Plant ionomics : From elemental profiling to environmental adaptation

FUNDING UK Biotechnology and Biological Sciences Research Council grant BB/L027739/1 and BB/L000113/1 (to D.E.S.), the US National Institutes of Health grant 2R01GM078536 (to D.E.S.), and the US National Science Foundation grant IOB 0419695 (to D.E.S.) ACKNOWLEDGMENTS We wish to thank our collaborators Mary Lou Guerinot, Niko Geldner, and Christian Hermans for kindly allowing us to incorporate in this update unpublished data on BRUTUS, SGN1, and SGN3, respectively. We also thank Mary Lou Guerinot, Niko Geldner, Takehiro Kamiya, and the ERACAPS Root Barrier project for productive discussions relating to ionomics and the plant ionome. No conflict of interest declared.

Dynamics of the last four glacial terminations recorded in Lake Van, Turkey

A well-dated suite of Lake Van climate-proxy data covering the last 360 ka documents environmental changes over 4 glacial/interglacial cycles in Eastern Anatolia, Turkey. The picture of cold and dry glacials and warm and wet interglacials emerging from pollen, organic carbon, authigenic carbonate content, elemental profiling by XRF and lithological analyses is inconsistent with classical interpretation of ox- ygen isotopic composition of carbonates pointing to a more complex pattern in Lake Van region. Detailed analysis of glacial terminations allows for the constraining of a depositional model explaining different patterns observed in all the proxies. We hypothesize that variations in relative contribution of rainfall, snowmelt and glacier meltwater recharging the basin have a very important role for all sedimentary processes in Lake Van. Lake level of glacial Lake Van, predominantly fed by snowmelt, was low, the water column was oxic, and carbonates precipitating in the epilimnion recorded the light isotopic signature of inflow. During terminations, increasing rainfall and significant supply of mountain glaciers' meltwater contributed to lake level rise. Increased rainfall enhanced density gradients in the water column, and hindered mixing leading to development of bottom-water anoxia. Carbonates precipitating during terminations show large fluctuations in their isotopic composition. Full interglacial conditions in Lake Van are characterized by high or slowly falling lake level. Rainfall and snowmelt feed the lake but due to re-established mixing, the isotopic composition of authigenic carbonates is heavier and closer to that of evaporation-influenced lake water than that of runoff representing snowmelt and atmospheric precipitation.

Discrimination of honey of different floral origins by a combination of various chemical parameters

Abstract Honey is a high value food commodity with recognized nutraceutical properties. A primary driver of the value of honey is its floral origin. The feasibility of applying multivariate data analysis to various chemical parameters for the discrimination of honeys was explored. This approach was applied to four authentic honeys with different floral origins (rata, kamahi, clover and manuka) obtained from producers in New Zealand. Results from elemental profiling, stable isotope analysis, metabolomics (UPLC-QToF MS), and NIR, FT-IR, and Raman spectroscopic fingerprinting were analyzed. Orthogonal partial least square discriminant analysis (OPLS-DA) was used to determine which technique or combination of techniques provided the best classification and prediction abilities. Good prediction values were achieved using metabolite data (for all four honeys, Q² = 0.52; for manuka and clover, Q² = 0.76) and the trace element/isotopic data (for manuka and clover, Q² = 0.65), while the other chemical parameters showed promise when combined (for manuka and clover, Q² = 0.43).

Elemental and metabolite profiling of nickel hyperaccumulators from New Caledonia

Leaf material from nine Ni hyperaccumulating species was collected in New Caledonia: Homalium kanaliense (Vieill.) Briq., Casearia silvana Schltr, Geissois hirsuta Brongn. & Gris, Hybanthus austrocaledonicusSeem, Psychotria douarrei (G. Beauvis.) Däniker, Pycnandra acuminata (Pierre ex Baill.) Swenson & Munzinger (syn Sebertia acuminata Pierre ex Baill.), Geissois pruinosa Brongn. & Gris, Homalium deplanchei (Viell) Warb. and Geissois bradfordii (H.C. Hopkins). The elemental concentration was determined by inductively-coupled plasma optical emission spectrometry (ICP-OES) and from these results it was foundthat the species contained Ni concentrations from to 250–28,000 mg/kg dry mass. Gas chromatography mass spectrometry (GC–MS)-based metabolite profiling was then used to analyse leaves of each species.The aim of this study was to target Ni-binding ligands through correlation analysis of the metabolite levels and leaf Ni concentration. Approximately 258 compounds were detected in each sample. As has been observed before, a correlation was found between the citric acid and Ni concentrations in the leaves for all species collected. However, the strongest Ni accumulator, P. douarrei, has been found to contain particularly high concentrations of malonic acid, suggesting an additional storage mechanism for Ni. A size exclusion chromatography separation protocol for the separation of Ni-complexes in P. acuminata sap was also applied to aqueous leaf extracts of each species. A number of metabolites were identified in complexes with Ni including Ni-malonate from P. douarrei. Furthermore, the levels for some metabolites were found to correlate with the leaf Ni concentration. These data show that Ni ions can be bound by a range of small molecules in Ni hyperaccumulation in plants.

Elemental and molecular profiling of licit, illicit, and niche tobacco

The recognition of differences between regulated large-scale mass manufactured products and the uncontrolled cultivation of tobaccos for illicit purposes plays a significant role within identification of provenance. This research highlights X-ray fluorescence and Fourier transform infrared spectroscopy as useful analytical techniques for the rapid identification of tobacco samples of unknown provenance. Identification of key discriminative features within each technique allowed for the development of typical characteristic profiles for each type of tobacco. Analysis using X-ray fluorescence highlights chlorine, potassium, calcium and iron as key elemental indicators of tobacco provenance. Significant levels of chlorine seen within Snüs samples prompted attempts to visualise chlorine containing regions and structures within the sample. Scanning electron microscopy images showed crystalline structures visible within the Snüs tobacco, structures which Energy dispersive X-ray spectroscopy qualitatively confirmed to contain chlorine. Chloride levels within Snüs samples were quantified using ion chromatography with levels found to range between 0.87mgmL‾¹ and 1.28mg. Additionally, FTIR indicated that absorbances attributed to carbonyl stretching at 1050-1150cm‾¹, alkane bending at 1350-1480cm‾¹and amide I stretching at 1600-1700cm‾¹ highlighting a spectral fingerprint region that allowed for the clear differentiation between different types of tobaccos using PCA analysis, but was limited by differentiation between provenance of cigarettes and hand rolled tobacco. X-ray fluorescence and Fourier transform infrared spectroscopy yielded different information with regards tobacco discrimination and provenance, however both methods overall analysis time and cost reduced indicating usefulness as potential handheld analytical techniques in the field.

Profiling the ionome of rice and its use in discriminating geographical origins at the regional scale, China

Element profile was investigated for their use to trace the geographical origin of rice (Oryza sativa L.) samples. The concentrations of 13 elements (calcium (Ca), potassium (K), magnesium (Mg), phosphorus (P), boron (B), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), arsenic (As), selenium (Se), molybdenum (Mo), and cadmium (Cd)) were determined in the rice samples by inductively coupled plasma optical emission and mass spectrometry. Most of the essential elements for human health in rice were within normal ranges except for Mo and Se. Mo concentrations were twice as high as those in rice from Vietnam and Spain. Meanwhile, Se concentrations were three times lower in the whole province compared to the Chinese average level of 0.088 mg/kg. About 12% of the rice samples failed the Chinese national food safety standard of 0.2 mg/kg for Cd. Combined with the multi-elemental profile in rice, the principal component analysis (PCA), discriminant function analysis (DFA) and Fibonacci index analysis (FIA) were applied to discriminate geographical origins of the samples. Results indicated that the FIA method could achieve a more effective geographical origin classification compared with PCA and DFA, due to its efficiency in making the grouping even when the elemental variability was so high that PCA and DFA showed little discriminatory power. Furthermore, some elements were identified as the most powerful indicators of geographical origin: Ca, Ni, Fe and Cd. This suggests that the newly established methodology of FIA based on the ionome profile can be applied to determine the geographical origin of rice.

High-Resolution Chemical Depth Profiling of Solid Material Using a Miniature Laser Ablation/Ionization Mass Spectrometer

High-resolution chemical depth profiling measurements of copper films are presented. The 10 μm thick copper test samples were electrodeposited on a Si-supported Cu seed under galvanostatic conditions in the presence of particular plating additives (SPS, Imep, PEI, and PAG) used in the semiconductor industry for the on-chip metallization of interconnects. To probe the trend of these plating additives toward inclusion into the deposit upon growth, quantitative elemental mass spectrometric measurements at trace level concentration were conducted by using a sensitive miniature laser ablation ionization mass spectrometer (LIMS), originally designed and developed for in situ space exploration. An ultrashort pulsed laser system (τ ∼ 190 fs, λ = 775 nm) was used for ablation and ionization of sample material. We show that with our LIMS system, quantitative chemical mass spectrometric analysis with an ablation rate at the subnanometer level per single laser shot can be conducted. The measurement capabilities of our instrument, including the high vertical depth resolution coupled with high detection sensitivity of ∼10 ppb, high dynamic range ≥10(8), measurement accuracy and precision, is of considerable interest in various fields of application, where investigations with high lateral and vertical resolution of the chemical composition of solid materials are required, these include, e.g., wafers from semiconductor industry or studies on space weathered samples in space research.

Task profiling : A task-Based approach to measuring the integration of ICT in the classroom

The measurement of ICT (information and communication technology) integration is emerging as an area of research interest with such systems as Education Queensland including it in their recently released list of research priorities. Studies to trial differing integration measurement instruments have taken place within Australia in the last few years, particularly Western Australia (Trinidad, Clarkson, & Newhouse, 2004; Trinidad, Newhouse & Clarkson, 2005), Tasmania (Fitzallen 2005) and Queensland (Finger, Proctor, & Watson, 2005). This paper will add to these investigations by describing an alternate and original methodological approach which was trialled in a small-scale pilot study conducted jointly by Queensland Catholic Education Commission (QCEC) and the Centre of Learning Innovation, Queensland University of Technology (QUT) in late 2005. The methodology described is based on tasks which, through a process of profiling, can be seen to be artefacts which embody the internal and external factors enabling and constraining ICT integration.

Computer profiling for forensic purposes

Computer forensics is the process of gathering and analysing evidence from computer systems to aid in the investigation of a crime. Typically, such investigations are undertaken by human forensic examiners using purpose-built software to discover evidence from a computer disk. This process is a manual one, and the time it takes for a forensic examiner to conduct such an investigation is proportional to the storage capacity of the computer's disk drives. The heterogeneity and complexity of various data formats stored on modern computer systems compounds the problems posed by the sheer volume of data. The decision to undertake a computer forensic examination of a computer system is a decision to commit significant quantities of a human examiner's time. Where there is no prior knowledge of the information contained on a computer system, this commitment of time and energy occurs with little idea of the potential benefit to the investigation. The key contribution of this research is the design and development of an automated process to describe a computer system and its activity for the purposes of a computer forensic investigation. The term proposed for this process is computer profiling. A model of a computer system and its activity has been developed over the course of this research. Using this model a computer system, which is the subj ect of investigation, can be automatically described in terms useful to a forensic investigator. The computer profiling process IS resilient to attempts to disguise malicious computer activity. This resilience is achieved by detecting inconsistencies in the information used to infer the apparent activity of the computer. The practicality of the computer profiling process has been demonstrated by a proof-of concept software implementation. The model and the prototype implementation utilising the model were tested with data from real computer systems. The resilience of the process to attempts to disguise malicious activity has also been demonstrated with practical experiments conducted with the same prototype software implementation.