Copolymerization of carbon dioxide and propylene oxide with neodymium trichloroacetate-based coordination catalyst

The copolymerizations of carbon dioxide (CO2) and propylene oxide (PO) were performed using new ternary rare-earth catalyst, It was found that the rare-earth coordination catalyst consisting of Nd(CCl3COO)(3), ZnEt2 and glycerine was very effective for the copolymerization of PO with CO2. The effects of the relative molar ratio and addition order of the catalyst components, copolymerization reaction time, and operating pressure as well as temperature on the copolymerization were systematically investigated. At an appropriate combination of all variables, the yield could be as high as 6875 g/mol Nd per hour at 90 degreesC in a 8 h reaction period.

Corrosion of carbon steel influenced by anaerobic biofilm in natural seawater

The bacteria in the anaerobic biofilm on rusted carbon steel immersed in natural seawater were characterized by culturing and molecular biology techniques. Two types of anaerobic bacterium, sulfate-reducing bacteria (SRB) Desulfovibrio caledoniensis and iron-reducing bacteria Clostridium sp. uncultured were found. The compositions of the rust layer were also analyzed and we found that iron oxide and sulfate green rust were the major components. To investigate the corrosion mechanisms, electrochemical impedance spectra was obtained based on the isolated sulfate-reducing bacteria and mixed bacteria cultured from rust layer in laboratory culture conditions. We found that single species produced iron sulfide and accelerated corrosion, but mixed species produced sulfate green rust and inhibited corrosion. The anaerobic corrosion mechanism of steel was proposed and its environmental significance was discussed. (c) 2008 Elsevier Ltd. All rights reserved.

Design and synthesis of hierarchical MnO2 nanospheres/carbon nanotubes/conducting polymer ternary composite for high performance electrochemical electrodes.

For efficient use of metal oxides, such as MnO(2) and RuO(2), in pseudocapacitors and other electrochemical applications, the poor conductivity of the metal oxide is a major problem. To tackle the problem, we have designed a ternary nanocomposite film composed of metal oxide (MnO(2)), carbon nanotube (CNT), and conducting polymer (CP). Each component in the MnO(2)/CNT/CP film provides unique and critical function to achieve optimized electrochemical properties. The electrochemical performance of the film is evaluated by cyclic voltammetry, and constant-current charge/discharge cycling techniques. Specific capacitance (SC) of the ternary composite electrode can reach 427 F/g. Even at high mass loading and high concentration of MnO(2) (60%), the film still showed SC value as high as 200 F/g. The electrode also exhibited excellent charge/discharge rate and good cycling stability, retaining over 99% of its initial charge after 1000 cycles. The results demonstrated that MnO(2) is effectively utilized with assistance of other components (fFWNTs and poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) in the electrode. Such ternary composite is very promising for the next generation high performance electrochemical supercapacitors.

Marine baseline and monitoring strategies for carbon dioxide capture and storage (CCS)

The QICS controlled release experiment demonstrates that leaks of carbon dioxide (CO2) gas can be detected by monitoring acoustic, geochemical and biological parameters within a given marine system. However the natural complexity and variability of marine system responses to (artificial) leakage strongly suggests that there are no absolute indicators of leakage or impact that can unequivocally and universally be used for all potential future storage sites. We suggest a multivariate, hierarchical approach to monitoring, escalating from anomaly detection to attribution, quantification and then impact assessment, as required. Given the spatial heterogeneity of many marine ecosystems it is essential that environmental monitoring programmes are supported by a temporally (tidal, seasonal and annual) and spatially resolved baseline of data from which changes can be accurately identified. In this paper we outline and discuss the options for monitoring methodologies and identify the components of an appropriate baseline survey.

Global carbon budget 2014

Accurate assessment of anthropogenic carbon dioxide (CO2) emissions and their redistribution among the atmosphere, ocean, and terrestrial biosphere is important to better understand the global carbon cycle, support the development of climate policies, and project future climate change. Here we describe data sets and a methodology to quantify all major components of the global carbon budget, including their uncertainties, based on the combination of a range of data, algorithms, statistics, and model estimates and their interpretation by a broad scientific community. We discuss changes compared to previous estimates, consistency within and among components, alongside methodology and data limitations. CO2 emissions from fossil fuel combustion and cement production (E-FF) are based on energy statistics and cement production data, respectively, while emissions from land-use change (E-LUC), mainly deforestation, are based on combined evidence from land-cover-change data, fire activity associated with deforestation, and models. The global atmospheric CO2 concentration is measured directly and its rate of growth (G(ATM)) is computed from the annual changes in concentration. The mean ocean CO2 sink (S-OCEAN) is based on observations from the 1990s, while the annual anomalies and trends are estimated with ocean models. The variability in S-OCEAN is evaluated with data products based on surveys of ocean CO2 measurements. The global residual terrestrial CO2 sink (S-LAND) is estimated by the difference of the other terms of the global carbon budget and compared to results of independent dynamic global vegetation models forced by observed climate, CO2, and land-cover-change (some including nitrogen-carbon interactions). We compare the mean land and ocean fluxes and their variability to estimates from three atmospheric inverse methods for three broad latitude bands. All uncertainties are reported as +/- 1 sigma, reflecting the current capacity to characterise the annual estimates of each component of the global carbon budget. For the last decade available (2004-2013), E-FF was 8.9 +/- 0.4 GtC yr(-1), E-LUC 0.9 +/- 0.5 GtC yr(-1), G(ATM) 4.3 +/- 0.1 GtC yr(-1), S-OCEAN 2.6 +/- 0.5 GtC yr(-1), and S-LAND 2.9 +/- 0.8 GtC yr(-1). For year 2013 alone, E-FF grew to 9.9 +/- 0.5 GtC yr(-1), 2.3% above 2012, continuing the growth trend in these emissions, E-LUC was 0.9 +/- 0.5 GtC yr(-1), G(ATM) was 5.4 +/- 0.2 GtC yr(-1), S-OCEAN was 2.9 +/- 0.5 GtC yr(-1), and S-LAND was 2.5 +/- 0.9 GtC yr(-1). G(ATM) was high in 2013, reflecting a steady increase in E-FF and smaller and opposite changes between S-OCEAN and S-LAND compared to the past decade (2004-2013). The global atmospheric CO2 concentration reached 395.31 +/- 0.10 ppm averaged over 2013. We estimate that E-FF will increase by 2.5% (1.3-3.5 %) to 10.1 +/- 0.6 GtC in 2014 (37.0 +/- 2.2 GtCO(2) yr(-1)), 65% above emissions in 1990, based on projections of world gross domestic product and recent changes in the carbon intensity of the global economy. From this projection of E-FF and assumed constant E-LUC for 2014, cumulative emissions of CO2 will reach about 545 +/- 55 GtC (2000 +/- 200 GtCO(2)) for 1870-2014, about 75% from E-FF and 25% from E-LUC. This paper documents changes in the methods and data sets used in this new carbon budget compared with previous publications of this living data set (Le Quere et al., 2013, 2014). All observations presented here can be downloaded from the Carbon Dioxide Information Analysis Center (doi:10.3334/CDIAC/GCP_2014).

Global Carbon Budget 2015

Accurate assessment of anthropogenic carbon dioxide (CO2) emissions and their redistribution among the atmosphere, ocean, and terrestrial biosphere is important to better understand the global carbon cycle, support the development of climate policies, and project future climate change. Here we describe data sets and a methodology to quantify all major components of the global carbon budget, including their uncertainties, based on the combination of a range of data, algorithms, statistics, and model estimates and their interpretation by a broad scientific community. We discuss changes compared to previous estimates as well as consistency within and among components, alongside methodology and data limitations. CO2 emissions from fossil fuels and industry (EFF) are based on energy statistics and cement production data, while emissions from land-use change (ELUC), mainly deforestation, are based on combined evidence from land-cover-change data, fire activity associated with deforestation, and models. The global atmospheric CO2 concentration is measured directly and its rate of growth (GATM) is computed from the annual changes in concentration. The mean ocean CO2 sink (SOCEAN) is based on observations from the 1990s, while the annual anomalies and trends are estimated with ocean models. The variability in SOCEAN is evaluated with data products based on surveys of ocean CO2 measurements. The global residual terrestrial CO2 sink (SLAND) is estimated by the difference of the other terms of the global carbon budget and compared to results of independent dynamic global vegetation models forced by observed climate, CO2, and land-cover change (some including nitrogen–carbon interactions). We compare the mean land and ocean fluxes and their variability to estimates from three atmospheric inverse methods for three broad latitude bands. All uncertainties are reported as ±1σ, reflecting the current capacity to characterise the annual estimates of each component of the global carbon budget. For the last decade available (2005–2014), EFF was 9.0 ± 0.5 GtC yr−1, ELUC was 0.9 ± 0.5 GtC yr−1, GATM was 4.4 ± 0.1 GtC yr−1, SOCEAN was 2.6 ± 0.5 GtC yr−1, and SLAND was 3.0 ± 0.8 GtC yr−1. For the year 2014 alone, EFF grew to 9.8 ± 0.5 GtC yr−1, 0.6 % above 2013, continuing the growth trend in these emissions, albeit at a slower rate compared to the average growth of 2.2 % yr−1 that took place during 2005–2014. Also, for 2014, ELUC was 1.1 ± 0.5 GtC yr−1, GATM was 3.9 ± 0.2 GtC yr−1, SOCEAN was 2.9 ± 0.5 GtC yr−1, and SLAND was 4.1 ± 0.9 GtC yr−1. GATM was lower in 2014 compared to the past decade (2005–2014), reflecting a larger SLAND for that year. The global atmospheric CO2 concentration reached 397.15 ± 0.10 ppm averaged over 2014. For 2015, preliminary data indicate that the growth in EFF will be near or slightly below zero, with a projection of −0.6 [range of −1.6 to +0.5] %, based on national emissions projections for China and the USA, and projections of gross domestic product corrected for recent changes in the carbon intensity of the global economy for the rest of the world. From this projection of EFF and assumed constant ELUC for 2015, cumulative emissions of CO2 will reach about 555 ± 55 GtC (2035 ± 205 GtCO2) for 1870–2015, about 75 % from EFF and 25 % from ELUC. This living data update documents changes in the methods and data sets used in this new carbon budget compared with previous publications of this data set (Le Quéré et al., 2015, 2014, 2013). All observations presented here can be downloaded from the Carbon Dioxide Information Analysis Center (doi:10.3334/CDIAC/GCP_2015).

Uptake of carbon, nitrogen and phosphorus by phytoplankton along the 20 degrees W meridian in the NE Atlantic between 57.5 degrees N and 37 degrees N

Phytoplankton biomass and rate of production were measured along a transect from 57.54 degreesN to 37.01 degreesN in the northeast Atlantic during July 1996 and at a series of stations over a 7-day period at 37 degreesN 20 degreesW. Surface nutrient concentrations ranged from 4 mu mol l(-1) NO3-, and 0.35 mu mol l(-1) PO43- at 57.54 degreesN to <10 nmol l(-1) NO3- and similar to 10 nmol l(-1) PO43- at 37.01 degreesN. The greatest phytoplankton biomass and production were measured in the vicinity of a frontal system at 50 degreesN, and there was a general decline in total phytoplankton biomass and production to the south of the transect. Production was measured in three size fractions. At the station with the highest chlorophyll concentrations (50.34 degreesN), phytoplankton cells larger than 5 mum dominated the assemblage, accounting for 72% of the chlorophyll concentration (22.9 mg m(-2)) and 51% of primary production (54.1 mmol Cm-2 d(-1)), but picophytoplankton production was also high (43%). At 57 degreesN, carbon fixation by the > 5 mum fraction accounted for 75% of the daily production of 60.75 mmol Cm-2 d(-1). At 37 degreesN, picophytoplankton was the dominant group, accounting for similar to 58% (10 mg m(-2)) of chlorophyll and similar to 64% (46 mmol Cm-2 d(-1)), of primary production. Nitrate, ammonium and phosphate uptake rates also were determined. Although high nitrate uptake rates were measured in the surface water at similar to 50 degreesN, the greatest uptake rates of both depth-integrated nitrate and ammonium were at the south of the transect. At 37 degreesN, a deep euphotic zone was present and light penetrated through the nitracline; total nitrate uptake was enhanced because of assimilation at the base of the euphotic zone. As a consequence, high values of depth-integrated f-ratio were measured in the oligotrophic waters at the south of the transect. Phosphate was predominantly incorporated into the picoplankton fraction, which included heterotrophic and autotrophic components, at all stations and a significant proportion of phosphate uptake occurred in the dark. The C:N:P assimilation ratios were variable throughout the region; phosphate uptake was generally greater than would be expected if nutrient assimilation were in proportion to the Redfield ratio. (C) 2001 Elsevier Science Ltd. All rights reserved.

Effect of acetonitrile on the solubility of carbon dioxide in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) amide

The effect of the addition of acetonitrile on the solubility of carbon dioxide in an ionic liquid, the 1-ethyl-3- methylimidazolium bis(trifluoromethanesulfonyl)amide, [C(2)mim][NTf2], was studied experimentally at pressures close to atmospheric and as a function of temperature between 290 and 335 K. It was observed that the solubility of carbon dioxide decreases linearly with the mole fraction of acetonitrile from a value of 2.6 x 10(-2) in the pure ionic liquid at 303 K to a mole fraction of 1.3 x 10(-2) in the mixture [C(2)mim][NTf2] + CH3CN with x(CH3CN) = 0.77 at the same temperature. The gas solubility decreases with temperature, and the thermodynamic properties of solvation could be calculated. The vapor pressures of the [ C2mim][ NTf2] + CH3CN mixtures were measured in the same temperature range, and strong negative deviations from Raoult's law were obtained: up to 36% for a mixture with x(CH3CN) = 0.46 at 334 K. Negative excess molar volumes of approximately -1 cm(3) mol(-1) at equimolar composition could also be calculated from density measurements of the pure components and of the mixtures. These observations are confirmed by neutron diffraction studies and are compatible with the existence of strong ion-dipole interactions in the mixed liquid solvent.

Textile wastewater treatment using granular activated carbon adsorption in fixed beds

This work involved the treatment of industrial wastewater from a nylon carpet printing plant which currently receives no treatment and is discharged to sea. As nylon is particularly difficult to dye, acid dyes are required for successful coloration and cause major problems with the plant's effluent disposal in terms of color removal. Granular activated carbon Filtrasorb 400 was used to treat a ternary solution of acid dyes and the process plant effluent containing the dyes in a fixed-bed column system. Experimental data were correlated using the bed depth service time (BDST) model to previously published work by the authors for single dye adsorption. The results were expressed in terms of the BDST adsorption capacity, in milligrams of adsorbate per gram of adsorbent, and indicated that there was a 12-25% decrease iri adsorption capacity in the ternary system compared to the single component system; This reduction has been attributed to competitive adsorption occurring in the ternary component system. Dye adsorption from the process plant effluent showed an approximate 65% decrease in adsorption capacity compared to the ternary solution system. This has been attributed to interference caused by the other colorless textile effluent pollutants found in the process wastewater. A chemical oxygen demand analysis on these components indicated that the dyes accounted for only 14% of the total oxygen demand.

Development of a Polymer-carbon Nanotubes based Economic Solar Collector

A low cost solar collector was developed by using polymeric components as opposed to metal and glass components of traditional solar collectors. In order to utilize polymers for the absorber of the solar collector, Carbon Nanotubes (CNT) has been added as a filler to improve the thermal conductivity and the solar absorptivity of polymers. The solar collector was designed as a multi-layer construction with considering the economic manufacturing. Through the mathematical heat transfer analysis, the performance and characteristics of the designed solar collector have been estimated. Furthermore, the prototypes of the proposed system were built and tested at a state-of-the-art solar simulator facility to evaluate the actual performance of the developed solar collector. The cost-effective polymer-CNT solar collector, which achieved efficiency as much as that of a conventional glazed flat plate solar panel, has been successfully developed.

14C as a tool to trace terrestrial carbon in a complex lake system: implications for food-web structure and carbon cycling

Globally lakes bury and remineralise significant quantities of terrestrial C, and the associated flux of terrestrial C strongly influences their functioning. Changing deposition chemistry, land use and climate induced impacts on hydrology will affect soil biogeochemistry and terrestrial C export¹ and hence lake ecology with potential feedbacks for regional and global C cycling. C and nitrogen stable isotope analysis (SIA) has identified the terrestrial subsidy of freshwater food webs. The approach relies on different ¹³C fractionation in aquatic and terrestrial primary producers, but also that inorganic C demands of aquatic primary producers are partly met by ¹³C depleted C from respiration of terrestrial C, and ‘old’ C derived from weathering of catchment geology. SIA thus fails to differentiate between the contributions of old and recently fixed terrestrial C. Natural abundance ¹⁴C can be used as an additional biomarker to untangle riverine food webs² where aquatic and terrestrial δ ¹³C overlap, but may also be valuable for examining the age and origin of C in the lake. Primary production in lakes is based on dissolved inorganic C (DIC). DIC in alkaline lakes is partially derived from weathering of carbonaceous bedrock, a proportion of which is¹⁴C-free. The low ¹⁴C activity yields an artificial age offset leading samples to appear hundreds to thousands of years older than their actual age. As such, ¹⁴C can be used to identify the proportion of autochthonous C in the food-web. With terrestrial C inputs likely to increase, the origin and utilisation of ‘fossil’ or ‘recent’ allochthonous C in the food-web can also be determined. Stable isotopes and 14C were measured for biota, particulate organic matter (POM), DIC and dissolved organic carbon (DOC) from Lough Erne, Northern Ireland, a humic alkaline lake. Temporal and spatial variation was evident in DIC, DOC and POM C isotopes with implications for the fluctuation in terrestrial export processes. Ramped pyrolysis of lake surface sediment indicates the burial of two C components. ¹⁴C activity (507 ± 30 BP) of sediment combusted at 400˚C was consistent with algal values and younger than bulk sediment values (1097 ± 30 BP). The sample was subsequently combusted at 850˚C, yielding 14C values (1471 ± 30 BP) older than the bulk sediment age, suggesting that fossil terrestrial carbon is also buried in the sediment. Stable isotopes in the food web indicate that terrestrial organic C is also utilised by lake organisms. High winter δ ¹⁵N values in calanoid zooplankton (δ ¹⁵N = 24%¸) relative to phytoplankton and POM (δ ¹⁵N = 6h and 12h respectively) may reflect several microbial trophic levels between terrestrial C and calanoids. Furthermore winter calanoid 14C ages are consistent with DOC from an inflowing river (75 ± 24 BP), not phytoplankton (367 ± 70 BP). Summer calanoid δ ^13C, δ ¹⁵N and ¹⁴C (345 ± 80 BP) indicate greater reliance on phytoplankton.

¹ Monteith, D.T et al., (2007) Dissolved organic carbon trends resulting from changes in atmospheric deposition chemistry. Nature, 450:537-535

² Caraco, N., et al.,(2010) Millennial-aged organic carbon subsidies to a modern river food web. Ecology,91: 2385-2393.

Distribution of assimilated carbon within the plant and rhizosphere of Lolium perenne:Influence of temperature

Perennial rye-grass plants were pulse labelled with [¹⁴C]-CO₂ over a range of temperatures (5-25°C). The fate of the label was determined within the plant and soil. The temperature at which plants were pulse labelled had a marked effect on the distribution of the label within the plant and soil system. Root-soil respiration increased from 5.7 to 24.15% when expressed as a percentage of net assimilated label. The percentage of label remaining in the plant root and in the soil was greater at 5 and 25°C, with a minimum for both these components at 15°C. At 15°C the percentage of net assimilated label that remained in the shoots was greater than at other temperatures, with this percentage decreasing at the lower and higher temperatures. © 1989.

Design, analysis and performance of a polymer-carbon nanotubes based economic solar collector

A low cost flat plate solar collector was developed by using polymeric components as opposed to metal and glass components of traditional flat plate solar collectors. In order to improve the thermal and optical properties of the polymer absorber of the solar collector, Carbon Nanotubes (CNT) were added as a filler. The solar collector was designed as a multi-layer construction with an emphasis on low manufacturing costs. Through the mathematical heat transfer analysis, the thermal performance of the collector and the characteristics of the design parameters were analyzed. Furthermore, the prototypes of the proposed collector were built and tested at a state-of-the-art solar simulator facility to evaluate its actual performance. The inclusion of CNT improved significantly the properties of the polymer absorber. The key design parameters and their effects on the thermal performance were identified via the heat transfer analysis. Based on the experimental and analytical results, the cost-effective polymer-CNT solar collector, which achieved a high thermal efficiency similar to that of a conventional glazed flat plate solar panel, was successfully developed.

Supercritical carbon dioxide extraction of bioactive compounds from microalgae and volatile oils from aromatic plants

A discussion of the most interesting results obtained in our laboratories, during the supercritical CO(2) extraction of bioactive compounds from microalgae and volatile oils from aromatic plants, was carried out. Concerning the microalgae, the studies on Botryococcus braunii and Chlorella vulgaris were selected. Hydrocarbons from the first microalgae, which are mainly linear alkadienes (C(23)-C(31)) with an odd number of carbon atoms, were selectively extracted at 313 K increasing the pressure up to 30.0 MPa. These hydrocarbons are easily extracted at this pressure, since they are located outside the cellular walls. The extraction of carotenoids, mainly canthaxanthin and astaxanthin, from C. vulgaris is more difficult. The extraction yield of these components at 313 K and 35.0 MPa increased with the degree of crushing of the microalga, since they are not extracellular. On the other hand, for the extraction of volatile oils from aromatic plants, studies on Mentha pulegium and Satureja montana L were chosen. For the first aromatic plant, the composition of the volatile and essential oils was similar, the main components being the pulegone and menthone. However, this volatile oil contained small amounts of waxes, which content decreased with decreasing particle size of the plant matrix. For S. montana L it was also observed that both oils have a similar composition, the main components being carvacrol and thymol. The main difference is the relative amount of thymoquinone, which content can be 15 times higher in volatile oil. This oxygenated monoterpene has important biological activities. Moreover, experimental studies on anticholinesterase activity of supercritical extracts of S. montana were also carried out. The supercritical nonvolatile fraction, which presented the highest content of the protocatechuic, vanilic, chlorogenic and (+)-catechin acids, is the most promising inhibitor of the enzyme butyrylcholinesterase. In contrast, the Soxhlet acetone extract did not affect the activity of this enzyme at the concentrations tested. (C) 2011 Elsevier B.V. All rights reserved.

The climate sensitivity and its components diagnosed from Earth Radiation Budget data

One of the major uncertainties in the ability to predict future climate change, and hence its impacts, is the lack of knowledge of the earth's climate sensitivity. Here, data are combined from the 1985-96 Earth Radiation Budget Experiment (ERBE) with surface temperature change information and estimates of radiative forcing to diagnose the climate sensitivity. Importantly, the estimate is completely independent of climate model results. A climate feedback parameter of 2.3 +/- 1.4 W m(-2) K-1 is found. This corresponds to a 1.0-4.1-K range for the equilibrium warming due to a doubling of carbon dioxide (assuming Gaussian errors in observable parameters, which is approximately equivalent to a uniform "prior" in feedback parameter). The uncertainty range is due to a combination of the short time period for the analysis as well as uncertainties in the surface temperature time series and radiative forcing time series, mostly the former. Radiative forcings may not all be fully accounted for; however, all argument is presented that the estimate of climate sensitivity is still likely to be representative of longer-term climate change. The methodology can be used to 1) retrieve shortwave and longwave components of climate feedback and 2) suggest clear-sky and cloud feedback terms. There is preliminary evidence of a neutral or even negative longwave feedback in the observations, suggesting that current climate models may not be representing some processes correctly if they give a net positive longwave feedback.