Chlorophyll-a in the rivers of eastern England

Chlorophyll-a concentration variations are described for two major river basins in England, the Humber and the Thames and related to catchment characteristics and nutrient concentrations across a range of rural, agricultural and urban/industrial settings. For all the rivers there are strong seasonal variations, with concentrations peaking in the spring and summer time when biological activity is at its highest. However, there are large variations in the magnitude of the seasonal effects across the rivers. For the spring-summer low-flow periods, average concentrations of chlorophyll-a correlate with soluble reactive phosphorus (SRP). Chlorophyll-a is also correlated with particulate nitrogen (PN), organic carbon (POC) and suspended sediments. However, the strongest relationships are with catchment area and flow, where two straight line relationships are observed. The results indicate the importance of residence times for determining planktonic growth within the rivers. This is also indicated by the lack of chlorophyll-a response to lowering of SRP concentrations in several of the rivers in the area due to phosphorus stripping of effluents at major sewage treatment works. A key control on chlorophyll-a concentration may be the input of canal and reservoir waters during the growing period: this too relates to issues of residence times. However, there may well be a complex series of factors influencing residence time across the catchments due to features such as inhomogeneous flow within the catchments, a fractal distribution of stream channels that leads to a distribution of residence times and differences in planktonic inoculation sources. Industrial pollution on the Aire and Calder seems to have affected the relationship of chlorophyll-a with PN and POC. The results are discussed in relation to the Water Framework Directive.     

Estimation of the concentration of donatable hydrogen in a coal solvent by n.m.r.

¹H and ¹³C nuclear magnetic resonance (n.m.r.) spectroscopies have been used to study the changes in composition of a hydrogenated anthracene oil solvent that occur during extraction of a UK bituminous coal. It has been shown that the principal hydrogen donor groups in the solvent are hydroaromatic and naphthenic rings in hydroaromatic species. Good agreement was achieved between the concentration of donatable hydrogen estimated from n.m.r., and the amount of hydrogen transferred from the solvent during exhaustive extraction.     

Molecular mass calibration in size-exclusion chromatography of coal derivatives

A number of procedures have been investigated for the calibration of a size-exclusion chromatography (s.e.c.) column in the determination of molecular mass (MM) distributions of coal derivatives. The behaviour of narrow fractions of coal extracts in the MM range 200–3000 was compared with a variety of the more generally available calibration standards. Calibration with preparative s.e.c. subfractions of materials similar to those under study has been recommended. Polystyrene standards are satisfactory, however, for MM < 1000, but above this range other polymer standards should be sought. Universal and molar volume calibration do not apply to coal-derived materials.     

Using short‐term resource scheduling for assessing effectiveness of CCS within electricity generation subsector

A new methodology for assessing the effectiveness of carbon capture and storage (CCS) that does explicitly consider the detailed operation of the target electricity system is proposed. The electricity system simulation consists of three phases, each one using a modified version of an economic dispatch problem that seeks to maximize the producers’ and consumers’ surplus while satisfying the technical constraints of the system. The economic dispatch is formulated as a dynamic mixed‐integer nonlinear programming problem and implemented in general algebraic modelling system (GAMS). The generating unit with CCS is designed and simulated using Aspen Plus®. In the first case study, the operation of the IEEE RTS ’96 (Institute of Electrical and Electronics Engineers One‐Area Reliability Test System—1996) is simulated with greenhouse gas (GHG) regulation implemented in the form of CO₂ permits that generators need to acquire for every unit of CO₂ that it is emitted. In the second case study, CCS is added at one of the buses and the operation of the modified IEEE RTS ’96 is again simulated with and without GHG regulation. The results suggest that the detailed operation of the target electricity system should be considered in future assessments of CCS and a general procedure for undertaking this for any GHG mitigation option is proposed. Future work will use the novel methodology for assessing the effectiveness of generating units with flexible CO₂ capture. © 2015 American Institute of Chemical Engineers AIChE J, 61: 4210–4234, 2015     

A Fourier-transform infrared study of CO2 and CO2/H2 interactions with caesium-doped copper catalysts

FTIR spectra are reported of CO₂ and CO₂/H₂ on a silica-supported caesium-doped copper catalyst. Adsorption of CO₂ on a “caesium”/silica surface resulted in the formation of CO₂ ⁻ and complexed CO species. Exposure of CO₂ to a caesium-doped reduced copper catalyst produced not only these species but also two forms of adsorbed carboxylate giving bands at 1550, 1510, 1365 and 1345 cm⁻¹. Reaction of carboxylate species with hydrogen at 388 K gave formate species on copper and caesium oxide in addition to methoxy groups associated with caesium oxide. Methoxy species were not detected on undoped copper catalyst suggesting that caesium may be a promoter for the methanol synthesis reaction. Methanol decomposition on a caesium-doped copper catalyst produced a small number of formate species on copper and caesium oxide. Methoxy groups on caesium oxide decomposed to CO and H₂, and subsequent reaction between CO and adsorbed oxygen resulted in carboxylate formation. Methoxy species located at interfacial sites appeared to exhibit unusual adsorption properties.     

Cessation of polyunsaturated fatty acid formation in four selected filamentous fungi when grown on plant oils

Four fungi,Conidiobolus nanodes, Entomophthora exitalis, Mortierella isabellina, andMucor circinelloides, were grown on various oils (triolein, sesame, safflower, linseed, and oil fromM. isabellina) and produced lipids in which the fatty acids were predominantly the same as those of the original staring substrate. Only in the first two cases was there evidence of a small amount of chain elongation and of fatty acid desaturation taking place. The extent of this was only about 10% of that seen in glucose-grown cells. The apparent repression of the fatty acid desaturases and elongases was not reversed by growing cells on glucose and oils as mixed substrates—the fatty acid profiles were the same as when the fungi had grown in oils alone. Neither was the cessation of polyunsaturated fatty acid synthesis due to the presence of nonoil components (NOC) in the oil. Only the NOC from sesame oil affected one single conversion, that of 20∶3n-3 to 20∶4n–6. We conclude that fatty acid desaturase and elongase systems are repressed either partially or completely in a filamentous fungi grown on triacylglycerol oils.     

An accurate volumetric differential pressure method for the determination of hydrogen storage capacity at high pressures in carbon materials

Widely different hydrogen adsorption capacities have been reported for a variety of carbon materials which have attracted attention for hydrogen storage. This has led to doubts as to the validity of some of the claims and it has been suggested that one possible reason for the disparate hydrogen sorption capacities may lie in the inaccurate measurement of the hydrogen adsorbed. The aim of the work described in this paper was to make a contribution to this debate by developing a means and method of producing repeatable, accurate measurements of hydrogen sorption capacity in carbon materials. The apparatus developed is a volumetric differential pressure set-up operating at up to 10 MPa and the method has a conservative limit of detection of 0.1 wt% and an accuracy of ±0.05 wt%, using 1.0-2.5 g samples of the carbon materials studied. These included a carbon nanofiber sample and a series of activated carbons, the latter displaying a direct correlation between the BET effective surface area and the hydrogen sorption capacity of the materials. The amount of hydrogen adsorbed was less than 1 wt% for all the carbons examined.     

Charge Density Influences C1 Domain Ligand Affinity and Membrane Interactions

The C1 domain, which represents the recognition motif on protein kinase C for the lipophilic second messenger diacylglycerol and its ultrapotent analogues, the phorbol esters, has emerged as a promising therapeutic target for cancer and other indications. Potential target selectivity is markedly enhanced both because binding reflects ternary complex formation between the ligand, C1 domain, and phospholipid, and because binding drives membrane insertion of the C1 domain, permitting aspects of the C1 domain surface outside the binding site, per se, to influence binding energetics. Here, focusing on charged residues identified in atypical C1 domains which contribute to their loss of ligand binding activity, we showed that increasing charge along the rim of the binding cleft of the protein kinase C δ C1 b domain raises the requirement for anionic phospholipids. Correspondingly, it shifts the selectivity of C1 domain translocation to the plasma membrane, which is more negatively charged than internal membranes. This change in localization is most pronounced in the case of more hydrophilic ligands, which provide weaker membrane stabilization than do the more hydrophobic ligands and thus contributes an element to the structure–activity relations for C1 domain ligands. Coexpressing pairs of C1‐containing constructs with differing charges each expressing a distinct fluorescent tag provided a powerful tool to demonstrate the effect of increasing charge in the C1 domain.     

Simultaneous multiple sample light scattering detection of LCST during copolymer synthesis

This work has two objectives in the investigation of polymer solution lower critical solution temperature (LCST): First, to develop a new instrument to monitor LCST onset during copolymer synthesis by coupling several thermostatted light scattering flow cells to the output stream of an ACOMP system (Automatic Continuous Online Monitoring of Polymerization reactions). Second, to use this to investigate effects on LCST when N-isopropylacrylamide (NIPAM) is copolymerized with a charged comonomer, styrene sulfonate (SS). This comonomer pair has widely separated reactivity ratios. SS is rapidly consumed, yielding composition drift toward NIPAM rich polymer. High content SS chains inhibited LCST, and SS was dramatically effective at suppressing LCST down to copolymers of 5% molar SS in 10 mM NaCl aqueous solvent. LCST for higher content SS chains was elevated and required significant additional ionic strength to occur. It was determined that the suppression of the LCST by SS is chiefly an intramolecular effect.