Effect of sugarcane cropping systems on herbicide losses in surface runoff

Herbicide runoff from cropping fields has been identified as a threat to the Great Barrier Reef ecosystem. A field investigation was carried out to monitor the changes in runoff water quality resulting from four different sugarcane cropping systems that included different herbicides and contrasting tillage and trash management practices. These include (i) Conventional - Tillage (beds and inter-rows) with residual herbicides used; (ii) Improved - only the beds were tilled (zonal) with reduced residual herbicides used; (iii) Aspirational - minimum tillage (one pass of a single tine ripper before planting) with trash mulch, no residual herbicides and a legume intercrop after cane establishment; and (iv) New Farming System (NFS) - minimum tillage as in Aspirational practice with a grain legume rotation and a combination of residual and knockdown herbicides. Results suggest soil and trash management had a larger effect on the herbicide losses in runoff than the physico-chemical properties of herbicides. Improved practices with 30% lower atrazine application rates than used in conventional systems produced reduced runoff volumes by 40% and atrazine loss by 62%. There were a 2-fold variation in atrazine and >10-fold variation in metribuzin loads in runoff water between reduced tillage systems differing in soil disturbance and surface residue cover from the previous rotation crops, despite the same herbicide application rates. The elevated risk of offsite losses from herbicides was illustrated by the high concentrations of diuron (14mugL-1) recorded in runoff that occurred >2.5months after herbicide application in a 1st ratoon crop. A cropping system employing less persistent non-selective herbicides and an inter-row soybean mulch resulted in no residual herbicide contamination in runoff water, but recorded 12.3% lower yield compared to Conventional practice. These findings reveal a trade-off between achieving good water quality with minimal herbicide contamination and maintaining farm profitability with good weed control.

Contactless Spectral-Dependent Measurement of Bulk Lifetime and Surface Recombination Velocity in Silicon Photovoltaic Materials

Charge carrier lifetime measurements in bulk or unfinished photovoltaic (PV) materials allow for a more accurate estimate of power conversion efficiency in completed solar cells. In this work, carrier lifetimes in PV- grade silicon wafers are obtained by way of quasi-steady state photoconductance measurements. These measurements use a contactless RF system coupled with varying narrow spectrum input LEDs, ranging in wavelength from 460 nm to 1030 nm. Spectral dependent lifetime measurements allow for determination of bulk and surface properties of the material, including the intrinsic bulk lifetime and the surface recombination velocity. The effective lifetimes are fit to an analytical physics-based model to determine the desired parameters. Passivated and non-passivated samples are both studied and are shown to have good agreement with the theoretical model.

The development of planar high-K/III-V p-channel MOSFETs for post-silicon CMOS

Conventional Si complementary-metal-oxide-semiconductor (CMOS) scaling is fast approaching its limits. The extension of the logic device roadmap for future enhancements in transistor performance requires non-Si materials and new device architectures. III-V materials, due to their superior electron transport properties, are well poised to replace Si as the channel material beyond the 10nm technology node to mitigate the performance loss of Si transistors from further reductions in supply voltage to minimise power dissipation in logic circuits. However several key challenges, including a high quality dielectric/III-V gate stack, a low-resistance source/drain (S/D) technology, heterointegration onto a Si platform and a viable III-V p-metal-oxide-semiconductor field-effect-transistor (MOSFET), need to be addressed before III-Vs can be employed in CMOS. This Thesis specifically addressed the development and demonstration of planar III-V p-MOSFETs, to complement the n-MOSFET, thereby enabling an all III-V CMOS technology to be realised. This work explored the application of InGaAs and InGaSb material systems as the channel, in conjunction with Al2O3/metal gate stacks, for p-MOSFET development based on the buried-channel flatband device architecture. The body of work undertaken comprised material development, process module development and integration into a robust fabrication flow for the demonstration of p-channel devices. The parameter space in the design of the device layer structure, based around the III-V channel/barrier material options of In_x≥0.53Ga_1-xAs/In_0.52Al_0.48As and In_x≥0.1Ga_1-xSb/AlSb, was systematically examined to improve hole channel transport. A mobility of 433 cm²/Vs, the highest room temperature hole mobility of any InGaAs quantum-well channel reported to date, was obtained for the In_0.85Ga_0.15As (2.1% strain) structure. S/D ohmic contacts were developed based on thermally annealed Au/Zn/Au metallisation and validated using transmission line model test structures. The effects of metallisation thickness, diffusion barriers and de-oxidation conditions were examined. Contacts to InGaSb-channel structures were found to be sensitive to de-oxidation conditions. A fabrication process, based on a lithographically-aligned double ohmic patterning approach, was realised for deep submicron gate-to-source/drain gap (L_side) scaling to minimise the access resistance, thereby mitigating the effects of parasitic S/D series resistance on transistor performance. The developed process yielded gaps as small as 20nm. For high-k integration on GaSb, ex-situ ammonium sulphide ((NH₄)₂S) treatments, in the range 1%-22%, for 10min at 295K were systematically explored for improving the electrical properties of the Al₂O₃/GaSb interface. Electrical and physical characterisation indicated the 1% treatment to be most effective with interface trap densities in the range of 4 - 10×10¹²cm^-2eV^-1 in the lower half of the bandgap. An extended study, comprising additional immersion times at each sulphide concentration, was further undertaken to determine the surface roughness and the etching nature of the treatments on GaSb. A number of p-MOSFETs based on III-V-channels with the most promising hole transport and integration of the developed process modules were successfully demonstrated in this work. Although the non-inverted InGaAs-channel devices showed good current modulation and switch-off characteristics, several aspects of performance were non-ideal; depletion-mode operation, modest drive current (I_d,sat=1.14mA/mm), double peaked transconductance (g_m=1.06mS/mm), high subthreshold swing (SS=301mV/dec) and high on-resistance (R_on=845kΩ.μm). Despite demonstrating substantial improvement in the on-state metrics of I_d,sat (11×), g_m (5.5×) and R_on (5.6×), inverted devices did not switch-off. Scaling gate-to-source/drain gap (L_side) from 1μm down to 70nm improved I_d,sat (72.4mA/mm) by a factor of 3.6 and gm (25.8mS/mm) by a factor of 4.1 in inverted InGaAs-channel devices. Well-controlled current modulation and good saturation behaviour was observed for InGaSb-channel devices. In the on-state In_0.3Ga_0.7Sb-channel (I_d,sat=49.4mA/mm, g_m=12.3mS/mm, R_on=31.7kΩ.μm) and In_0.4Ga_0.6Sb-channel (I_d,sat=38mA/mm, g_m=11.9mS/mm, R_on=73.5kΩ.μm) devices outperformed the InGaAs-channel devices. However the devices could not be switched off. These findings indicate that III-V p-MOSFETs based on InGaSb as opposed to InGaAs channels are more suited as the p-channel option for post-Si CMOS.

Seasonal changes of heat and moisture fluxes from the Caspian Sea surface and its effect on synoptic systems with heavy rainfalls in southern shores of the sea during 2005-2010

Caspian Sea with its unique characteristics is a significant source to supply required heat and moisture for passing weather systems over the north of Iran. Investigation of heat and moisture fluxes in the region and their effects on these systems that could lead to floods and major financial and human losses is essential in weather forecasting. Nowadays by improvement of numerical weather and climate prediction models and the increasing need to more accurate forecasting of heavy rainfall, the evaluation and verification of these models has been become much more important. In this study we have used the WRF model as a research-practical one with many valuable characteristics and flexibilities. In this research, the effects of heat and moisture fluxes of Caspian Sea on the synoptic and dynamical structure of 20 selective systems associated with heavy rainfall in the southern shores of Caspian Sea are investigated. These systems are selected based on the rainfall data gathered by three local stations named: Rasht, Babolsar and Gorgan in different seasons during a five-year period (2005-2010) with maximum amount of rainfall through the 24 hours of a day. In addition to synoptic analyses of these systems, the WRF model with and without surface flues was run using the two nested grids with the horizontal resolutions of 12 and 36 km. The results show that there are good consistencies between the predicted distribution of rainfall field, time of beginning and end of rainfall by the model and the observations. But the model underestimates the amounts of rainfall and the maximum difference with the observation is about 69%. Also, no significant changes in the results are seen when the domain and the resolution of computations are changed. The other noticeable point is that the systems are severely weakened by removing heat and moisture fluxes and thereby the amounts of large scale rainfall are decreased up to 77% and the convective rainfalls tend to zero.

In vitro effects of erosive challenge on the surface properties of sealants

Aim: To assess in vitro the surface roughness (Ra), Vickers hardness (VHN) and surface morphology of resin and glass ionomer materials used for sealants after dynamic erosive challenge. Methods: Twenty specimens of each material were prepared and divided into experimental (erosive challenge) and control groups (n=10): Protect Riva (SDI), Opallis Flow (3M ESPE), Fluroshield (Dentsply), Filtek Z350 XT Flow (3M ESPE). The erosive challenge was performed 4 times per day (90 s) in cola drink and for 2 h in artificial saliva for 7 days. The control specimens were maintained in artificial saliva. Ra and VHN readings were performed before and after erosion. The percentage of hardness loss (%VHN) was obtained after erosion. The surface morphology was evaluated by scanning electron microscopy (SEM). The data were analyzed by ANOVA, Tukey and paired t tests (α=0.05). Results: After erosion and saliva immersion, there was an increase in Ra values for all groups and Riva group showed the highest Ra values. After erosive challenge, Riva and Filtek groups showed significant decrease in VHN values, but Filtek group showed the greatest %VHN. For all groups there was inorganic particle protrusion and matrix degradation after erosion visualized by SEM images. Conclusions: Erosive challenge affected the surface properties of all materials used as sealants, particularly in the Riva and Filtek groups.

Pore size distributions derived from adsorption isotherms, immersion calorimetry, and isosteric heats: A comparative study

We compare the pore size distribution of a well-characterized activated carbon derived from model-dependent, adsorption integral equation (AIE) methods with those from model-independent, immersion calorimetry and isosteric heat analyses. The AIE approach applied to nitrogen gave a mean pore width of 0.57 nm; the CO2 distribution exhibited wider dispersion. Spherical model application to CO2 and diffusion limitations for nitrogen and argon were proposed as primary reasons for inconsistency. Immersion enthalpy revealed a sharp decrease in available area equivalent to a cut-off due to molecular exclusion when the accessible surface was assessed against probe kinetic diameter. Mean pore width was identified as 0.58 ± 0.02 nm, endorsing the underlying assumptions for the nitrogen-based AIE approach. A comparison of the zero-coverage isosteric heat of adsorption for various non-polar adsorptives by the porous test sample was compared with the same adsorptives in contact with a non-porous reference adsorbent, leading to an energy ratio or adsorption enhancement factor. A linear relationship between the energy ratio and probe kinetic diameter indicated a primary pore size at 0.59 nm. The advantage of this enthalpy, model-independent methods over AIE were due to no assumptions regarding probe molecular shape, and no assumptions for pore shape and/or connectivity.

Controlled surface nanotopography and oxygen plasma treatment of PEEK to improve cellular response

Poly(aryl-ether-ether-ketone) (PEEK) is a semi crystalline polymer which exhibits properties that make it an attractive choice for use as an implant material. It displays natural radiolucency, and MRI compatibility, as well as good chemical and sterilization resistance, both of which make it of particular interest in orthopaedic implants. However, PEEK has demonstrated poor cellular adhesion both in vitro and in vivo. This is problematic as implant surfaces that do not develop a layer of adhesive cells are at risk of undergoing fibrous encapsulation, which in turn leads to lack of a strong interface between the implant device and the patient tissue, which can in turn lead to failure of the implant and revision surgery . As incorporating nanotopography into a polymer surface has been demonstrated to be able to direct the differentiation behaviour of stem cells, a possible solution to PEEKs underlying issues with poor cellular response would be to incorporate specific nanoscale topography into the material surface through injection moulding, and then analysing if this is a viable method for addressing PEEKs issues with cellular response. In addition to nanoscale topography, the experimental PEEK surfaces were treated with oxygen plasma to address the underlying cytophobicity of the material. As this type of treatment has been documented to be capable of etching the PEEK surface, experiments were carried out to quantify the effect of this treatment, both on the ability of cells to adhere to the PEEK surface, as well as the effect it has upon the nanotopography present at the PEEK surface. The results demonstrated that there were a range of plasma treatments which would significantly improve the ability of cells to adhere to the PEEK surface without causing unacceptable damage to the nanotopography. Three different types of cells with osteogenic capacity were tested with the PEEK surfaces to gauge the ability of the topography to alter their behaviour: SAOS-2, osteoprogenitors and 271+ MSCs. Due to PEEKs material properties (it is non transparent, exhibits birefringence and is strongly autofluorescent) a number of histological techniques were used to investigate a number of different stages that take place in osteogenesis. The different cell types did display slightly different responses to the topographies. The SAOS-2 cells cultured on surfaces that had been plasma treated for 2 minutes at 200W had statistically significantly higher levels of von Kossa staining on the NSQ surface compared to the planar surface, and the same experiment employing alizarin red staining, showed a statistically significantly lower level of staining on the SQ surface compared to the planar surface. Using primary osteoprogenitor cells designed to look into if whether or not the presence of nanotopography effected the osteogenic response of these cells, we saw a lack of statistically significant difference produced by the surfaces investigated. By utilising HRP based immunostaining, we were able to investigate, in a quantitative fashion, the production of the two osteogenic markers osteopontin and osteocalcin by cells. When stained for osteocalcin, the SQ nanotopography had total percentage of the surface with stained material, average area and average perimeter all statistically significantly lower than the planar surface. For the cells that were stained for osteopontin, the SQ nanotopgraphy had a total percentage of the surface with stained material, average area and average perimeter all highly statistically significantly lower than those of the planar surface. Additionally, for this marker the NSQ nanotopography had average areas and average perimeters that were highly significantly higher than those of the planar surface. There were no significant differences for any of the values investigated for the 271+ MSC’s When plasma treatment was varied, the SAOS-2 cells demonstrated an overall trend i.e. increasing the energy of plasma treatment in turn leads to an increase in the overall percentage of staining. A similar experiment employing stem cells isolated from human bone marrow instead of SAOS-2 cells showed that for polycarbonate surfaces , used as a control, mineralization is statistically significantly higher on the NSQ nanopattern compared to the planar surface, whereas on the PEEK surfaces we observe the opposite trend i.e. the NSQ nanotopography having a statistically significantly lower amount of mineralization compared to the planar surface at the 200W 2min and 30W 1min plasma treatments. The standout trend from the PEEK results in this experiment was that the statistically significant differences on the PEEK substrates were clustered around the lower energy plasma treatments, which could suggest that the plasma treatment disrupted a function of the nanotopograhy which is why, as the energy increases, there are less statistically significant differences between the NSQ nanotopography and the Planar surface This thesis documents the response of a number of different types of cells to specific nanoscale topographies incorporated into the PEEK surface which had been treated with oxygen plasma. It outlines the development of a number of histological methods which measure different aspects of osteogenesis, and were selected to both work with PEEK, and produce quantitative results through the use of Cell Profiler. The methods that have been employed in this body of work would be of interest to other researchers working with this material, as well as those working with similarly autofluorescent materials.

Assessing the role of Mediterranean evergreen oaks canopy cover in land surface albedo and temperature using a remote sensing-based approach

Modifications in vegetation cover can have an impact on the climate through changes in biogeochemical and biogeophysical processes. In this paper, the tree canopy cover percentage of a savannah-like ecosystem (montado/dehesa) was estimated at Landsat pixel level for 2011, and the role of different canopy cover percentages on land surface albedo (LSA) and land surface temperature (LST) were analysed. A modelling procedure using a SGB machine-learning algorithm and Landsat 5-TM spectral bands and derived vegetation indices as explanatory variables, showed that the estimation of montado canopy cover was obtained with good agreement (R2 = 78.4%). Overall, montado canopy cover estimations showed that low canopy cover class (MT_1) is the most representative with 50.63% of total montado area. MODIS LSA and LST products were used to investigate the magnitude of differences in mean annual LSA and LST values between contrasting montado canopy cover percentages. As a result, it was found a significant statistical relationship between montado canopy cover percentage and mean annual surface albedo (R2 = 0.866, p < 0.001) and surface temperature (R2 = 0.942, p < 0.001). The comparisons between the four contrasting montado canopy cover classes showed marked differences in LSA (χ2 = 192.17, df = 3, p < 0.001) and LST (χ2 = 318.18, df = 3, p < 0.001). The highest montado canopy cover percentage (MT_4) generally had lower albedo than lowest canopy cover class, presenting a difference of −11.2% in mean annual albedo values. It was also showed that MT_4 and MT_3 are the cooler canopy cover classes, and MT_2 and MT_1 the warmer, where MT_1 class had a difference of 3.42 °C compared with MT_4 class. Overall, this research highlighted the role that potential changes in montado canopy cover may play in local land surface albedo and temperature variations, as an increase in these two biogeophysical parameters may potentially bring about, in the long term, local/regional climatic changes moving towards greater aridity.

Cloud parameter retrievals from Meteosat and their effects on the shortwave radiation at the surface

A method based on Spinning Enhanced Visible and Infrared Imager (SEVIRI) measured reflectance at 0.6 and 3.9 µm is used to retrieve the cloud optical thickness (COT) and cloud effective radius (re) over the Iberian Peninsula. A sensitivity analysis of simulated retrievals to the input parameters demonstrates that the cloud top height is an important factor in satellite retrievals of COT and re with uncertainties around 10% for small values of COT and re; for water clouds these uncertainties can be greater than 10% for small values of re. The uncertainties found related with geometries are around 3%. The COT and re are assessed using well-known satellite cloud products, showing that the method used characterize the cloud field with more than 80% (82%) of the absolute differences between COT (re) mean values of all clouds (water plus ice clouds) centred in the range from ±10 (±10 µm), with absolute bias lower than 2 (2 μm) for COT (re) and root mean square error values lower than 10 (8 μm) for COT (re). The cloud water path (CWP), derived from satellite retrievals, and the shortwave cloud radiative effect at the surface (CRESW) are related for high fractional sky covers (Fsc >0.8), showing that water clouds produce more negative CRESW than ice clouds. The COT retrieved was also related to the cloud modification factor, which exhibits reductions and enhancements of the surface SW radiation of the order of 80% and 30%, respectively, for COT values lower than 10. A selected case study shows, using a ground-based sky camera that some situations classified by the satellite with high Fsc values correspond to situations of broken clouds where the enhancements actually occur. For this case study, a closure between the liquid water path (LWP) obtained from the satellite retrievals and the same cloud quantity obtained from ground-based microwave measurements was performed showing a good agreement between both LWP data set values.

Development and optimisation of protocols for surface cleaning of cultural heritage metals

The conservation and valorisation of cultural heritage is of fundamental importance for our society, since it is witness to the legacies of human societies. In the case of metallic artefacts, because corrosion is a never-ending problem, the correct strategies for their cleaning and preservation must be chosen. Thus, the aim of this project was the development of protocols for cleaning archaeological copper artefacts by laser and plasma cleaning, since they allow the treatment of artefacts in a controlled and selective manner. Additionally, electrochemical characterisation of the artificial patinas was performed in order to obtain information on the protective properties of the corrosion layers. Reference copper samples with different artificial corrosion layers were used to evaluate the tested parameters. Laser cleaning tests resulted in partial removal of the corrosion products, but the lasermaterial interactions resulted in melting of the desired corrosion layers. The main obstacle for this process is that the materials that must be preserved show lower ablation thresholds than the undesired layers, which makes the proper elimination of dangerous corrosion products very difficult without damaging the artefacts. Different protocols should be developed for different patinas, and real artefacts should be characterised previous to any treatment to determine the best course of action. Low pressure hydrogen plasma cleaning treatments were performed on two kinds of patinas. In both cases the corrosion layers were partially removed. The total removal of the undesired corrosion products can probably be achieved by increasing the treatment time or applied power, or increasing the hydrogen pressure. Since the process is non-invasive and does not modify the bulk material, modifying the cleaning parameters is easy. EIS measurements show that, for the artificial patinas, the impedance increases while the patina is growing on the surface and then drops, probably due to diffusion reactions and a slow dissolution of copper. It appears from these results that the dissolution of copper is heavily influenced by diffusion phenomena and the corrosion product film porosity. Both techniques show good results for cleaning, as long as the proper parameters are used. These depend on the nature of the artefact and the corrosion layers that are found on its surface.