Ian M. Jamie

Advancing chemistry by enhancing learning in the laboratory (ACELL): A model for providing professional and personal development and facilitating improved student laboratory learning outcomes

The Advancing Chemistry by Enhancing Learning in the Laboratory (ACELL) project aims to improve the quality of learning in undergraduate laboratories through two interlocking mechanisms. The first is to build a database of experiments that are both chemically and educationally sound by testing them in a third-party laboratory, usually through an ACELL workshop involving both academic staff and students, to ensure that they work. The second mechanism provides personal and professional development for staff and students through a workshop process, and reinforced through on-going engagement with the ACELL community via the project website and experiment assessment and evaluation. The ACELL workshops include discussion of educational issues, both in abstract (through discussing laboratory learning in general) and concrete (through debriefing of each experiment tested) terms. This paper discusses the design of the ACELL project, and illustrates some of the successes of the staff and student personal and professional development aims. [Chem. Educ. Res. Pract., 2007, 8 (2), 232-254]

Nitrous oxide emissions from grazed pastures: measurements at different scales

Abstract Estimates made by the Intergovernmental Panel on Climate Change (IPCC) and the Australian National Greenhouse Gas Inventory Committee (NGGIC) suggest that grazed pastures are substantial anthropogenic sources of nitrous oxide (N2O), contributing 28% of all anthropogenic N2O emissions globally and >43% for Australia. These estimates are based almost wholly on extrapolations of enclosure experiments to the field scale and uncertainty levels are high. Verification with direct field measurements is needed. This paper reports micrometeorological studies of N2O emissions from Australian grazed pastures made at the same location on a variety of space scales. They included a mass-balance study employing a small test plot approximately 0.05 ha in area in which 14 sheep were grazed, tower-based flux measurements representing areas between 25 ha and 5 km2 and convective boundary-layer budgets representing regions of order 100 km2. The mass-balance study, which was considered to be the most reliable micrometeorological approach, gave an average emission over 8 days of 1.87 g N2O–N head−1 d−1 corresponding to 11.5% of the nitrogen (N) voided by the animals in urine and dung. However, the data set included two days after rain on which emissions were an order of magnitude larger than on the other days in the study. For the latter, the emission of N2O accounted for 3.9% of the N excreted. Although uncertainty levels remain high due to large temporal and spatial variability, the micrometeorological measurements suggested that N2O emissions might be considerably larger than those predicted by NGGIC algorithms which use emission factors of 0.4% for urine and 1.25% for dung, but appear to be predicted more closely by IPCC algorithms which use 2% for both. The study has indicated ways to improve the precision of relevant micrometeorological approaches.

Verifying inventory predictions of animal methane emissions with meteorological measurements.

The paper examines the strengths and weaknesses of a rangeof meteorological flux measurement techniques that mightbe used to verify predictions of greenhouse gas inventories.Recent research into emissions of methane (CH4)produced by enteric fermentation in grazing cattle and sheepis used to illustrate various methodologies. Quantifying thisimportant source presents special difficulties because the animalsconstitute moving, heterogeneously distributed, intermittent, pointsources. There are two general approaches: one, from the bottom up,involves direct measurements of emissions from a known number ofanimals, and the other, from the top down, infers areal emissions ofCH4 from its atmospheric signature. A mass-balance methodproved successful for bottom-up verification. It permits undisturbedgrazing, has a simple theoretical basis and is appropriate for fluxmeasurements on small plots and where there are scattered pointsources. The top-down methodologies include conventional flux-gradientapproaches and convective and nocturnal boundary-layer (CBL and NBL)budgeting schemes. Particular attention is given to CBL budget methods inboth differential and integral form. All top-down methodologies require ideal weather conditions for their application, and they suffer from the scattered nature of the source, varying wind directions and low instrument resolution. As for mass-balance, flux-gradient micrometeorological measurements were in good agreement with inventory predictions of CH4 production by livestock, but the standard errors associated with both methods were too large to permit detection of changes of a few per cent in emission rate, which might be important for inventory, regulatory or research purposes. Fluxes calculated by CBL and NBL methods were of the same order of magnitude as inventory predictions, but more improvement is needed before their use can be endorsed. Opportunities for improving the precision of both bottom-up and top-down methodologies are discussed.

Real-time field measurements of stable isotopes in water and CO2 by Fourier transform infrared spectrometry

Continuous records of isotope behaviour in the environment are invaluable to understanding mass and energy fluxes. Although techniques such as isotope ratio mass spectrometry provide high precision data, they are not well suited to the analysis of a large number of samples and are currently restricted to use in the laboratory. Fourier transform infrared spectrometers are relatively cheap and sufficiently portable and robust to be taken into the field to collect continuous records of gas-phase isotope behaviour. Several examples of the application of this technique will be presented. One data set provides half-hourly determinations of vertical profiles of D/H in water vapour above agricultural fields over a 3-week period; the same infrared spectra can also be used to determine 13C/12C in CO2. The technique has also been applied to the study of CO2 in ambient air and in a limestone cave system. Some of the features and complications associated with the method will also be considered.

Increased ratio of electron transport to net assimilation rate supports elevated isoprenoid emission rate in eucalypts under drought

Volatile isoprenoids emitted by plants, enhanced by photosynthesis under drought, have a significant influence on ozone pollution and global climate. Plants undergoing heat and low-CO2 stresses emit large amounts of volatile isoprenoids compared with those in stress-free conditions. One hypothesis posits that the balance between reducing power availability and its use in carbon assimilation determines constitutive isoprenoid emission rates in plants and potentially even their maximum emission capacity under brief periods of stress. To test this, we used abiotic stresses to manipulate the availability of reducing power. Specifically, we examined the effects of mild to severe drought on photosynthetic electron transport rate (ETR) and net carbon assimilation rate (NAR) and the relationship between estimated energy pools and constitutive volatile isoprenoid emission rates in two species of eucalypts: Eucalyptus occidentalis (drought tolerant) and Eucalyptus camaldulensis (drought sensitive). Isoprenoid emission rates were insensitive to mild drought, and the rates increased when the decline in NAR reached a certain species-specific threshold. ETR was sustained under drought and the ETR-NAR ratio increased, driving constitutive isoprenoid emission until severe drought caused carbon limitation of the methylerythritol phosphate pathway. The estimated residual reducing power unused for carbon assimilation, based on the energetic status model, significantly correlated with constitutive isoprenoid emission rates across gradients of drought (r2 > 0.8) and photorespiratory stress (r2 > 0.9). Carbon availability could critically limit emission rates under severe drought and photorespiratory stresses. Under most instances of moderate abiotic stress levels, increased isoprenoid emission rates compete with photorespiration for the residual reducing power not invested in carbon assimilation. A similar mechanism also explains the individual positive effects of low-CO2, heat, and drought stresses on isoprenoid emission.

Solvation and ion association in solutions containing oxyanions

Ion solvation and association behaviour has been studied for solutions of lithium perchlorate and lithium nitrate in N,N-dimethylformamide (DMF) methanol and ethanol. The techniques of Raman spectroscopy and multinuclear n.m.r. have been employed, and in some studies the cation has been caged in the cryptand Kryptofix 221. Solvation in DMF was examined through quantitative analysis of the OCN bending vibrational band of the DMF in the Raman spectra. A range of univalent and divalent cations was employed and solvation numbers and some information on solvation geometries were obtained. In alcohol solutions determination of solvation numbers was not possible but the involvement of Li+ and NO–3 produced observable spectroscopic changes, while the ClO–4 anion appeared to have only a weak solvation. Evidence for at least two associated species was obtained for both salts in DMF and ethanol and the concentration dependence of the species was determined. In methanol association was much less with the behaviour approaching that observed in aqueous solution.

Remote open-path cavity-ringdown spectroscopic sensing of trace gases in air, based on distributed passive sensors linked by km-long optical fibers.

A continuous-wave, rapidly swept cavity-ringdown spectroscopic technique has been developed for localized atmospheric sensing of trace gases at remote sites. It uses one or more passive open-path optical sensor units, coupled by optical fiber over distances of >1 km to a single transmitter/receiver console incorporating a photodetector and a swept-frequency diode laser tuned to molecule-specific near-infrared wavelengths. Ways to avoid interference from stimulated Brillouin scattering in long optical fibers have been devised. This rugged open-path system, deployable in agricultural, industrial, and natural atmospheric environments, is used to monitor ammonia in air. A noise-limited minimum detectable mixing ratio of ~11 ppbv is attained for ammonia in nitrogen at atmospheric pressure.

Raspberry Ketone Trifluoroacetate, a New Attractant for the Queensland Fruit Fly, Bactrocera Tryoni (Froggatt)

Queensland fruit fly, Bactrocera tryoni (Q-fly), is a major pest of horticultural crops in eastern Australia. Lures that attract male Q-fly are important for detection of incursions and outbreaks, monitoring of populations, and control by mass trapping and male annihilation. Cuelure, an analog of naturally occurring raspberry ketone, is the standard Q-fly lure, but it has limited efficacy compared with lures that are available for some other fruit flies such as methyl eugenol for B. dorsalis. Melolure is a more recently developed raspberry ketone analog that has shown better attraction than cuelure in some field studies but not in others. A novel fluorinated analog of raspberry ketone, raspberry ketone trifluoroacetate (RKTA), has been developed as a potential improvement on cuelure and melolure. RKTA placed on laboratory cages containing 2-week-old Q-flies elicited strong behavioral responses from males. Quantification of Q-fly responses in these cages, using digital images to estimate numbers of flies aggregated near different lures, showed RKTA attracted and arrested significantly more flies than did cuelure or melolure. RKTA shows good potential as a new lure for improved surveillance and control of Q-fly.

Species-specific photorespiratory rate, drought tolerance and isoprene emission rate in plants

The effect of drought on plant isoprene emission varies tremendously across species and environments. It was recently shown that an increased ratio of photosynthetic electron transport rate (ETR) to net carbon assimilation rate (NAR) consistently supported increased emission under drought. In this commentary, we highlight some of the physiological aspects of drought tolerance that are central to the observed variability. We briefly discuss some of the issues that must be addressed in order to refine our understanding of plant isoprene emission response to drought and increasing global temperature.

Effects of acyl chain length on the conformation of myelin basic protein bound to lysolipid micelles

The interactions of myelin basic protein with micelles of lysophosphatidylcholine detergents of different acyl chain lengths were investigated by circular dichroism (CD), small-angle X-ray scattering, Fourier transform infrared spectroscopy (FT-IR), and 1H, 13C and 31P nuclear magnetic resonance spectroscopy (NMR). Circular dichroic, FT-IR, and 1H NMR measurements indicated that the conformational changes induced in the protein molecules by association with micelles depended on the acyl chain length of the detergents. Size is one of the physical properties of micelles which is a function of the length of the acyl chains. The radii of gyration of detergent micelles in complexes with the protein measured by small-angle X-ray scattering indicated that the average size of the micelles was a quadratic function of the acyl chain length. The dependence of the protein conformational changes on micelle size was used to ascertain the order in which different protein segments associate with the detergents. Several procedures were employed to change the fluidity of micelles formed with detergents of given acyl chain lengths. The conformational changes observed on the MBP molecule by varying the micelle properties without changing the length of the chain, suggested that the changes depended on the size and fluidity of the micelles.