a greater proportion of the bacteriohopanepolyol which, unlike other polyisoprenoids, is present mainly in the cytoplasm rather than in membranes and is synthesized when cells are larger. Chlorophyll a is depleted relative to average biomass by O.7%. Given the observed depletion of 13C in phytol, the heteroaromatic, chlorophyllide portion of chlorophyll must be enriched in 13C by 2.7%. This enrichment is large relative to that in chlorophyllides produced by eukaryotes and may be related to a parallel enrichment of 13C in cyanobacterial glutamic acid. As in many previous investigations of cyanobacterial lipids, long-chain n-alkanes (C22-C29) are found in the extracts. They are, however, enriched in 13C relative to biomass and have isotopic compositions suggesting that they are contaminants of petrochemical origin. Available results indicate that cyanobacterial lipids will be depleted relative to dissolved CO2 that has served as a carbon source by 22-30% and that a wider range of depletions will be characteristic of eukaryotic products. The absence of long-chain n-alkanes in cyanobacteria reduces the possibility that petroleum ever formed from pre-eukaryotic sedimentary debris.     

Assessing coral reef health across onshore to offshore stress gradients in the US Virgin Islands

Managing the effects of anthropogenic disturbance on coral reefs is highly dependant on effective strategies to assess degradation and recovery. We used five years of field data in the US Virgin Islands to investigate coral reef response to a potential gradient of stress. We found that the prevalence of old partial mortality, bleaching, and all forms of coral health impairment (a novel category) increased with nearshore anthropogenic processes, such as a five-fold higher rate of clay and silt sedimentation. Other patterns of coral health, such as recent partial mortality, other diseases, and benthic cover, did not respond to this potential gradient of stress or their response could not be resolved at the frequency or scale of monitoring. We suggest that persistent signs of disturbance are more useful to short-term, non-intensive (annual) coral reef assessments, but more intensive (semi-annual) assessments are necessary to resolve patterns of transient signs of coral health impairment.     

A multivariate assessment of the coral ecosystem health of two embayments on the lee of the island of Hawai'i

Four coral-dominated coastal sites within two embayments (Kealakekua Bay and Honokōhau Bay) on the lee of the island of Hawai'i were studied to assess evidence of anthropogenic impacts in these relatively pristine locales. Nutrient-loading parameters were analyzed in relation to benthic composition data. Statistically, there were significant positive relationships between nitrate+nitrite, silicate, and ammonium with the abundance of macroalgae, coralline algae, and dead coral, and between delta(15)N and dead coral abundance. The north outside site of Kealakekua Bay and the south outside site of Honokōhau Bay appear to be most impacted by nutrient-loading factors in each bay, respectively. Comparisons with past nutrient data indicate that nutrient inputs have increased to the two bays, and that early impacts of these increased loadings are evident. It is predicted that at current nutrient-loading rates, the north sites of Kealakekua Bay and the south sites of Honokōhau Bay will exhibit evidence of further degradation in future years.     

Beach disturbance caused by off-road vehicles (ORVs) on sandy shores: relationship with traffic volumes and a new method to quantify impacts using image-based data acquisition and analysis

Vehicles cause environmental damage on sandy beaches, including physical displacement and compaction of the sediment. Such physical habitat disturbance provides a relatively simple indicator of ORV-related impacts that is potentially useful in monitoring the efficacy of beach traffic management interventions; such interventions also require data on the relationship between traffic volumes and the resulting levels of impact. Here we determined how the extent of beach disturbance is linked to traffic volumes and tested the utility of image-based data acquisition to monitor beach surfaces. Experimental traffic application resulted in disturbance effects ranging from 15% of the intertidal zone being rutted after 10 vehicle passes to 85% after 100 passes. A new camera platform, specifically designed for beach surveys, was field tested and the resulting image-based data compared with traditional line-intercept methods and in situ measurements using quadrats. All techniques gave similar results in terms of quantifying the relationship between traffic intensity and beach disturbance. However, the physical, in situ measurements, using quadrats, generally produced higher (+4.68%) estimates than photos taken with the camera platform coupled with off-site image analysis. Image-based methods can be more costly, but in politically and socially sensitive monitoring applications, such as ORV use on sandy beaches, they are superior in providing unbiased and permanent records of environmental conditions in relation to anthropogenic pressures.     

'Our shared responsibility': participation in ecological projects as a means of empowering communities to contribute to coastal management processes

The objective of this project was to empower people of Blyth Valley in Northumberland (northeast England) to contribute to the management of their coastal heritage. A group of volunteers, the Links Conservation Group, working in collaboration with the environmental managers (Blyth Valley Borough Council), scientists, local specialists and other volunteers, surveyed the biodiversity, social, cultural and industrial history and profiles of the dunes, as well as their perceived value to local residents. The Group used this information to develop management plans for the dunes. The recommendations have contributed to planning processes at three levels: (i) national coastal management plans; (ii) regional plans; and (iii) plans for further action at the local community level.