Effects of CO2 enrichment on photosynthesis, growth, and nitrogen metabolism of the seagrass Zostera noltii

Seagrass ecosystems are expected to benefit from the global increase in CO2 in the ocean because the photosynthetic rate of these plants may be Ci-limited at the current CO2 level. As well, it is expected that lower external pH will facilitate the nitrate uptake of seagrasses if nitrate is cotransported with H+ across the membrane as in terrestrial plants. Here, we investigate the effects of CO2 enrichment on both carbon and nitrogen metabolism of the seagrass Zostera noltii in a mesocosm experiment where plants were exposed for 5 months to two experimental CO2 concentrations (360 and 700 ppm). Both the maximum photosynthetic rate (Pm) and photosynthetic efficiency (a) were higher (1.3- and 4.1-fold, respectively) in plants exposed to CO2-enriched conditions. On the other hand, no significant effects of CO2 enrichment on leaf growth rates were observed, probably due to nitrogen limitation as revealed by the low nitrogen content of leaves. The leaf ammonium uptake rate and glutamine synthetase activity were not significantly affected by increased CO2 concentrations. On the other hand, the leaf nitrate uptake rate of plants exposed to CO2-enriched conditions was fourfold lower than the uptake of plants exposed to current CO2 level, suggesting that in the seagrass Z. noltii nitrate is not cotransported with H+ as in terrestrial plants. In contrast, the activity of nitrate reductase was threefold higher in plant leaves grown at high-CO2 concentrations. Our results suggest that the global effects of CO2 on seagrass production may be spatially heterogeneous and depend on the specific nitrogen availability of each system. Under a CO2 increase scenario, the natural levels of nutrients will probably become limiting for Z. noltii. This potential limitation becomes more relevant because the expected positive effect of CO2 increase on nitrate uptake rate was not confirmed.

Responses of three tropical seagrass species to CO2 enrichment

Increased atmospheric carbon dioxide leads to ocean acidification and carbon dioxide (CO2) enrichment of seawater. Given the important ecological functions of seagrass meadows, understanding their responses to CO2 will be critical for the management of coastal ecosystems. This study examined the physiological responses of three tropical seagrasses to a range of seawater pCO2 levels in a laboratory. Cymodocea serrulata, Halodule uninervis and Thalassia hemprichii were exposed to four different pCO2 treatments (442-1204 µatm) for 2 weeks, approximating the range of end-of-century emission scenarios. Photosynthetic responses were quantified using optode-based oxygen flux measurements. Across all three species, net productivity and energetic surplus (PG:R) significantly increased with a rise in pCO2 (linear models, P < 0.05). Photosynthesis-irradiance curve-derived photosynthetic parameters-maximum photosynthetic rates (P max) and efficiency (alpha) also increased as pCO2 increased (linear models, P < 0.05). The response for productivity measures was similar across species, i.e. similar slopes in linear models. A decrease in compensation light requirement (Ec) with increasing pCO2 was evident in C. serrulata and H. uninervis, but not in T. hemprichii. Despite higher productivity with pCO2 enrichment, leaf growth rates in C. serrulata did not increase, while those in H. uninervis and T. hemprichii significantly increased with increasing pCO2 levels. While seagrasses can be carbon-limited and productivity can respond positively to CO2 enrichment, varying carbon allocation strategies amongst species suggest differential growth response between species. Thus, future increase in seawater CO2 concentration may lead to an overall increase in seagrass biomass and productivity, as well as community changes in seagrass meadows.

PeECE II - Pelagic Ecosystem CO2 Enrichment Study, Raunefjord, Bergen, Norway

The effects of CO2-induced seawater acidification on plankton communities were also addressed in a series of 3 mesocosm experiments, called the Pelagic Ecosystem CO2 Enrichment (PeECE I-III) studies, which were conducted in the Large-Scale Mesocosm Facilities of the University of Bergen, Norway in 2001, 2003 and 2005, respectively. Each experiment consisted of 9 mesocosms, in which CO2 was manipulated to initial concentrations of 190, 350 and 750 µatm in 2001 and 2003, and 350, 700 and 1050 µatm in 2005. The present dataset concerns PeECE II.

PeECE III - Pelagic Ecosystem CO2 Enrichment Study, Raunefjord, Bergen, Norway, 2005

The effects of CO2-induced seawater acidification on plankton communities were also addressed in a series of 3 mesocosm experiments, called the Pelagic Ecosystem CO2 Enrichment (PeECE I-III) studies, which were conducted in the Large-Scale Mesocosm Facilities of the University of Bergen, Norway in 2001, 2003 and 2005, respectively. Each experiment consisted of 9 mesocosms, in which CO2 was manipulated to initial concentrations of 190, 350 and 750 µatm in 2001 and 2003, and 350, 700 and 1050 µatm in 2005. The present dataset concerns PeECE III.

Ferredoxin-dependent glutamate synthase: involvement in ammonium assimilation in Haloferax mediterranei

Glutamate synthase (GOGAT) is one of the two important enzymes involved in the ammonium assimilation pathway glutamine synthetase (GS)/GOGAT, which enables Hfx. mediterranei to thrive in media with low ammonium concentration or containing just nitrate as single nitrogen source. The gene coding for this enzyme, gltS, has been sequenced, analysed and compared with other GOGATs from different organisms from the three domains of life. According to its amino acid sequence, Hfx. mediterranei GOGAT displays high homology with those from other archaeal halophilic organisms and with the bacterial alpha-like subunit. Hfx. mediterranei GOGAT and GS expression was induced under conditions of ammonium restriction. The GOGAT protein was found to be a monomer with a molecular mass of 163.78 kDa, which is consistent with that estimated by gel filtration, 198 ± 30 kDa. The enzyme is highly ferredoxin dependent: activity was only observed with one of the two different 2Fe–2S ferredoxins chromatographically isolated from Hfx. mediterranei. The enzyme also displayed typical halophilic behaviour, being fully stable, and producing maximal activity, at salt concentrations from 3 to 4 M NaCl, pH 7.5 and a temperature of 50 °C.

Analysis of N-nitrosames in water using micellar electrokinetic chromatography (MEKC) and development of online and offline methods of extraction and enrichment of neutral polar analytes

Evaluation of the quality of the environment is essential for human wellness as pollutants in trace amounts can cause serious health problem. Nitrosamines are a group of compounds that are considered potential carcinogens and can be found in drinking water (as disinfection byproducts), foods, beverages and cosmetics. To monitor the level of these compounds to minimize daily intakes, fast and reliable analytical techniques are required. As these compounds are relatively highly polar, extraction and enrichment from environmental samples (aqueous) are challenging. Also, the trend of analytical techniques toward the reduction of sample size and minimization of organic solvent use demands new methods of analysis. In light of fulfilling these requirements, a new method of online preconcentration tailored to an electrokinetic chromatography is introduced. In this method, electroosmotic flow (EOF) was suppressed to increase the interaction time between analyte and micellar phase, therefore the only force to mobilize the neutral analytes is the interaction of analyte with moving micelles. In absence of EOF, polarity of applied potential was switched (negative or positive) to force (anionic or cationic) micelles to move toward the detector. To avoid the excessive band broadening due to longer analysis time caused by slow moving micelles, auxiliary pressure was introduced to boost the micelle movement toward the detector using an in house designed and built apparatus. Applying the external auxiliary pressure significantly reduced the analysis times without compromising separation efficiency. Parameters, such as type of surfactants, composition of background electrolyte (BGE), type of capillary, matrix effect, organic modifiers, etc., were evaluated in optimization of the method. The enrichment factors for targeted analytes were impressive, particularly; cationic surfactants were shown to be suitable for analysis of nitrosamines due to their ability to act as hydrogen bond donors. Ammonium perfluorooctanoate (APFO) also showed remarkable results in term of peak shapes and number of theoretical plates. It was shown that the separation results were best when a high conductivity sample was paired with a BGE of lower conductivity. Using higher surfactant concentrations (up to 200 mM SDS) than usual (50 mM SDS) for micellar electrokinetic chromatography (MEKC) improved the sweeping. A new method for micro-extraction and enrichment of highly polar neutral analytes (N-Nitrosamines in particular) based on three-phase drop micro-extraction was introduced and its performance studied. In this method, a new device using some easy-to-find components was fabricated and its operation and application demonstrated. Compared to conventional extraction methods (liquid-liquid extraction), consumption of organic solvents and operation times were significantly lower.

Information enrichment for quality recommender systems

The explosive growth of the World-Wide-Web and the emergence of ecommerce are the major two factors that have led to the development of recommender systems (Resnick and Varian, 1997). The main task of recommender systems is to learn from users and recommend items (e.g. information, products or books) that match the users’ personal preferences. Recommender systems have been an active research area for more than a decade. Many different techniques and systems with distinct strengths have been developed to generate better quality recommendations. One of the main factors that affect recommenders’ recommendation quality is the amount of information resources that are available to the recommenders. The main feature of the recommender systems is their ability to make personalised recommendations for different individuals. However, for many ecommerce sites, it is difficult for them to obtain sufficient knowledge about their users. Hence, the recommendations they provided to their users are often poor and not personalised. This information insufficiency problem is commonly referred to as the cold-start problem. Most existing research on recommender systems focus on developing techniques to better utilise the available information resources to achieve better recommendation quality. However, while the amount of available data and information remains insufficient, these techniques can only provide limited improvements to the overall recommendation quality. In this thesis, a novel and intuitive approach towards improving recommendation quality and alleviating the cold-start problem is attempted. This approach is enriching the information resources. It can be easily observed that when there is sufficient information and knowledge base to support recommendation making, even the simplest recommender systems can outperform the sophisticated ones with limited information resources. Two possible strategies are suggested in this thesis to achieve the proposed information enrichment for recommenders: • The first strategy suggests that information resources can be enriched by considering other information or data facets. Specifically, a taxonomy-based recommender, Hybrid Taxonomy Recommender (HTR), is presented in this thesis. HTR exploits the relationship between users’ taxonomic preferences and item preferences from the combination of the widely available product taxonomic information and the existing user rating data, and it then utilises this taxonomic preference to item preference relation to generate high quality recommendations. • The second strategy suggests that information resources can be enriched simply by obtaining information resources from other parties. In this thesis, a distributed recommender framework, Ecommerce-oriented Distributed Recommender System (EDRS), is proposed. The proposed EDRS allows multiple recommenders from different parties (i.e. organisations or ecommerce sites) to share recommendations and information resources with each other in order to improve their recommendation quality. Based on the results obtained from the experiments conducted in this thesis, the proposed systems and techniques have achieved great improvement in both making quality recommendations and alleviating the cold-start problem.

Thermoanalytical studies of natural potassium, sodium and ammonium alunites

Dynamic and controlled rate thermal analysis (CRTA) has been used to characterise alunites of formula [M(Al)3(SO4)2(OH)6 ] where M+ is the cations K+, Na+ or NH4+. Thermal decomposition occurs in a series of steps. (a) dehydration, (b) well defined dehydroxylation and (c) desulphation. CRTA offers a better resolution and a more detailed interpretation of water formation processes via approaching equilibrium conditions of decomposition through the elimination of the slow transfer of heat to the sample as a controlling parameter on the process of decomposition. Constant-rate decomposition processes of water formation reveal the subtle nature of dehydration and dehydroxylation.

rac-Ammonium cis-2-carboxycyclohexane-1-carboxylate

In the structure of the title compound, cis NH4+ C8H11O4-, the carboxylic acid and carboxyl groups of the cation adopt C-C-C-O torsion angles of 174.9(2) and -145.4(2)deg. respecticely with the alicyclic ring. The ammonium H atoms of the cations give a total of five hydrogen-bonding associations with carboxyl O-atom acceptors of the anion which, together with a carboxylic acid O-H...O(carboxyl) interaction give two-dimensional sheet structures which lie in the (101) planes in the unit cell.

Recovery and reuse of ammonium from wastewater treatment plants : an application for agriculture

In wastewater treatment plants based on anaerobic digestion, supernatant and outflows from sludge dewatering systems contain significantly high amount of ammonium. Generally, these waters are returned to the head of wastewater treatment plant (WWTP), thereby increasing the total nitrogen load of the influent flow. Ammonium from these waters can be recovered and commercially utilised using novel ion-exchange materials. Mackinnon et al. have described an approach for removal and recovery of ammonium from side stream centrate returns obtained from anaerobic digester of a typical WWTP. Most of the ammonium from side streams can potentially be removed, which significantly reduces overall inlet demand at a WWTP. However, the extent of reduction achieved depends on the level of ammonium and flow-rate in the side stream. The exchange efficiency of the ion-exchange material, MesoLite, used in the ammonium recovery process deteriorates with long-term use due to mechanical degradation and use of regenerant. To ensure that a sustainable process is utilised a range of potential applications for this “spent” MesoLite have been evaluated. The primary focus of evaluations has been use of ammonium-loaded MesoLite as a source of nitrogen and growth medium for plants. A MesoLite fertiliser has advantage over soluble fertilisers in that N is held on an insoluble matrix and is gradually released according to exchange equilibria. Many conventional N fertilisers are water-soluble and thus, instantly release all applied N into the soil solution. Loss of nutrient commonly occurs through volatilisation and/or leaching. On average, up to half of the N delivered by a typical soluble fertiliser can be lost through these processes. In this context, use of ammonium-loaded MesoLite as a fertiliser has been evaluated using standard greenhouse and field-based experiments for low fertility soils. Rye grass, a suitable test species for greenhouse trials, was grown in 1kg pots over a period of several weeks with regular irrigation. Nitrogen was applied at a range of rates using a chemical fertiliser as a control and using two MesoLite fertilisers. All other nutrients were applied in adequate amounts. All treatments were replicated three times. Plants were harvested after four weeks, and dry plant mass and N concentrations were determined. At all nitrogen application rates, ammonium-loaded MesoLite produced higher plant mass than plants fertilised by the chemical fertiliser. The lower fertiliser effectiveness of the chemical fertliser is attributed to possible loss of some N through volatilisation. The MesoLite fertilisers did not show any adverse effect on availability of macro and trace nutrients, as shown by lack of deficiency symptoms, dry matter yield and plant analyses. Nitrogen loaded on to MesoLite in the form of exchanged ammonium is readily available to plants while remaining protected from losses via leaching and volatilisation. Spent MesoLite appears to be a suitable and effective fertiliser for a wide range of soils, particularly sandy soils with poor nutrient holding capacity.

Effect of Fe3O4 addition on removal of ammonium by zeolite NaA

Magnetic zeolite NaA with different Fe3O4 loadings was prepared by hydrothermal synthesis based on metakaolin and Fe3O4. The effect of added Fe3O4 on the removal of ammonium by zeolite NaA was investigated by varying the Fe3O4 loading, pH, adsorption temperature, initial concentration, adsorption time. Langmuir, Freundlich, and pseudo-second-order modeling were used to describe the nature and mechanism of ammonium ion exchange using both zeolite and magnetic zeolite. Thermodynamic parameters such as change in Gibbs free energy, enthalpy and entropy were calculated. The results show that all the selected factors affect the ammonium ion exchange by zeolite and magnetic zeolite, however, the added Fe3O4 apparently does not affect the ion exchange performance of zeolite to the ammonium ion. Freundlich model provides a better description of the adsorption process than Langmuir model. Moreover, kinetic analysis indicates the exchange of ammonium on the two materials follows a pseudosecond-order model. Thermodynamic analysis makes it clear that the adsorption process of ammonium is spontaneous and exothermic. Regardless of kinetic or thermodynamic analysis, all the results suggest that no considerable effect on the adsorption of the ammonium ion by zeolite is found after the addition of Fe3O4. According to the results, magnetic zeolite NaA can be used for the removal of ammonium due to the good adsorption performance and easy separation method from aqueous solution.

Hydrogen bonding in two ammonium salts of 5-sulfosalicylic acid : ammonium 3-carboxy-4-hydroxybenzenesulfonate monohydrate and triammonium 3-carboxy-4-hydroxybenzenesulfonate 3-carboxylato-4-hydroxybenzenesulfonate

The structures of two ammonium salts of 3-carboxy-4-hydroxybenzenesulfonic acid (5-sulfosalicylic acid, 5-SSA) have been determined at 200 K. In the 1:1 hydrated salt, ammonium 3-carboxy-4-hydroxybenzenesulfonate monohydrate, NH4+·C7H5O6S-·H2O, (I), the 5-SSA- monoanions give two types of head-to-tail laterally linked cyclic hydrogen-bonding associations, both with graph-set R44(20). The first involves both carboxylic acid O-HOwater and water O-HOsulfonate hydrogen bonds at one end, and ammonium N-HOsulfonate and N-HOcarboxy hydrogen bonds at the other. The second association is centrosymmetric, with end linkages through water O-HOsulfonate hydrogen bonds. These conjoined units form stacks down c and are extended into a three-dimensional framework structure through N-HO and water O-HO hydrogen bonds to sulfonate O-atom acceptors. Anhydrous triammonium 3-carboxy-4-hydroxybenzenesulfonate 3-carboxylato-4-hydroxybenzenesulfonate, 3NH4+·C7H4O6S2-·C7H5O6S-, (II), is unusual, having both dianionic 5-SSA2- and monoanionic 5-SSA- species. These are linked by a carboxylic acid O-HO hydrogen bond and, together with the three ammonium cations (two on general sites and the third comprising two independent half-cations lying on crystallographic twofold rotation axes), give a pseudo-centrosymmetric asymmetric unit. Cation-anion hydrogen bonding within this layered unit involves a cyclic R33(8) association which, together with extensive peripheral N-HO hydrogen bonding involving both sulfonate and carboxy/carboxylate acceptors, gives a three-dimensional framework structure. This work further demonstrates the utility of the 5-SSA- monoanion for the generation of stable hydrogen-bonded crystalline materials, and provides the structure of a dianionic 5-SSA2- species of which there are only a few examples in the crystallographic literature.

Practical applications for clay-derived zeolite N : an ammonium-selective ion exchanger for industry use

Over the past ten years, scaled-up utilisation of a previously under-exploited zeolite, Zeolite N1, has been demonstrated for selective ion exchange of ammonium and other ions in aqueous environments. As with many zeolite syntheses, the required source material should contain predictable levels of aluminium and silicon and, for full-scale industrial applications, kaolin and/or montmorillonite serve such a purpose. Field, pilot and commercial scale trials of kaolin-derived Zeolite N have focused on applications in agriculture and water treatment as these sectors are primary producers or users of ammonium. The format for the material – as fine powders, granules or extrudates – depends on the specific application albeit each has been evaluated.

Enrichment, distribution and sources of heavy metals in the sediments of Deception Bay, Queensland, Australia

Sediment samples from 13 sampling sites in Deception Bay, Australia were analysed for the presence of heavy metals. Enrichment factors, modified contamination indices and Nemerow pollution indices were calculated for each sampling site to determine sediment quality. The results indicate significant pollution of most sites by lead (average enrichment factor (EF) of 13), but there is also enrichment of arsenic (average EF 2.3), zinc (average EF 2.7) and other heavy metals. The modified degree of contamination indices (average 1.0) suggests that there is little contamination. By contrast, the Nemerow pollution index (average 5.8) suggests that Deception Bay is heavily contaminated. Cluster analysis was undertaken to identify groups of elements. Strong correlation between some elements and two distinct clusters of sampling sites based on sediment type was evident. These results have implications for pollution in complex marine environments where there is significant influx of sand and sediment into an estuarine environment.