Tracking the Fate of Microbially Sequestered Carbon Dioxide in Soil Organic Matter

The microbial contribution to soil organic matter (SOM) has recently been shown to be much larger than previously thought and thus its role in carbon sequestration may also be underestimated. In this study we employ C-13 ((CO2)-C-13) to assess the potential CO2 sequestration capacity of soil chemoautotrophic bacteria and combine nuclear magnetic resonance (NMR) with stable isotope probing (SIP), techniques that independently make use of the isotopic enrichment of soil microbial biomass. In this way molecular information generated from NMR is linked with identification of microbes responsible for carbon capture. A mathematical model is developed to determine real-time CO2 flux so that net sequestration can be calculated. Twenty-eight groups of bacteria showing close homologies with existing species were identified. Surprisingly, Ralstonia eutropha was the dominant group. Through NMR we observed the formation of lipids, carbohydrates, and proteins produced directly from CO2 utilized by microbial biomass. The component of SOM directly associated with CO2 capture was calculated at 2.86 mg C (89.21 mg kg(-1)) after 48 h. This approach can,differentiate between SOM derived through microbial uptake of CO2 and other SOM constituents and represents a first step in tracking the fate and dynamics of microbial biomass in soil.

Ecological and societal benefits of jellyfish blooms

Jellyfish are often considered as stressors on marine ecosystems or as indicators of highly perturbed systems. Far less attention is given to the potential of such species to provide beneficial ecosystem services in their own right. In an attempt to redress this imbalance we take the liberty of portraying jellyfish in a positive light and suggest that the story is not entirely one of doom and gloom. More specifically, we outline how gelatinous marine species contribute to the four categories of ecosystem services (regulating, supporting, provisioning and cultural) defined by the Millennium Ecosystem Assessment. This discussion ranges from the role of jellyfish in carbon capture and advection to the deep ocean through to the creation of micro habitat for developing fishes and the advancement of citizen science programmes. Attention is paid also to incorporation of gelatinous species into fisheries or ecosystem level models and the mechanisms by which we can improve the transfer of information between jellyfish researchers and the wider non-specialist community.

Encapsulation of phase change materials using rice-husk-char

This paper explored a new approach to prepare phase change microcapsules using carbon-based particles via Pickering emulsions for energy storage applications. Rice-husk-char, a by-product in biofuel production, containing 53.58 wt% of carbon was used as a model carbon-based material to encapsulate hexadecane. As a model phase change material, hexadecane was emulsified in aqueous suspensions of rice-husk-char nanoparticles. Water soluble polymers poly(diallyldimethyl-ammonium chloride) and poly(sodium styrene sulfonate) were used to fix the rice-husk-char nanoparticles on the emulsion droplets through layer-by-layer assembly to enhance the structural stability of the microcapsules. The microcapsules formed are composed of a thin shell encompassing a large core consisting of hexadecane. Thermal gravimetrical and differential scanning calorimeter analyses showed the phase change enthalpy of 80.9 kJ kg−1 or 120.0 MJ m−3. Design criteria of phase change microcapsules and preparation considerations were discussed in terms of desired applications. This work demonstrated possible utilisations of biomass-originated carbon-based material for thermal energy recovery and storage applications, which can be a new route of carbon capture and utilisation.

Carbon nanotube modified carbon composite monoliths as superior adsorbents for carbon dioxide capture

Carbon composite monoliths were prepared from a commercial phenolic resin mixed with just 1 wt% of carbon nanotubes (CNTs) followed by carbonization and physical activation with CO. The products possess a hierarchical macroporous-microporous structure and superior CO adsorption properties. In particular, they show the top-ranked CO capacity (52 mg CO per g adsorbent at 25 °C and 114 mmHg) under low CO partial pressures, which is of more relevance for flue gas applications. This matches or exceeds those of carbons produced by complex chemical activation and functionalization. Our study demonstrates an effective way to create narrow micropores through structural modification of carbon composites by CNTs. © 2013 The Royal Society of Chemistry.

Low pressure carbon dioxide solubility in lithium-ion batteries based electrolytes as a function of temperature. Measurement and prediction

We present in this study the effect of nature and concentration of lithium salt, such as the lithium hexafluorophosphate, LiPF6; lithium tris(pentafluoroethane)-trifluorurophosphate LiFAP; lithium bis(trifluoromethylsulfonyl)imide, LiTFSI, on the CO2 solubility in four electrolytes for lithium ion batteries based on pure solvent that include ethylene carbonate (EC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), as well as, in the EC:DMC, EC:EMC and EC:DEC (50:50) wt.% binary mixtures as a function of temperature from (283 to 353) K and atmospheric pressure. Based on experimental solubility values, the Henry’s law constant of the carbon dioxide in these solutions with the presence or absence of lithium salt was then deduced and compared with reported values from the literature, as well as with those predicted by using COSMO-RS methodology within COSMOThermX software. From this study, it appears that the addition of 1 mol · dm-3 LiPF6 salt in alkylcarbonate solvents decreases their CO2 capture capacity. By using the same experimental conditions, an opposite CO2 solubility trend was generally observed in the case of the addition of LiFAP or LiTFSI salts in these solutions. Additionally, in all solutions investigated during this work, the CO2 solubility is greater in electrolytes containing the LiFAP salt, followed by those based on the LiTFSI case. The precision and accuracy of the experimental data reported therein, which are close to (1 and 15)%, respectively. From the variation of the Henry’s law constant with temperature, the partial molar thermodynamic functions of dissolution such as the standard Gibbs energy, the enthalpy, and the entropy, as well as the mixing enthalpy of the solvent with CO2 in its hypothetical liquid state were calculated. Finally, a quantitative analysis of the CO2 solubility evolution was carried out in the EC:DMC (50:50) wt.% binary mixture as the function of the LiPF6 or LiTFSI concentration in solution to elucidate how ionic species modify the CO2 solubility in alkylcarbonates-based Li-ion electrolytes by investigating the salting effects at T = 298.15 K and atmospheric pressure.

Understanding the synthesis of directly spinnable carbon nanotube forests

Carbon nanotube forests that can be spun directly from the growth substrate into pure, highly aligned webs, ribbons or yarn promise novel applications that capture the strength and other characteristics of this material. The precise conditions for high spinnability over a maximum proportion of the reactor space are extremely sensitive. The roles of catalyst, substrate, temperature, gas flow rates, reaction time with acetylene etc. were studied to identify and understand the key parameters and develop a robust, scalable process. Using a 44 mm (id) reactor, the optimum values for these variables were determined as comprising a 2.3 nm thick iron catalyst layer on a silicon substrate with 50 nm of thermal oxide; 670 °C running temperature; 650 sccm helium and 34 sccm acetylene for 20 min. The effects of deviating from these optima were explored and the role of amorphous carbon deposition clarified. Crown Copyright © 2009.

CO2 Capture in Wet and Dry Superbase Ionic Liquids

The solubility of carbon dioxide in five tetraalkylphosphonium superbase ionic liquids, namely the trihexyltetradecylphoshonium phenoxide, trihexyltetradecylphoshonium benzotriazolide, trihexyltetradecylphoshonium benzimidazolide, trihexyltetradecylphoshonium 1,2,3-triazolide, and trihexyltetradecylphoshonium 1,2,4-triazolide was studied experimentally under dry and wet conditions at 22 A degrees C and at atmospheric pressure, using a gravimetric saturation technique. The effects of anion structure and of the presence or absence of water in the solution on the carbon dioxide solubility were then deduced from the data. H-1 and C-13-NMR spectroscopy and ab initio calculations were also conducted to probe the interactions in these solutions, as carbon dioxide and water can compete in the ionic liquid structure during the absorption process. Additionally, the viscosity of selected superbase ionic liquids was measured under dry and wet conditions, in the presence or absence of CO2, to evaluate their practical application in carbon dioxide capture processes. Finally, the recyclability of the trihexyltetradecylphoshonium 1,2,4-triazolide under dry and wet conditions was determined to probe the ability of selected solvents to solubilize chemically a high concentration of carbon dioxide and then release it in a low energy demand process.

PALLADIUM CATALYZED TANDEM CYCLIZATION-ANION CAPTURE PROCESSES .1. BACKGROUND AND HYDRIDE ION CAPTURE BY ALKYL-PALLADIUM AND PI-ALLYL-PALLADIUM SPECIES

A new, wide ranging, synthetically powerful, catalytic tandem cyclisation-anion capture process is proposed which depends on the rate of cyclisation of an organopalladium specifies (RPdX) onto a proximate alkene or diene being significantly faster than anion exchange and reductive elimination in the sequence RPdX --> RPdY --> RY + Pd(0). The catalytic cyclisation - anion capture sequence is illustrated for hydride capture by a wide variety of substrates giving rise to fused- and spiro-, carbo- and hetero-cyclic systems, regio- and stereo-specifically.

CO2 capture and electrochemical conversion using superbasic [P66614][124Triz]

The ionic liquid trihexyltetradecylphosphonium 1,2,4-triazolide, [P66614][124Triz], has been shown to chemisorb CO2 through equimolar binding of the carbon dioxide with the 1,2,4-triazolide anion. This leads to a possible new, low energy pathway for the electrochemical reduction of carbon dioxide to formate and syngas at low overpotentials, utilizing this reactive ionic liquid media. Herein, an electrochemical investigation of water and carbon dioxide addition to the [P66614][124Triz] on gold and platinum working electrodes is reported. Electrolysis measurements have been performed using CO2 saturated [P66614][124Triz] based solutions at −0.9 V and −1.9 V on gold and platinum electrodes. The effects of the electrode material on the formation of formate and syngas using these solutions are presented and discussed.

Magnitude, form and bioavailability of fluvial carbon exports from Irish organic soils under pasture

Organic soils are widespread in Ireland and vulnerable to degradation via drainage for agriculture. The soil-landuse combination of pasture on organic soils may play a disproportionate role in regional C dynamics but is yet to receive study. Fluvial C fluxes and labile organic fractions were determined for two such sites at nested field (c.4 ha) and subcatchment scales (>40 ha); one relatively dry and nutrient rich, the other wetter and nutrient poor. Field scale flux from the nutrient poor site over 2 years was 38.9 ± 6.6 g C m⁻² yr⁻¹ with DIC > DOC > POC at 57, 32 and 11 % respectively, and 72 % DIC was comprised of above equilibrium CO₂. At the nutrient rich site, which overlies limestone geology, field scale export over an individual year was 90.4 g C m⁻² with DIC > DOC > POC at 49, 42 and 9 %, but with 90 % DIC as bicarbonate. By comparison with the nutrient poor site, the magnitude and composition of inorganic C exports from the nutrient rich site implied considerable export of soil-respiratory C as bicarbonate, and lower evasion losses due to carbonate system buffering. Labile DOC determined using dark incubations indicated small fractions (5–10 %) available for remineralisation over typical downstream transit times of days to weeks. These fractions are probably conservative as photolysis in the environment can increase the proportion of labile compounds via photocleavage and directly remineralise organic matter. This study demonstrates that monitoring at soil–water interfaces can aid capture of total landscape fluvial fluxes by precluding the need to incorporate prior C evasion, although rapid runoff responses at field scales can necessitate high resolution flow proportional, and hydrograph sampling to constrain uncertainty of flux estimates.

Effect of the Presence of MEA on the CO2 Capture Ability of Superbase Ionic Liquids

The miscibility of monoethanolamine (MEA) in five superbase ionic liquids (ILs), namely the trihexyl-tetradecylphosphonium benzotriazolide ([P66614][Bentriz]), trihexyl-tetradecylphosphonium benzimidazolide ([P66614][Benzim]), trihexyl-tetradecylphosphonium 1,2,3-triazolide ([P66614][123Triz]), trihexyl-tetradecylphosphonium 1,2,4-triazolide ([P66614][124Triz]), and trihexyl-tetradecylphosphonium imidazolide ([P66614][Im]) was determined at 295.15 K using 1H NMR spectroscopy. The solubility of carbon dioxide (CO2) in equimolar (IL + MEA) mixtures was then studied experimentally using a gravimetric technique at 295.15 K and 0.1 MPa. The effect of MEA on the CO2 capture ability of these ILs was investigated together with the viscosity of these systems in the presence or absence of CO2 to evaluate their practical application in CO2 capture processes. The effect of the presence of MEA on the rate of CO2 uptake was also studied. The study showed that the MEA can enhance CO2 absorption over the ideal values in the case of [P66614][123Triz] and [P66614][Bentriz] while in the other systems the mixtures behave ideally. A comparison of the effect of MEA addition with the addition of water to these superbase ILs showed that similar trends were observed in each case for the individual ILs studied.