CO2 pipelines material and safety considerations

This paper presents an overview of some of the most important factors and areas of uncertainty affecting integrity and accurate hazard assessment of CO2 pipelines employed as part of the Carbon Capture and Sequestration (CCS) chain. These include corrosion, hydrate formation, hydrogen embrittlement and propensity to fast running ductile and brittle factures. Special consideration is given to the impact of impurities within the CO2 feed from the various capture technologies on these possible hazards. Knowledge gaps in the modelling of outflow and subsequent dispersion of CO2 following the accidental rupture of pressurised CO2 pipelines, central to their safety assessment, are also presented

Elucidation of a Low Spin Cobalt(II) System in a Distorted Tetrahedral Geometry

We have prepared a series of divalent cobalt(II) complexes supported by the [PhBP_3] ligand ([PhBP_3] = [PhB(CH_2PPh_2)_3]-) to probe certain structural and electronic phenomena that arise from this strong field, anionic tris(phosphine) donor ligand. The solid-state structure of the complex [PhBP_3]CoI (1), accompanied by SQUID, EPR, and optical data, indicates that it is a pseudotetrahedral cobalt(II) species with a doublet ground state the first of its type. To our knowledge, all previous examples of 4-coordinate cobalt(II) complexes with doublet ground states have adopted square planar structure types. Complex 1 provided a useful precursor to the corresponding bromide and chloride complexes, {[PhBP_3]Co(μ-Br)}_2, (2), and {[PhBP_3]Co(μ-Cl)}_2, (3). These complexes were similarly characterized and shown to be dimeric in the solid-state. In solution, however, the monomeric low spin form of 2 and 3 dominates at 25 °C. There is spectroscopic evidence for a temperature-dependent monomer/dimer equilibrium in solution for complex 3. Furthermore, the dimers 2 and 3 did not display appreciable antiferromagnetic coupling that is typical of halide and oxo-bridged copper(II) and cobalt(II) dimers. Rather, the EPR and SQUID data for solid samples of 2 and 3 suggest that they have triplet ground states. Complexes 1, 2, and 3 are extremely oxygen sensitive. Thus, stoichiometric oxidation of 1 by dioxygen produced the 4-coordinate, high spin complex [PhB(CH_2P(O)Ph_2)_2(CH_2PPh_2)]CoI, (4), in which the [PhBP_3] ligand had undergone a 4-electron oxidation. Reaction of 1 with TlOAr (Ar = 2,6-Me_2Ph) afforded an example of a 4-coordinate, high spin complex, [PhBP_3]Co(O-2,6-Me_2Ph) (5), with an intact [PhBP_3] ligand. The latter two complexes were spectroscopically and structurally characterized for comparison to complexes 1, 2, and 3. Our data for these complexes collectively suggest that the [PhBP_3] ligand provides an unusually strong ligand-field to these divalent cobalt complexes that is chemically distinct from typical tris(phosphine) donor ligand sets, and distinct from tridentate borato ligands that have been previously studied. Coupling this strong ligand-field with a pronounced axial distortion away from tetrahedral symmetry, a geometric consequence that is enforced by the [PhBP_3] ligand, provides access to monomeric [PhBP_3]CoX complexes with doublet rather than quartet ground states

Methodology for global sensitivity analysis of consequence models

Research Highlights A methodology for global sensitivity analysis of consequence models is presented using a statistical emulator The methodology is demonstrated on the Phast consequence model for steady-state discharges of high-pressure carbon dioxide Dispersion model input parameters that have a significant effect on the extent of the plume are identified The study demonstrates that Bayesian analysis of model sensitivity can be conducted quickly and easily There is the potential for this to become a routine part of consequence modelling Abstract A methodology is presented for global sensitivity analysis of consequence models used in process safety applications. It involves running a consequence model around a hundred times and using the results to construct a statistical emulator, which is essentially a sophisticated curve fit to the data. The emulator is then used to undertake the sensitivity analysis and identify which input parameters (e.g. operating temperature and pressure, wind speed) have

Strategic review of enhancements and culture-based fisheries

Enhancements are interventions in the life cycle of common-pool aquatic resources. Enhancement technologies include culture-based fisheries, habitat modifications, fertilization, feeding and elimination of predators/competitors. Enhancements are estimated to yield about two million mt per year, mostly from culture-based fisheries in fresh waters where they account for some 20 percent of capture, or 10 percent of combined capture and culture production. Marine enhancements are still at an experimental stage, but some have reached commercial production. Enhancements use limited external feed and energy inputs, and can provide very high returns for labour and capital input. Moreover, enhancement initiatives can facilitate institutional change and a more active management of aquatic resources, leading to increased productivity, conservation and wider social benefits. Enhancements may help to maintain population abundance, community structure and ecosystem functioning in the face of heavy exploitation and/or environmental degradation. Negative environmental impacts may arise from ecological and genetic interactions between enhanced and wild stocks. Many enhancements have not realised their full potential because of a failure to address specific institutional, technological, management and research requirements emanating from two key characteristics. Firstly, enhancement involves investment in common-pool resources and can only be sustained under institutional arrangements that allow regulation of use and a flow of benefits to those who bear the costs of enhancement. Secondly, interventions are limited to certain aspects of the life cycle of stocks, and outcomes are strongly dependent on natural conditions beyond management control. Hence, management must be adapted to local conditions to be effective, and certain conditions may preclude successful enhancement altogether. Governments have a major role to play in facilitating enhancement initiatives through the establishment of conducive institutional arrangements, appropriate research support, and the management of environmental and other impacts on and from enhancements.<br /

Outer-Sphere Contributions to the Electronic Structure of Type Zero Copper Proteins

Bioinorganic canon states that active-site thiolate coordination promotes rapid electron transfer (ET) to and from type 1 copper proteins. In recent work, we have found that copper ET sites in proteins also can be constructed without thiolate ligation (called “type zero” sites). Here we report multifrequency electron paramagnetic resonance (EPR), magnetic circular dichroism (MCD), and nuclear magnetic resonance (NMR) spectroscopic data together with density functional theory (DFT) and spectroscopy-oriented configuration interaction (SORCI) calculations for type zero Pseudomonas aeruginosa azurin variants. Wild-type (type 1) and type zero copper centers experience virtually identical ligand fields. Moreover, O-donor covalency is enhanced in type zero centers relative that in the C112D (type 2) protein. At the same time, N-donor covalency is reduced in a similar fashion to type 1 centers. QM/MM and SORCI calculations show that the electronic structures of type zero and type 2 are intimately linked to the orientation and coordination mode of the carboxylate ligand, which in turn is influenced by outer-sphere hydrogen bonding

CPX-351 treatment in secondary acute myeloblastic leukemia is effective and improves the feasibility of allogeneic stem cell transplantation: results of the Italian compassionate use program

Secondary acute myeloid leukemia (sAML) poorly responds to conventional treatments and allogeneic stem cell transplantation (HSCT). We evaluated toxicity and efficacy of CPX-351 in 71 elderly patients (median age 66 years) with sAML enrolled in the Italian Named (Compassionate) Use Program. Sixty days treatment-related mortality was 7% (5/71). The response rate at the end of treatment was: CR/CRi in 50/71 patients (70.4%), PR in 6/71 (8.5%), and NR in 10/71 (19.7%). After a median follow-up of 11 months relapse was observed in 10/50 patients (20%) and 12 months cumulative incidence of relapse (CIR) was 23.6%. Median duration of response was not reached. In competing risk analysis, CIR was reduced when HSCT was performed in first CR (12 months CIR of 5% and 37.4%, respectively, for patients receiving (=20) or not (=30) HSCT, p = 0.012). Twelve-months OS was 68.6% (median not reached). In landmark analysis, HSCT in CR1 was the only significant predictor of longer survival (12 months OS of 100 and 70.5%, for patients undergoing or not HSCT in CR1, respectively, p = 0.011). In conclusion, we extend to a real-life setting, the notion that CPX is an effective regimen for high risk AML patients and may improve the results of HSCT

Properties of Photogenerated Tryptophan and Tyrosyl Radicals in Structurally Characterized Proteins Containing Rhenium(I) Tricarbonyl Diimines

Aromatic amino acid radicals are key intermediates in nucleic acid biosynthesis, DNA repair, dioxygen reduction by cytochrome oxidase, water oxidation by PSII, as well as other biological procesess. In our work on electron tunneling in proteins, we have developed laser flash/quench methods that potentially could facilitate the study of such highly reactive radicals. To test our methods, we are investigating two structurally characterized proteins, [Re(CO)_3(L)(H83)]^+AzM^(2+) and [Re(CO)_3(L)(H107)]^+AzM^(2+) (L ) 1,10-phenanthroline (phen) or 4,7-Me_2phen; Az ) Pseudomonas aeruginosa azurin; M ) Cu or Zn). Of special interest is that calculations and experiments on the H107 protein show that Cu^+ oxidation via electron transfer (ET) through an intervening tyrosine (Cu^+ → Y108^(./) → Re(2+)) is over 2 orders of magnitude faster than optimized (Cu^+ → Re^(2+)) electron tunneling

Alien Planktonic Species in the Marine Realm: What Do They Mean for Ecosystem Services Provision?

Human well-being is significantly affected by the contributions provided by ecosystems, or ecosystem services. In this well-illustrated atlas, world-class experts identify and discuss key driving forces, trade-offs, and synergies of ecosystem services. Through interdisciplinary case studies varying across ecosystems and scales, this atlas narrows the knowledge gap between ecosystem services management and related fields of study. This atlas begins with conceptual background and proceeds to present drivers and their risks for ecosystems, their functions and services, and biodiversity. Trade-offs and synergies among ecosystem services and societal responses to the drivers and trade-offs are discussed. Sustainable land management and governance concepts are demonstrated throughout the atlas. Environmental scientists, practitioners and policy makers worldwide will appreciate the solutions and best practices identified throughout the chapters. Students of environmental sciences, socio-economics and landscape planning will find this atlas to be a valuable read, as well