Fifth-order cyclicity and organic matter contents relationship (Lower Eocene, Pyrenees)

The Upper Limestone Member of the Corones Formation of the Spanish Pyrenees consists of various units (Lower and Upper Foraminifera Units, Shale Unit, Cherty-ostracode Unit, Ostracode Unit and Chara-ostracode Unit) and offers strong facies and lateral thickness (20 to 80 m) variations. Detailed facies analyses, fifth-order cycles and organic geochemical determinations in the central domain of the Corones platform carbonates (Cherty-ostracode Unit), lower Eocene in age, were carried out to establish a case of close relationship between variations in organic matter productivity and cyclicity with annual period. The Cherty-ostracode Unit displays a continuous and pervasive fifth-order cyclicity, represented by 5 cycles. Each cycle consists of a lower part (mollusc facies) and an upper part (laminated ostracode facies). The calculated fifth-order cycle period ranges from about 17,000 to 28,000 years, which falls within the Milankovitch Band. Variations in organic matter content related to these carbonate cycles have been established. The lower mollusc facies members show a low organic carbon content and Hydrogen Index (HI) below 0.6% in weight and 261, respectively. By contrast, the upper laminated ostracode facies members show high organic carbon contents (up to 2% in weight) and high HI (between 164 and 373), and are also characterized by important silicification processes (the content in chert is up to 30%). The organic geochemistry resulting from these organic rich levels reflects a contribution of algal marine input.

Bioavailability of sinking organic matter in the Blanes canyon and the adjacent open slope (NW Mediterranean Sea)

Submarine canyons are sites of intense energy and material exchange between the shelf and the deep adjacent basins. To test the hypothesis that active submarine canyons represent preferential conduits of available food for the deep-sea benthos, two mooring lines were deployed at 1200 m depth from November 2008 to November 2009 inside the Blanes canyon and on the adjacent open slope (Catalan Margin, NW Mediterranean Sea). We investigated the fluxes, biochemical composition and food quality of sinking organic carbon (OC). OC fluxes in the canyon and the open slope varied among sampling periods, though not onsistently in the two sites. In particular, while in the open slope the highest OC fluxes were observed in August 2009, in the canyon the highest OC fluxes occurred in AprilMay 2009. For almost the entire study period, the OC fluxes in the canyon were significantly higher than those in the open slope, whereas OC contents of sinking particles collected in the open slope were consistently higher than those in the canyon. This result confirms that submarine canyons are effective conveyors of OC to the deep sea. Particles transferred to the deep sea floor through the canyons are predominantly of inorganic origin, significantly higher than that reaching the open slope at a similar water depth. Using multivariate statistical tests, two major clusters of sampling periods were identified: one in the canyon that grouped trap samples collected in December 2008, oncurrently with the occurrence of a major storm at the sea surface, and associated with increased fluxes of nutritionally available particles from the upper shelf. Another cluster grouped samples from both the canyon and the open slope collected in March 2009, concurrently with the occurrence of the seasonal phytoplankton bloom at the sea surface, and associated with increased fluxes of total phytopigments. Our results confirm the key ecological role of submarine canyons for the functioning of deep-sea ecosystems, and highlight the importance of canyons in linking episodic storms and primary production occurring at the sea surface to the deep sea floor.

Self-Organising Maps and Correlation Analysis as a Tool to Explore Patterns in Excitation-Emission Matrix Data Sets and to Discriminate Dissolved Organic Matter Fluorescence Components

Dissolved organic matter (DOM) is a complex mixture of organic compounds, ubiquitous in marine and freshwater systems. Fluorescence spectroscopy, by means of Excitation-Emission Matrices (EEM), has become an indispensable tool to study DOM sources, transport and fate in aquatic ecosystems. However the statistical treatment of large and heterogeneous EEM data sets still represents an important challenge for biogeochemists. Recently, Self-Organising Maps (SOM) has been proposed as a tool to explore patterns in large EEM data sets. SOM is a pattern recognition method which clusterizes and reduces the dimensionality of input EEMs without relying on any assumption about the data structure. In this paper, we show how SOM, coupled with a correlation analysis of the component planes, can be used both to explore patterns among samples, as well as to identify individual fluorescence components. We analysed a large and heterogeneous EEM data set, including samples from a river catchment collected under a range of hydrological conditions, along a 60-km downstream gradient, and under the influence of different degrees of anthropogenic impact. According to our results, chemical industry effluents appeared to have unique and distinctive spectral characteristics. On the other hand, river samples collected under flash flood conditions showed homogeneous EEM shapes. The correlation analysis of the component planes suggested the presence of four fluorescence components, consistent with DOM components previously described in the literature. A remarkable strength of this methodology was that outlier samples appeared naturally integrated in the analysis. We conclude that SOM coupled with a correlation analysis procedure is a promising tool for studying large and heterogeneous EEM data sets.

Technical Note: Dissolved organic matter fluorescence a finite mixture approach to deconvolve excitation-emission matrices

The analysis of the shape of excitation-emission matrices (EEMs) is a relevant tool for exploring the origin, transport and fate of dissolved organic matter (DOM) in aquatic ecosystems. Within this context, the decomposition of EEMs is acquiring a notable relevance. A simple mathematical algorithm that automatically deconvolves individual EEMs is described, creating new possibilities for the comparison of DOM fluorescence properties and EEMs that are very different from each other. A mixture model approach is adopted to decompose complex surfaces into sub-peaks. The laplacian operator and the Nelder-Mead optimisation algorithm are implemented to individuate and automatically locate potential peaks in the EEM landscape. The EEMs of a simple artificial mixture of fluorophores and DOM samples collected in a Mediterranean river are used to describe the model application and to illustrate a strategy that optimises the search for the optimal output.

Bioavailability of sinking organic matter in the Blanes canyon and the adjacent open slope (NW Mediterranean Sea)

Submarine canyons are sites of intense energy and material exchange between the shelf and the deep adjacent basins. To test the hypothesis that active submarine canyons represent preferential conduits of available food for the deep-sea benthos, two mooring lines were deployed at 1200 m depth from November 2008 to November 2009 inside the Blanes canyon and on the adjacent open slope (Catalan Margin, NW Mediterranean Sea). We investigated the fluxes, biochemical composition and food quality of sinking organic carbon (OC). OC fluxes in the canyon and the open slope varied among sampling periods, though not onsistently in the two sites. In particular, while in the open slope the highest OC fluxes were observed in August 2009, in the canyon the highest OC fluxes occurred in April-May 2009. For almost the entire study period, the OC fluxes in the canyon were significantly higher than those in the open slope, whereas OC contents of sinking particles collected in the open slope were consistently higher than those in the canyon. This result confirms that submarine canyons are effective conveyors of OC to the deep sea. Particles transferred to the deep sea floor through the canyons are predominantly of inorganic origin, significantly higher than that reaching the open slope at a similar water depth. Using multivariate statistical tests, two major clusters of sampling periods were identified: one in the canyon that grouped trap samples collected in December 2008, oncurrently with the occurrence of a major storm at the sea surface, and associated with increased fluxes of nutritionally available particles from the upper shelf. Another cluster grouped samples from both the canyon and the open slope collected in March 2009, concurrently with the occurrence of the seasonal phytoplankton bloom at the sea surface, and associated with increased fluxes of total phytopigments. Our results confirm the key ecological role of submarine canyons for the functioning of deep-sea ecosystems, and highlight the importance of canyons in linking episodic storms and primary production occurring at the sea surface to the deep sea floor.

Self-Organising Maps and Correlation Analysis as a Tool to Explore Patterns in Excitation-Emission Matrix Data Sets and to Discriminate Dissolved Organic Matter Fluorescence Components

Dissolved organic matter (DOM) is a complex mixture of organic compounds, ubiquitous in marine and freshwater systems. Fluorescence spectroscopy, by means of Excitation-Emission Matrices (EEM), has become an indispensable tool to study DOM sources, transport and fate in aquatic ecosystems. However the statistical treatment of large and heterogeneous EEM data sets still represents an important challenge for biogeochemists. Recently, Self-Organising Maps (SOM) has been proposed as a tool to explore patterns in large EEM data sets. SOM is a pattern recognition method which clusterizes and reduces the dimensionality of input EEMs without relying on any assumption about the data structure. In this paper, we show how SOM, coupled with a correlation analysis of the component planes, can be used both to explore patterns among samples, as well as to identify individual fluorescence components. We analysed a large and heterogeneous EEM data set, including samples from a river catchment collected under a range of hydrological conditions, along a 60-km downstream gradient, and under the influence of different degrees of anthropogenic impact. According to our results, chemical industry effluents appeared to have unique and distinctive spectral characteristics. On the other hand, river samples collected under flash flood conditions showed homogeneous EEM shapes. The correlation analysis of the component planes suggested the presence of four fluorescence components, consistent with DOM components previously described in the literature. A remarkable strength of this methodology was that outlier samples appeared naturally integrated in the analysis. We conclude that SOM coupled with a correlation analysis procedure is a promising tool for studying large and heterogeneous EEM data sets.

The influence of substratum type and nutrient supply on biofilm organic matter utilization in streams

We investigated the effect of benthic substratum type (sand and rocks) and nutrient supply (N and P) on biofilm structure and heterotrophic metabolism in a field experiment in a forested Mediterranean stream (Fuirosos). Rock and sand colonization and biofilm formation was intensively studied for 44 d at two stream reaches: control and experimental (continuous addition of phosphate, ammonia, and nitrate). Structural (C, N, and polysaccharide content and bacterial and chlorophyll density) and metabolic biofilm parameters (b-glucosidase, peptidase, and phosphatase enzyme activities) were analyzed throughout the colonization process. The epilithic biofilm (grown on rocks) had a higher peptidase activity at the impacted reach, together with a higher algal and bacterial biomass. The positive relationship between the peptidase activity per cell and the N content of the epilithic biofilm suggested that heterotrophic utilization of proteinaceous compounds from within the biofilm was occurring. In contrast, nutrient addition caused the epipsammic biofilm (grown on sand) to exhibit lower b-glucosidase and phosphatase activities, without a significant increase in bacterial and algal biomass. The differential response to nutrient addition was related to different structural characteristics within each biofilm. The epipsammic biofilm had a constant and high C:N ratio (22.7) throughout the colonization. The epilithic biofilm had a higher C:N ratio at the beginning of the colonization (43.2) and evolved toward a more complex structure (high polysaccharide content and low C:N ratio) during later stages. The epipsammic biofilm was a site for the accumulation and degradation of organic matter: polysaccharides and organic phosphorus compounds had higher degradation activities

Benthos of Spanish lakes and reservoirs

A summary of the results from the study of benthos of lakes and reservoirs in Spain is provided, with a list of the species found to date. Spanish natural lakes are smaller than European lakes; the largest is Lake Sanabria, of glacial origin, which is 3 Km long and half a kilorneter wide. Many are very small and situated in the mountains; more than 200 hundred have been recorded in Spain, but only in Lake Sanabria and Lake Banyoles have the benthos been studied. Lake Sanabria is a cold oligotrophic, monomictic lake with oxygen always present in the deepest zones. Its fauna is similar to that of other central European lakes, with Mici.opsectra c.orztractu (a chironomid) as the dominan1 species. Lake Banyoles is a karstic, monomictic and multibasin lake; despite the low primary productivity, due to the abundante of sulphate in the water, the allochthonous inflow of organic matter and the inflow of water from bottom springs, the profunda1 environinent is very stressing for benthic fauna. Very low oxygen concentrations and high sulphide content in the water and sediments dueto meromixis mean that only the larva of the dipteran Chaohoi.lcs flai7icans was present in one of the 5 basins of the lake. In other basins, when oxygen is available (no meromixis), the fauna is similar to that of tlie inineralized lakes of the Aegean region and some lakes in central Italia. On the other hand, preliminary data from the Pyrenean lakes and from Sierra Nevada ponds reveal no differences with northern cold lakes. Tlie largest lakes in Spain are the reservoirs. There are nearly 1000 and data are available on 100 of them, including the kargest. In addition to oxygen and sulphide content in the bottom waters, water level fluctuation and high sedimentation rates are disturbance factors that prevented the organization of the community. Allochthonous inputs of organic matter are also an important factor both in the reservoirs and also in the small, oligotrophic lakes like Banyoles and Sanabria. As a result the meiofaunal loop is very important in many of the Spanish water bodies . For this reason the natural lakes and reservoirs of Spain are dominated by Oligochaeta, small crustaceans and the microcarnivore chironomids (such as Procladi~ls, Cladopelma and Mi(,rnc.hil-onnmus) that feed on these meoifaunal elements. The phytophagous chironomids, like Chironomus, are only abundan1 in the shallow areas of mesotrophic and eutrophic reservoirs. This situation makes it difficult to apply the typological system of SAETHER which predicts with some confidence only the benthic communities of Spanish natural lakes above 1500 m in the Pyrenees or the ponds above 2000 m in Sierra Nevada mountains. Higher temperatures (which originate a longer stratification period), the presence of sulphate in the waters of the eastern part of Spain and high inputs of sediments and allochthonous organic matter seem to be the factors that originated the differences between the benthic profunda1 faunas of Spanish lakes and reservoirs and those of the temperate lakes of north and central Europe.

Hydrology, light and the use of organic and inorganic materials as structuring factors of biological communities in Mediterranean streams

Hydrological disturbances, light availability and nutrients are the most relevant factors determining the structure of the biological communities in Mediterranean rivers. While some hydrological disturbances are able to induce catastrophic effects, which may cause a complete reset in physical and biological conditions, continued enrichment or changes in light availability are factors leading to the progressive shift in the communities of autotrophs and heterotrophs in the systems. Primary production in Mediterranean streams shows relevant seasonal changes which mainly follows the variations in light availability. In most forested streams, the algal community is shade-adapted. Nutrient enrichment (especially phosphorus) leads to marked increases in primary production, but this increase is not lineal and there is a saturation of algal biomass even in the most enriched systems. The heterotrophs (bacteria, fungi) are related to the pattern of DOC availability (which most depends on the seasonal discharge and leaf fall dynamics) and to the available substrata in the stream. It has been repeatedly observed that shorttime increases of extracellular enzyme activities are related to the accumulation of autochthonous (algal) and/or allochthonous (leaves) organic matter on the streambed during spring and summer, this being more remarkable in dry than in wetter years. Flow reduction favours detritus concentration in pools, and the subsequent increase in the density and biomass of the macroinvertebrate community. In Mediterranean streams collectors are accounting for the highest density and biomass, this being more remarkable in the least permanent systems, in accordance with the effect of floods on the organic matter availability. Nutrients, through the effect on the primary producers, also affect the trophic food web in the streams by favouring the predominance of grazers

Effects of inorganic nitrogen (NH4Cl) and biodegradable organic carbon (CH3COONa) additions on a pilot-scale seawater biofilter

Biofilters degrade only a small fraction of the natural organic matter (NOM) contained in seawater which is the leading cause of biofouling in downstream processes. This work studies the effects of chemical additions on NOM biodegradation by biofilters. In this work, biofiltration of seawater with an empty bed contact time (EBCT) of 6 min and a hydraulic loading rate of 10 m h-1 reduces the biological oxygen demand (BOD7) by 8%, the dissolved organic carbon (DOC) by 6% and the UV absorbance at 254 nm (A254) by 7%. Different amounts of ammonium chloride are added to the seawater (up to twice the total dissolved nitrogen in untreated seawater) to study its possible effect on the removal of NOM by a pilot-scale biofilter. Seawater is amended with different amounts of easily biodegradable dissolved organic carbon (BDOC) supplied as sodium acetate (up to twice the DOC) for the same purpose. The results of this work reveal that the ammonium chloride additions do not significantly affect NOM removal and the sodium acetate is completely consumed by the biofiltration process. For both types of chemical additions, the BOD7, DOC and A254 in the outlet stream of the biofilter are similar to the values for the untreated control. These results indicate that this biofilter easily removes the BDOC from the seawater when the EBCT is not above 6 min. Furthermore, nitrogen does not limit the NOM biodegradation in seawater under these experimental conditions.