The Ocean Colour Climate Change Initiative: III. A round-robin comparison on in-water bio-optical algorithms

Satellite-derived remote-sensing reflectance (Rrs) can be used for mapping biogeochemically relevant variables, such as the chlorophyll concentration and the Inherent Optical Properties (IOPs) of the water, at global scale for use in climate-change studies. Prior to generating such products, suitable algorithms have to be selected that are appropriate for the purpose. Algorithm selection needs to account for both qualitative and quantitative requirements. In this paper we develop an objective methodology designed to rank the quantitative performance of a suite of bio-optical models. The objective classification is applied using the NASA bio-Optical Marine Algorithm Dataset (NOMAD). Using in situRrs as input to the models, the performance of eleven semi-analytical models, as well as five empirical chlorophyll algorithms and an empirical diffuse attenuation coefficient algorithm, is ranked for spectrally-resolved IOPs, chlorophyll concentration and the diffuse attenuation coefficient at 489 nm. The sensitivity of the objective classification and the uncertainty in the ranking are tested using a Monte-Carlo approach (bootstrapping). Results indicate that the performance of the semi-analytical models varies depending on the product and wavelength of interest. For chlorophyll retrieval, empirical algorithms perform better than semi-analytical models, in general. The performance of these empirical models reflects either their immunity to scale errors or instrument noise in Rrs data, or simply that the data used for model parameterisation were not independent of NOMAD. Nonetheless, uncertainty in the classification suggests that the performance of some semi-analytical algorithms at retrieving chlorophyll is comparable with the empirical algorithms. For phytoplankton absorption at 443 nm, some semi-analytical models also perform with similar accuracy to an empirical model. We discuss the potential biases, limitations and uncertainty in the approach, as well as additional qualitative considerations for algorithm selection for climate-change studies. Our classification has the potential to be routinely implemented, such that the performance of emerging algorithms can be compared with existing algorithms as they become available. In the long-term, such an approach will further aid algorithm development for ocean-colour studies.

An intercomparison of bio-optical techniques for detecting dominant phytoplankton size class from satellite remote sensing

Satellite remote sensing of ocean colour is the only method currently available for synoptically measuring wide-area properties of ocean ecosystems, such as phytoplankton chlorophyll biomass. Recently, a variety of bio-optical and ecological methods have been established that use satellite data to identify and differentiate between either phytoplankton functional types (PFTs) or phytoplankton size classes (PSCs). In this study, several of these techniques were evaluated against in situ observations to determine their ability to detect dominant phytoplankton size classes (micro-, nano- and picoplankton). The techniques are applied to a 10-year ocean-colour data series from the SeaWiFS satellite sensor and compared with in situ data (6504 samples) from a variety of locations in the global ocean. Results show that spectral-response, ecological and abundance-based approaches can all perform with similar accuracy. Detection of microplankton and picoplankton were generally better than detection of nanoplankton. Abundance-based approaches were shown to provide better spatial retrieval of PSCs. Individual model performance varied according to PSC, input satellite data sources and in situ validation data types. Uncertainty in the comparison procedure and data sources was considered. Improved availability of in situ observations would aid ongoing research in this field.

Large bio-geographical shifts in the north-eastern Atlantic Ocean: From the subpolar gyre, via plankton, to blue whiting and pilot whales

Pronounced changes in fauna, extending from the English Channel in the south to the Barents Sea in the north-east and off Greenland in the north-west, have occurred in the late 1920s, the late 1960s and again in the late 1990s. We attribute these events to exchanges of subarctic and subtropical water masses in the north-eastern North Atlantic Ocean, associated with changes in the strength and extent of the subpolar gyre. These exchanges lead to variations in the influence exerted by the subarctic or Lusitanian biomes on the intermediate faunistic zone in the north-eastern Atlantic. This strong and persistent bottom-up bio-physical link is demonstrated using a numerical ocean general circulation model and data on four trophically connected levels in the food chain – phytoplankton, zooplankton, blue whiting, and pilot whales. The plankton data give a unique basin-scale depiction of these changes, and a long pilot whale record from the Faroe Islands offers an exceptional temporal perspective over three centuries. Recent advances in simulating the dynamics of the subpolar gyre suggests a potential for predicting the distribution of the main faunistic zones in the north-eastern Atlantic a few years into the future, which might facilitate a more rational management of the commercially important fisheries in this region.

Effect of phytoplankton size classes on bio-optical properties of phytoplankton in the Western Iberian coast: Application of models

Chlorophyll-a satellite products are routinely used in oceanography, providing a synoptic and global view of phytoplankton abundance. However, these products lack information on the community structure of the phytoplankton, which is crucial for ecological modelling and ecosystem studies. To assess the usefulness of existing methods to differentiate phytoplankton functional types (PFT) or phytoplankton size classes from satellite data, in-situ phytoplankton samples collected in the Western Iberian coast, on the North-East Atlantic, were analysed for pigments and absorption spectra. Water samples were collected in five different locations, four of which were located near the shore and another in an open-ocean, seamount region. Three different modelling approaches for deriving phytoplankton size classes were applied to the in situ data. Approaches tested provide phytoplankton size class information based on the input of pigments data (Brewin et al., 2010), absorption spectra data (Ciotti et al., 2002) or both (Uitz et al., 2008). Following Uitz et al. (2008), results revealed high variability in microphytoplankton chlorophyll-specific absorption coefficients, ranging from 0.01 to 0.09 m2 (mg chl)− 1 between 400 and 500 nm. This spectral analysis suggested, in one of the regions, the existence of small cells (< 20 μm) in the fraction of phytoplankton presumed to be microphytoplankton (based on diagnostic pigments). Ciotti et al. (2002) approach yielded the highest differences between modelled and measured absorption spectra for the locations where samples had high variability in community structure and cell size. The Brewin et al. (2010) pigment-based model was adjusted and a set of model coefficients are presented and recommended for future studies in offshore water of the Western Iberian coast.

Steam reforming of model compounds and fast pyrolysis bio-oil on supported noble metal catalysts

The production of hydrogen by steam reforming of bio-oils obtained from the fast pyrolysis of biomass requires the development of efficient catalysts able to cope with the complex chemical nature of the reactant. The present work focuses on the use of noble metal-based catalysts for the steam reforming of a few model compounds and that of an actual bio-oil. The steam reforming of the model compounds was investigated in the temperature range 650-950 degrees C over Pt, Pd and Rh supported on alumina and a ceria-zirconia sample. The model compounds used were acetic acid, phenol, acetone and ethanol. The nature of the support appeared to play a significant role in the activity of these catalysts. The use of ceria-zirconia, a redox mixed oxide, lead to higher H-2 yields as compared to the case of the alumina-supported catalysts. The supported Rh and Pt catalysts were the most active for the steam reforming of these compounds, while Pd-based catalysts poorly performed. The activity of the promising Pt and Rh catalysts was also investigated for the steam reforming of a bio-oil obtained from beech wood fast pyrolysis. Temperatures close to, or higher than, 800 degrees C were required to achieve significant conversions to COx and H-2 (e.g., H-2 yields around 70%). The ceria-zirconia materials showed a higher activity than the corresponding alumina samples. A Pt/ceria-zirconia sample used for over 9 h showed essentially constant activity, while extensive carbonaceous deposits were observed on the quartz reactor walls from early time on stream. In the present case, no benefit was observed by adding a small amount of O-2 to the steam/bio-oil feed (autothermal reforming, ATR), probably partly due to the already high concentration of oxygen in the bio-oil composition. (c) 2005 Elsevier B.V. All rights reserved.

Dilute acid hydrolysis of cellulose and cellulosic bio-waste using a microwave reactor system

The dilute acid hydrolysis of grass and cellulose with phosphoric acid was undertaken in a microwave reactor system. The experimental data and reaction kinetic analysis indicate that this is a potential process for cellulose and hemi-cellulose hydrolysis, due to a rapid hydrolysis reaction at moderate temperatures. The optimum conditions for grass hydrolysis were found to be 2.5% phosphoric acid at a temperature of 175 degrees C. It was found that sugar degradation occurred at acid concentrations greater than 2.5% (v/v) and temperatures greater than 175 degrees C. In a further series of experiments, the kinetics of dilute acid hydrolysis of cellulose was investigated varying phosphoric acid concentration and reaction temperatures. The experimental data indicate that the use of microwave technology can successfully facilitate dilute acid hydrolysis of cellulose allowing high yields of glucose in short reaction times. The optimum conditions gave a yield of 90% glucose. A pseudo-homogeneous consecutive first order reaction was assumed and the reaction rate constants were calculated as: k(1) = 0.0813 s(-1); k(2) = 0.0075 s(-1), which compare favourably with reaction rate constants found in conventional non-microwave reaction systems. The kinetic analysis would indicate that the primary advantages of employing microwave heating were to: achieve a high rate constant at moderate temperatures: and to prevent 'hot spot' formation within the reactor, which would have cause localised degradation of glucose.