Proton transfer reaction mass spectrometry and the unambiguous real-time detection of 2,4,6 trinitrotoluene

Fears of terrorist attacks have led to the development of various technologies for the real-time detection of explosives, but all suffer from potential ambiguities in the assignment of threat agents. Using proton transfer reaction mass spectrometry (PTR-MS), an unusual bias dependence in the detection sensitivity of 2,4,6 trinitrotoluene (TNT) on the reduced electric field (E/N) has been observed. For protonated TNT, rather than decreasing signal intensity with increasing E/N, which is the more usual sensitivity pattern observed in PTR-MS studies, an anomalous behavior is first observed, whereby the signal intensity initially rises with increasing E/N. We relate this to unexpected ion-molecule chemistry based upon comparisons of measurements taken with related nitroaromatic compounds (1,3,5 trinitrobenzene, 1,3 dinitrobenzene, and 2,4 dinitrotoluene) and electronic structure calculations. This dependence provides an easily measurable signature that can be used to provide a rapid highly selective analytical procedure to minimize false positives for the detection of TNT. This has major implications for Homeland Security and, in addition, has the potential of making instrumentation cost-effective for use in security areas. This study shows that an understanding of fundamental ion-molecule chemistry occurring in low-pressure drift tubes is needed to exploit selectivity and sensitivity for analytical purposes.     

The characterisation of the interfacial chemistry of adhesion of rigid polyurethane foam to aluminium

The interfacial interactions between a rigid polyurethane foam (RPUF) and aluminium have been studied to understand the mechanisms of adhesion. Three different blowing systems are used in the production of the foam: chemical blowing, physical blowing and a mix of chemical and physical blowing systems. In addition an unfoamed system has been examined for comparison of the catalysts behaviour with and without blowing agents and the surfactant. Peeled failure surfaces have been examined by X-ray photoelectron spectroscopy (XPS) and time of flight secondary ion mass spectrometry (ToF–SIMS). To examine the intact interfacial regions of the RPUFs cured against aluminium, samples have been sectioned by microtomy. The failure surfaces of the aluminium sides exhibit relatively clean aluminium surfaces with RPUF residues observed for all three foamed systems; such thin RPUF layers (ca. 1 nm) indicate good adhesion (and a cohesive failure) between foam and substrate and that the interfacial adhesion is higher than the cohesive strength of the foam. The unfoamed system behaves in a similar manner but has a higher peel strength. A fragment indicative of covalent bond formation between isocyanate and aluminium (nominal mass at 102 u: AlCHNO₃ ⁻) is observed on the failure surface of aluminium side, where RPUF/aluminium interface region is present, for all foams. The catalyst used in these formulations, pentamethyldiethylenetriamine (PMDETA), is concentrated at the interface area. Whilst examination of the sectioned specimens shows that the silicone surfactant is concentrated within the cell area fulfilling its role on cell formation and stabilisation, and is not segregated at the RPUF/aluminium interface.     

Processability studies of silica‐thermoset polymer matrix nanocomposites

The aim of this study is to investigate the processability of silica‐thermoset polymer matrix nanocomposites in terms of dispersion of silica nanoparticles and their effect on curing. Two thermosetting resins were considered, an epoxy and a polyester resin, with 5% silica, although 1% silica was also used in preliminary studies in the polyester system. Various combinations of mechanical mixing and sonication were investigated for the dispersion of silica nanoparticles under different processing conditions and times in solvent‐free and solvent‐containing systems. It was found that the best dispersion route involved a solvent‐aided dispersion technique. Consequently, different procedures for the solvent removal were investigated. Optical microscopy and SEM were used to characterize the resulting nanocomposites. DSC and rheological DMTA tests demonstrated that the silica nanoparticles shorten the gel time and promote curing in these thermosetting systems. POLYM. ENG. SCI., 2008. © 2007 Society of Plastics Engineers     

Towards risk‐based water resources planning in England and Wales under a changing climate

The publication of the UKCP09 climate change projections for the United Kingdom provides the opportunity for more rigorous inclusion of climate change uncertainty in water resources planning. We set out how the current approach to incorporating climate change and other uncertainties in water resources planning may be updated to incorporate the UKCP09 projections. In an uncertain future, the frequency with which customers will experience water shortages cannot be predicted for sure, so a water company cannot predict definitely whether it will or will not fulfil its Level of Service commitments. We therefore go on to propose that the probability of failing to meet Level of Service (for given populations of customers) provides an appropriate metric of risk, which conveniently summarises the uncertainties associated with supply and demand, including climate change uncertainties. We sketch out how this risk metric can be calculated based upon simulation modelling of the water resource system.     

Coal-tar-based pavement sealcoat and PAHs: implications for the environment, human health, and stormwater management

Coal-tar-based sealcoat products, widely used in the central and eastern U.S. on parking lots, driveways, and even playgrounds, are typically 20-35% coal-tar pitch, a known human carcinogen that contains about 200 polycyclic aromatic hydrocarbon (PAH) compounds. Research continues to identify environmental compartments-including stormwater runoff, lake sediment, soil, house dust, and most recently, air-contaminated by PAHs from coal-tar-based sealcoat and to demonstrate potential risks to biological communities and human health. In many cases, the levels of contamination associated with sealed pavement are striking relative to levels near unsealed pavement: PAH concentrations in air over pavement with freshly applied coal-tar-based sealcoat, for example, were hundreds to thousands of times higher than those in air over unsealed pavement. Even a small amount of sealcoated pavement can be the dominant source of PAHs to sediment in stormwater-retention ponds; proper disposal of such PAH-contaminated sediment can be extremely costly. Several local governments, the District of Columbia, and the State of Washington have banned use of these products, and several national and regional hardware and home-improvement retailers have voluntarily ceased selling them.     

Reduction in Lentil Cooking Time Using Micronization: Comparison of 2 Micronization Temperatures

Laird No. 1 lentils micronized (high‐intensity infrared heat) to give internal temperatures of 138 and 170 °C were compared to unprocessed lentils stored at room temperature. Micronized lentils, which had been tempered to 33% moisture for 16 h, required less force to compress after cooking and contained increased levels of gelatinized starch and pectic substances but decreased levels of soluble protein, phytic acid, and neutral detergent fiber compared to the unprocessed lentils. Cell walls in the micronized lentil were less susceptible to fracture, and the microstructure was more open. Properties of the micronized lentils were better when the internal temperature reached 138 °C. When micronized to an internal temperature of 170 °C, cooked lentils were harder, possibly due to greater moisture losses and a change in the neutral detergent fiber. Micronization resulted in a slight darkening of the lentils, and this was accentuated at 170 °C.