An evaluation of DGT performance using a dynamic numerical model

A numerical model of the transport and dynamics of metal complexes in the resin and gel layers of a DGT (diffusive gradients in thin films) device was developed and used to investigate how the chelating resin and metal-ligand complexes in solution affect metal uptake. Decreasing the stability constant or concentration of the binding resin increases the competition for free metal ions by ligands in solution, lowering the rate of mass uptake. Such effects would be rarely observed for moderately or strongly binding resins (K> 10(12)), including Chelex, which out-compete labile ligands in solution. With weakly binding resins, strongly bound solution complexes can diffuse into the resin layer before a measurable amount of dissociation occurs, such that concentrations of bound metal at the rear and front surfaces of the resin layer are equal. With more strongly binding resins, metal mainly binds to the front surface of the resin. Only complexes with the largest binding constants penetrate the gel layer containing Chelex, buttheir lack of lability means thatthe DGT sensitivity to the complex is, in any case, very low. The slow diffusion of complexes, such as those of fulvic acids, which increases the time required to establish steady state, compromises the use of the simple DGT equation. Errors are negligible for 24 h deployments, when diffusive layer thicknesses are less than 1 mm, but 3 day deployments are required to ensure accuracy with 2.4 mm thick layers. The extent to which the commonly used equation, that accounts for the concentration and diffusion of metal-complex species, overestimates DGT uptake if the rate of dissociation is slow, was estimated.     

Carbon dioxide adsorption on mesoporous silica surfaces containing amine-like motifs

The postcombustion separation of CO₂ from a flue gas mixture is a unit operation in carbon capture. Today, CO₂ is normally separated with alkanolamines in aqueous solutions. These absorption processes are energy intensive and costly. Increased environmental considerations and the significant footprints of many energy sources warrant the development of new gas separation techniques for the competitive implementation of carbon capture and storage technologies. Improved adsorbent-mediated separation processes are candidates for such new low-energy low-cost processes. In this study, porous silica-based adsorbents with amine-like motifs were synthesized. The temperature- and pressure-dependent adsorption of CO₂ and CO₂/H₂O mixtures were determined and compared for these materials. The experimental uptake capacities of the materials modified with primary propyl amine moieties were significantly higher than those of materials modified with bis-ethanol amine or amidine. The propyl-amine-modified samples also showed good selectivity for CO₂ over nitrogen gas.     

Screening for organic phosphorus compounds in aquatic sediments by liquid chromatography coupled to ICP-AES and ESI-MS/MS

The structures of organic phosphorous (P) compounds in aquatic sediments are to a large extent unknown although these compounds are considered to play an important role in regulating lake trophic status. To enhance identification of these compounds, a liquid chromatography (LC) method for their separation was developed. The stationary phase was porous graphitic carbon (PGC), and the mobile phases used in the gradient elution were compatible with both inductive coupled plasma atomic emission spectroscopy (ICP-AES) and electrospray ionization tandem mass spectrometry (ESI-MS/MS). With LC-ICP-AES, eight different P containing peaks could be observed in the P chromatogram indicating that at least eight different P compounds were separated. With the setup of an information dependent acquisition (IDA) with ESI-MS/MS, the mass over charge ( m/ z) of compounds containing a phosphate group (H 2PO 3 (-), m/ z 97) could be measured and further fragmentation experiments gave additional information on the structure of almost 40 separated P compounds, several were verified to be nucleotides. ICP-AES was very suitable in the development of the LC method and allowed screening and quantification of P compounds. The presented LC-ESI-MS/MS technique was able to identify several sediment organic P compounds.     

Probe diffusion in κ-carrageenan gels determined by fluorescence recovery after photobleaching

The effects of free volume and heterogeneity on probe diffusion in κ-carrageenan gels were determined by fluorescence recovery after photobleaching (FRAP) and rheology. By changing the ionic conditions, biopolymer concentration and end temperature, different microstructures and aggregation kinetics in the κ-carrageenan gels were evaluated. The results of the FRAP measurements were compared to transmission electron microscopy (TEM) and nuclear magnetic resonance diffusometry (NMRd) data from previous studies. The results showed that the free diffusion rates of the probe (FITC dextran) in water were influenced by both temperature and ionic conditions. The free diffusion values were used for normalization of the diffusion rates in the κ-carrageenan gel measurements. The compatibility between FITC dextran with different molecular weights (10 and 500 kDa) and κ-carrageenan was evaluated. The results showed that the larger FITC dextran probe phase separates; therefore only the 10 kDa FITC dextran probe was used in the FRAP experiments. FRAP measurements and NMRd probe diffusion in combination with TEM in κ-carrageenan revealed that the void space, degree of aggregation and heterogeneity influence the probe diffusion rate. The κ-carrageenan gelation was analyzed at different end temperatures using rheology and FRAP. The FITC dextran probe diffusion was not influenced by κ-carrageenan aggregation, regardless of rheological gelation kinetics and storage modulus near the gel point. This indicates that the average void space between the gel strands is larger than the size of the probe. Good correlation between the microstructure and the probe diffusion rate in κ-carrageenan gel with different ionic conditions and constant biopolymer concentration were obtained with TEM and FRAP.     

Spillover effects when IKEA enters: Do incumbent retailers win or lose?

We investigate the effects of IKEA entry in three Swedish municipalities, finding that revenues for incumbent retailers located 1 km from the new IKEA store experienced a 7% increase due to positive spillover. The effect was insignificant for retailers located in city centres or more than 1 km from IKEA. Moreover, the positive agglomeration effects only dominate the negative competition effects for stores that sell complementary products, while same-market retailers located between 2 and 5 km from the new IKEA store experienced revenue loss due to IKEA entry. In contrast to retail revenues, the effects on employment were statistically insignificant.     

Individual Driving Behaviour in Wildfire Smoke

Fire Technology - This work presents the results of a virtual reality (VR) experiment aiming at investigating how individual driving behaviour is affected by the presence of wildfire smoke. The...     

A quantitative assessment of the hydrogen storage capacity of the UK continental shelf

Increased penetration of renewable energy sources and decarbonisation of the UK's gas supply will require large-scale energy storage. Using hydrogen as an energy storage vector, we estimate that 150 TWh of seasonal storage is required to replace seasonal variations in natural gas production. Large-scale storage is best suited to porous rock reservoirs. We present a method to quantify the hydrogen storage capacity of gas fields and saline aquifers using data previously used to assess CO₂ storage potential. We calculate a P50 value of 6900 TWh of working gas capacity in gas fields and 2200 TWh in saline aquifers on the UK continental shelf, assuming a cushion gas requirement of 50%. Sensitivity analysis reveals low temperature storage sites with sealing rocks that can withstand high pressures are ideal sites. Gas fields in the Southern North Sea could utilise existing infrastructure and large offshore wind developments to develop large-scale offshore hydrogen production.