Morphology and phosphate distribution in bottom ash particles from fixed-bed co-combustion of sewage sludge and two agricultural residues.

The purpose of this study was to provide detailed knowledge of the morphological properties of ash particles, including the volumetric fractions and 3D distributions of phosphates that lay within them. The ash particles came from digested sewage sludge co-combusted with K- and Si-rich wheat straw or K-rich sunflower husks. X-ray micro-tomography were combined with elemental composition and crystalline phase information to analyse the ash particles in 3D. Analyses of differences in the X-ray attenuation enabled calculation of 3D phosphate distributions that showed high heterogeneity in the slag particles. This is underscored by a distinct absence of phosphates in iron-rich and silicon-rich parts. The slag from silicate-based wheat straw mixtures had lower average attenuation than that from sunflower husks mixtures, which contained more calcium. Calculated shares of phosphates between 7 and 17 vol% were obtained, where the highest value for a single assigned phosphate was observed in hard slag from wheat straw with 10 % sewage sludge. The porosity was notably higher for particles from pure wheat straw combustion (62 vol%), compared to the other samples (15-35 vol%). A high open pore volume fraction (60-97 vol%) indicates that a large part of the pores can be accessed by the surroundings. For all samples, more than 60 % of the discrete (closed) pores had an equivalent diameter < 30 µm, while the largest volume fraction consisted of pores with an equivalent diameter > 75 µm. Slag from sunflower husk mixtures had larger pore volumes and a greater relative number of discrete pores >75 µm compared to wheat straw mixtures.

Ash Transformation during Fixed-Bed Co-combustion of Sewage Sludge and Agricultural Residues with a Focus on Phosphorus.

This work investigates the ash transformation during fixed-bed co-combustion of sewage sludge mixtures with the agricultural residues wheat straw and sunflower husks, focusing on the fate of phosphorus (P) in the resulting ash fractions. The study aims to determine suitable process parameters for fixed-bed combustion of fuels previously investigated in single-pellet experiments. The pure fuels and fuel mixtures were combusted in a 20 kWth residential pellet burner while monitoring the flue gas composition, temperature, and particulate matter formation. Subsequently, the different ash fractions were collected and characterized by CHN, SEM/EDS, and XRD analysis. The results showed that co-combustion of sewage sludge and agricultural residues reduced the formation of particulate matter as well as the formation of slag. Co-combustion of sewage sludge with either agricultural residue resulted in a change in phosphate speciation, displaying higher shares of Ca and lower shares of Fe and Al in the formed orthophosphates as well as amorphous phases containing higher shares of K. The formation of K-bearing phosphates was hindered by the spatial association of P with Ca and Fe in the sewage sludge, the incorporation of available K in K-Al silicates, and the depletion of K in the P-rich melt phase. Compared to mono-combustion, co-combustion experiments showed the potential for improving the combustion performance and reducing the risk of slag formation. The outcome suggests that co-combustion is a feasible path to integrate waste streams in fixed-bed energy conversion with simultaneous formation of phosphates enabling P recovery.

Leaching of metal(loid)s from ashes of spent sorbent and stabilisation effect of calcium-rich additives.

Contaminated water with multiple contaminants, including As, Cr, Cu and Zn, was treated with a sorbent prepared by coating peat with Fe oxides. Because As has a relatively little explored market, the regeneration of the spent sorbent was not feasible. Meanwhile, the disposal of As wastes in landfills can cause landfill leachate treatment problems. Under the reducing conditions prevailing at landfills, As(V) is reduced to As(III), which is a toxic and more mobile form. In this study, incineration was explored as a management option to treat the spent sorbent that was loaded with As, Cr, Cu and Zn. The first objective of this study was to evaluate the leaching of these metal(loid)s from the ashes and compare it with the leaching from the spent sorbents before incineration. The second objective was to evaluate the leaching behaviour when the spent sorbent was co-incinerated with a Ca-rich additive (lime). To achieve these objectives, the obtained ashes were subjected to leaching tests, sequential extraction, and X-ray diffraction analyses. After the incineration, the ash content ranged from 9 to 19% of the initial mass of the spent sorbents. The leaching of As, Cu and Zn decreased compared with that from the spent sorbents before the thermal treatment because of the high incineration temperatures and/or co-incineration with lime. However, the leaching of Cr increased, which would hinder the disposal of the obtained ashes in a landfill because the limit value for disposal at a landfill for hazardous wastes was exceeded by 50 times. However, co-incineration with 10 wt% lime significantly decreased the leaching of Cr as a result of the formation of water-insoluble Ca-Cr compounds.

Combustion of Biosolids in a Bubbling Fluidized Bed, Part 1: Main Ash-Forming Elements and Ash Distribution with a Focus on Phosphorus.

This is the first in a series of three papers describing combustion of biosolids in a 5-kW bubbling fluidized bed, the ash chemistry, and possible application of the ash produced as a fertilizing agent. This part of the study aims to clarify whether the distribution of main ash forming elements from biosolids can be changed by modifying the fuel matrix, the crystalline compounds of which can be identified in the raw materials and what role the total composition may play for which compounds are formed during combustion. The biosolids were subjected to low-temperature ashing to investigate which crystalline compounds that were present in the raw materials. Combustion experiments of two different types of biosolids were conducted in a 5-kW benchscale bubbling fluidized bed at two different bed temperatures and with two different additives. The additives were chosen to investigate whether the addition of alkali (K2CO3) and alkaline-earth metal (CaCO3) would affect the speciation of phosphorus, so the molar ratios targeted in modified fuels were P:K = 1:1 and P:K:Ca = 1:1:1, respectively. After combustion the ash fractions were collected, the ash distribution was determined and the ash fractions were analyzed with regards to elemental composition (ICP-AES and SEM-EDS) and part of the bed ash was also analyzed qualitatively using XRD. There was no evidence of zeolites in the unmodified fuels, based on low-temperature ashing. During combustion, the biosolid pellets formed large bed ash particles, ash pellets, which contained most of the total ash content (54%-95% (w/w)). This ash fraction contained most of the phosphorus found in the ash and the only phosphate that was identified was a whitlockite, Ca9(K,Mg,Fe)(PO4)7, for all fuels and fuel mixtures. With the addition of potassium, cristobalite (SiO2) could no longer be identified via X-ray diffraction (XRD) in the bed ash particles and leucite (KAlSi2O6) was formed. Most of the alkaline-earth metals calcium and magnesium were also found in the bed ash. Both the formation of aluminum-containing alkali silicates and inclusion of calcium and magnesium in bed ash could assist in preventing bed agglomeration during co-combustion of biosolids with other renewable fuels in a full-scale bubbling fluidized bed.

Characterization of Scots pine stump-root biomass as feed-stock for gasification.

The main objective was to explore the potential for gasifying Scots pine stump-root biomass (SRB). Washed thin roots, coarse roots, stump heartwood and stump sapwood were characterized (solid wood, milling and powder characteristics) before and during industrial processing. Non-slagging gasification of the SRB fuels and a reference stem wood was successful, and the gasification parameters (synthesis gas and bottom ash characteristics) were similar. However, the heartwood fuel had high levels of extractives (≈19%) compared to the other fuels (2-8%) and thereby ≈16% higher energy contents but caused disturbances during milling, storage, feeding and gasification. SRB fuels could be sorted automatically according to their extractives and moisture contents using near-infrared spectroscopy, and their amounts and quality in forests can be predicted using routinely collected stand data, biomass functions and drill core analyses. Thus, SRB gasification has great potential and the proposed characterizations exploit it.

Methacrylate monolithic stationary phases for gradient elution separations in microfluidic devices.

Methacrylate monolithic stationary phases were produced in fused-silica chips by UV initiation. Poly(butyl methacrylate-co-ethylene dimethacrylate) (BMA) and poly(lauryl methacrylate-co-ethylene dimethacrylate) (LMA) monoliths containing 30, 35 and 40% monomers were evaluated for the separation of peptides under gradient conditions. The peak capacity was used as an objective tool for the evaluation of the separation performance. LMA monoliths of the highest density gave the highest peak capacities (≈40) in gradients of 15 min and all LMA monoliths gave higher peak capacities than the BMA monoliths with the same percentage of monomers. Increasing the gradient duration to 30 min did not increase the peak capacity significantly. However, running fast (5 min) gradients provides moderate peak capacities (≈20) in a short time. Due to the system dead volume of 1 µL and the low bed volume of the chip, early eluting peptides migrated over a significant part of the column during the dwell time under isocratic conditions. It was shown that this could explain an increased band broadening on the monolithic stationary phase materials used. The effect is stronger with BMA monoliths, which partly explains the inferior performance of this material with respect to peak capacity. The configuration of the connections on the chip appeared to be critical when fast analyses were performed at pressures above 20 bar.

Extinction vulnerability of coral reef fishes.

With rapidly increasing rates of contemporary extinction, predicting extinction vulnerability and identifying how multiple stressors drive non-random species loss have become key challenges in ecology. These assessments are crucial for avoiding the loss of key functional groups that sustain ecosystem processes and services. We developed a novel predictive framework of species extinction vulnerability and applied it to coral reef fishes. Although relatively few coral reef fishes are at risk of global extinction from climate disturbances, a negative convex relationship between fish species locally vulnerable to climate change vs. fisheries exploitation indicates that the entire community is vulnerable on the many reefs where both stressors co-occur. Fishes involved in maintaining key ecosystem functions are more at risk from fishing than climate disturbances. This finding is encouraging as local and regional commitment to fisheries management action can maintain reef ecosystem functions pending progress towards the more complex global problem of stabilizing the climate.

Methacrylate monolithic capillary columns for gradient peptide separations.

For the separation of peptides with gradient-elution liquid chromatography a poly(butyl methacrylate-co-ethylene dimethacrylate) (BMA) monolithic capillary column was prepared and tested. The conditional peak capacity was used as a metric for the performance of this column, which was compared with a capillary column packed with C18-modified silica particles. The retention of the peptides was found to be smaller on the BMA column than on the particulate C18 column. To obtain the same retention in isocratic elution an approximately 15% (v/v) lower acetonitrile concentration had to be used in the mobile phase. The retention window in gradient elution was correspondingly smaller with the BMA column. The relation between peak width and retention under gradient conditions was studied in detail. It was found that in shallow gradients, with gradient times of 30min and more, the peak widths of the least retained compounds are strongly increased with the BMA column. This was attributed to the fact that these compounds migrate and elute with an unfavorable high retention factor. More retained compounds are eluted later in the gradient, but with a lower effective retention factor. With shallow gradients the peak capacity of the BMA column ( approximately 90) was clearly lower than that of a conventional packed column ( approximately 150). On the other hand, with steep gradients, when components elute with a low effective retention factor, the performance of the BMA column is relatively good. With a gradient time of 15min similar peak widths and thus similar peak capacities ( approximately 75) were found for the packed and the monolithic column. Two strategies were investigated to obtain higher peak capacities with methacrylate monolithic columns. The use of lauryl methacrylate (LMA) instead of butyl methacrylate (BMA) gave an increase in retention and narrower peaks for early eluting peptides. The peak capacity of the LMA column was approximately 125 in a 60min gradient. Another approach was to use a longer BMA column which resulted in a peak capacity of approximately 135 could be obtained in 60min.

Climate warming, marine protected areas and the ocean-scale integrity of coral reef ecosystems.

Coral reefs have emerged as one of the ecosystems most vulnerable to climate variation and change. While the contribution of a warming climate to the loss of live coral cover has been well documented across large spatial and temporal scales, the associated effects on fish have not. Here, we respond to recent and repeated calls to assess the importance of local management in conserving coral reefs in the context of global climate change. Such information is important, as coral reef fish assemblages are the most species dense vertebrate communities on earth, contributing critical ecosystem functions and providing crucial ecosystem services to human societies in tropical countries. Our assessment of the impacts of the 1998 mass bleaching event on coral cover, reef structural complexity, and reef associated fishes spans 7 countries, 66 sites and 26 degrees of latitude in the Indian Ocean. Using Bayesian meta-analysis we show that changes in the size structure, diversity and trophic composition of the reef fish community have followed coral declines. Although the ocean scale integrity of these coral reef ecosystems has been lost, it is positive to see the effects are spatially variable at multiple scales, with impacts and vulnerability affected by geography but not management regime. Existing no-take marine protected areas still support high biomass of fish, however they had no positive affect on the ecosystem response to large-scale disturbance. This suggests a need for future conservation and management efforts to identify and protect regional refugia, which should be integrated into existing management frameworks and combined with policies to improve system-wide resilience to climate variation and change.

Offshore windmills and the effects of electromagnetic fields on fish.

With the large scale developments of offshore windpower the number of underwater electric cables is increasing with various technologies applied. A wind farm is associated with different types of cables used for intraturbine, array-to-transformer, and transformer-to-shore transmissions. As the electric currents in submarine cables induce electromagnetic fields there is a concern of how they may influence fishes. Studies have shown that there are fish species that are magneto-sensitive using geomagnetic field information for the purpose of orientation. This implies that if the geomagnetic field is locally altered it could influence spatial patterns in fish. There are also physiological aspects to consider, especially for species that are less inclined to move as the exposure could be persistent in a particular area. Even though studies have shown that magnetic fields could affect fish, there is at present limited evidence that fish are influenced by the electromagnetic fields that underwater cables from windmills generate. Studies on European eel in the Baltic Sea have indicated some minor effects. In this article we give an overview on the type of submarine cables that are used for electric transmissions in the sea. We also describe the character of the magnetic fields they induce. The effects of magnetic fields on fish are reviewed and how this may relate to the cables used for offshore wind power is discussed.

Determination of flavonoids in citrus juices by micro-HPLC-ESI/MS.

Flavonoids are a large class of naturally occurring aromatic secondary plant metabolites. They constitute one of the most characteristic classes found in nature and more than 4000 flavonoids have been identified and divided into several subclasses. Flavonoids have several effects on human health, mainly related to their antioxidant activity. As a result of the increased interest in the biologically active compounds in food, many research studies have investigated the detection and quantification of antioxidants. Citrus plants are of great interest since they accumulate large amounts of flavonoids and fruit and juices of these species are consumed in large quantities. Despite the extensive research performed on Citrus flavonoids, many compounds still remain unidentified. In this work, flavonoids of five citrus juices: lemon, grapefruit, bergamot, orange, and mandarin were analyzed by microHPLC coupled on-line with an MS detector equipped with an ESI source operating in negative mode. The use of microcolumn HPLC greatly enhanced detection performance. In total, 20 flavonoids of two different subclasses (flavanone and flavone glycosides) were identified with the help of retention data and MS spectral information.

Comparison of native and recombinant chlorite dismutase from Ideonella dechloratans.

A detailed comparison between native chlorite dismutase from Ideonella dechloratans, and the recombinant version of the protein produced in Escherichia coli, suggests the presence of a covalent modification in the native enzyme. Although the native and recombinant N- and C-terminal sequences are identical, the enzymes display different electrophoretic mobilities, and produce different peptide maps upon digestion with trypsin and separation of fragments using capillary electrophoresis. Comparison of MALDI mass spectra of tryptic peptides from the native and recombinant enzymes suggests two locations for modification in the native protein. Mass spectrometric analysis of isolated peptides from a tryptic digest of the native enzyme identifies a possible cross-linked dipeptide, suggesting an intrachain cross-link in the parent protein. Spectrophotometric titration of the native enzyme in the denatured state reveals two titrating components absorbing at 295 nm, suggesting the presence of about one tyrosine residue per subunit with an anomalously low pK(a). The EPR spectrum for the recombinant enzyme is different from that of the native enzyme, and contains a substantial contribution of a low-spin species with the characteristics of bis-histidine coordination. These results are discussed in terms of a covalent cross-link between a histidine and a tyrosine sidechain, similar to those found in other heme enzymes operating under highly oxidizing conditions.

Separation of conjugated trienoic fatty acid isomers by capillary electrophoresis.

A method for direct resolution of conjugated trienoic fatty acid isomers by capillary electrophoresis has been developed. To obtain complete separation a dual cyclodextrin system was used. This contained heptakis-(6-sulfo)-beta-cyclodextrin (charged). Beta-cyclodextrin (uncharged) and sodium dodecylsulfate. Under optimized conditions, all seven isomers were well separated. On average, separation efficiency was 2.9 x 10(5) plates/m.

Marine fisheries in Tanzania.

Fishery resources are a vital source of food and make valuable economic contributions to the local communities involved in fishery activities along the 850 km stretch of the Tanzania coastline and numerous islands. Small-scale artisanal fishery accounts for the majority of fish catch produced by more than 43 000 fishermen in the country, mainly operating in shallow waters within the continental shelf, using traditional fishing vessels including small boats, dhows, canoes, outrigger canoes and dinghys. Various fishing techniques are applied using uncomplicated passive fishing gears such as basket traps, fence traps, nets as well as different hook and line techniques. Species composition and size of the fish varies with gear type and location. More than 500 species of fish are utilized for food with reef fishes being the most important category including emperors, snappers, sweetlips, parrotfish, surgeonfish, rabbitfish, groupers and goatfish. Most of the fish products are used for subsistence purposes. However, some are exported. Destructive fishing methods such as drag nets and dynamite fishing pose a serious problem as they destroy important habitats for fish and other organisms, and there is a long-term trend of overharvested fishery resources. However, fishing pressure varies within the country as fishery resources are utilized in a sustainable manner in some areas. For this report more than 340 references about Tanzanian fishery and fish ecology were covered. There are many gaps in terms of information needed for successful fishery management regarding both basic and applied research. Most research results have been presented as grey literature (57%) with limited distribution; only one-fifth were scientific publications in international journals.

Environmental effects on the distribution of corallimorpharians in Tanzania.

This study examined the distribution and abundance of corallimorpharians (Cnidaria, Anthozoa) in Tanzania in relation to different aspects of the coral reef environment. Five reefs under varying degrees of human disturbance were investigated using the line intercept transect and point technique. Corallimorpharian growth and the composition of the substratum were quantified in different habitats within reefs: the inner and middle reef flat, the reef crest, and at the 2 and 4 m depths on the reef slope. Corallimorpharians occurred on all the reefs and 5 species were identified: Rhodactis rhodostoma, R. mussoides, Ricordea yuma, Actinodiscus unguja and A. nummiforme. R. rhodostoma was the dominant corallimorpharian at all sites. Within reefs, they had the highest densities in the shallow habitats. While R. rhodostoma occurred in all habitats, the other corallimorpharian species showed uneven distributions. Corallimorpharians ranked second, after scleractinian coral, in percent living cover. Results from this study suggested that corallimorpharians benefitted from disturbance compared with other sessile organisms. They preferred inhabiting areas with dead coral, rock and rubble whilst live coral was avoided. There was a positive relationship between percent cover of corallimorpharians and water turbidity and they dominated the more disturbed reefs, i.e. reefs that were affected by higher nutrient loads and fishing.

Seagrass ecosystems in the Western Indian Ocean.

Seagrasses are marine angiosperms widely distributed in both tropical and temperate coastal waters creating one of the most productive aquatic ecosystems on earth. In the Western Indian Ocean (WIO) region, with its 13 reported seagrass species, these ecosystems cover wide areas of near-shore soft bottoms through the 12 000 km coastline. Seagrass beds are found intertidally as well as subtidally, sometimes down to about 40 m, and do often occur in close connection to coral reefs and mangroves. Due to the high primary production and a complex habitat structure, seagrass beds support a variety of benthic, demersal and pelagic organisms. Many fish and shellfish species, including those of commercial interest, are attracted to seagrass habitats for foraging and shelter, especially during their juvenile life stages. Examples of abundant and widespread fish species associated to seagrass beds in the WIO belong to the families Apogonidae, Blenniidae, Centriscidae, Gerreidae, Gobiidae, Labridae, Lethrinidae Lutjanidae, Monacanthidae, Scaridae, Scorpaenidae, Siganidae, Syngnathidae and Teraponidae. Consequently, seagrass ecosystems in the WIO are valuable resources for fisheries at both local and regional scales. Still, seagrass research in the WIO is scarce compared to other regions and it is mainly focusing on botanic diversity and ecology. This article reviews the research status of seagrass beds in the WIO with particular emphasis on fish and fisheries. Most research on this topic has been conducted along the East African coast, i.e. in Kenya, Tanzania, Mozambique and eastern South Africa, while less research was carried out in Somalia and the Island States of the WIO (Seychelles, Comoros, Reunion (France), Mauritius and Madagascar). Published papers on seagrass fish ecology in the region are few and mainly descriptive. Hence, there is a need of more scientific knowledge in the form of describing patterns and processes through both field and experimental work. Quantitative seagrass fish community studies in the WIO such as the case study presented in this paper are negligible, but necessitated for the perspective of fisheries management. It is also highlighted that the pressure on seagrass beds in the region is increasing due to growing coastal populations and human disturbance from e.g. pollution, eutrophication, sedimentation, fishing activities and collection of invertebrates, and its effect are little understood. Thus, there is a demand for more research that will generate information useful for sustainable management of seagrass ecosystems in the WIO.