Comparison of compost and a sandy loam as turf underlay materials on salt-affected parkland

Turfgrasses range from extremely salt sensitive to highly salt tolerant. However, the selection of a salt tolerant turf is not a 'silver bullet' solution to successful turf growth on salt-affected parklands. Interactions between factors such as cultivar, construction practices, establishment, and maintenance can be complex and should not be considered in isolation of one another. Taking this holistic approach, a study investigating cultivar evaluation for salt-affected sites also included a comparison of topsoil materials as turf underlay, as well as pre-treatment of the sod. The turf species and cultivars used in the study were: Cynodon dactylon, cultivar 'Oz Tuff (I) '; Paspalum vaginatum, cultivars 'Sea Isle 1 (I) ' and 'Velvetene (I) '; Zoysia matrella cultivar 'A-1 (I) '; and Zoysia japonica, cultivar 'Empire (I) '. The two underlay materials were compost (100%) or a sandy clay topsoil each applied above a coastal sand profile to a depth of 10 cm. Rooting depth or root dry weight did not significantly differ among turf cultivars. Compost profile treatment had significantly greater root mass than the topsoil among all turf cultivars. This higher root production was reflected by improved quality of all turf at the final evaluation. Turfgrass grown on compost had a higher normalised difference vegetation index (NDVI), regardless of whether full sod or bare-rooted turfgrass was used. The use of a quality underlay was paramount to the successful growth of the turf cultivars investigated. While each cultivar had superior performance in sub-optimal conditions, the key to success was the selection of the right species and cultivar for each situation combined with proper establishment and maintenance of each turf grass.

Novel fluorinated surfactants tentatively identified in firefighters using liquid chromatography quadrupole time-of flight tandem mass spectrometry and a case-control approach

Fluorinated surfactant-based aqueous film-forming foams (AFFFs) are made up of per- and polyfluorinated alkyl substances (PFAS) and are used to extinguish fires involving highly flammable liquids. The use of perfluorooctanesulfonic acid (PFOS) and other perfluoroalkyl acids (PFAAs) in some AFFF formulations has been linked to substantial environmental contamination. Recent studies have identified a large number of novel and infrequently reported fluorinated surfactants in different AFFF formulations. In this study, a strategy based on a case-control approach using quadrupole time-of-flight tandem mass spectrometry (QTOF-MS/MS) and advanced statistical methods has been used to extract and identify known and unknown PFAS in human serum associated with AFFF-exposed firefighters. Two target sulfonic acids [PFOS and perfluorohexanesulfonic acid (PFHxS)], three non-target acids [perfluoropentanesulfonic acid (PFPeS), perfluoroheptanesulfonic acid (PFHpS), and perfluorononanesulfonic acid (PFNS)], and four unknown sulfonic acids (Cl-PFOS, ketone-PFOS, ether-PFHxS, and Cl-PFHxS) were exclusively or significantly more frequently detected at higher levels in firefighters compared to controls. The application of this strategy has allowed for identification of previously unreported fluorinated chemicals in a timely and cost-efficient way.

Active vibration suppression of non-linear beams using optimal dynamic inversion

Euler–Bernoulli beams are distributed parameter systems that are governed by a non-linear partial differential equation (PDE) of motion. This paper presents a vibration control approach for such beams that directly utilizes the non-linear PDE of motion, and hence, it is free from approximation errors (such as model reduction, linearization etc.). Two state feedback controllers are presented based on a newly developed optimal dynamic inversion technique which leads to closed-form solutions for the control variable. In one formulation a continuous controller structure is assumed in the spatial domain, whereas in the other approach it is assumed that the control force is applied through a finite number of discrete actuators located at predefined discrete locations in the spatial domain. An implicit finite difference technique with unconditional stability has been used to solve the PDE with control actions. Numerical simulation studies show that the beam vibration can effectively be decreased using either of the two formulations.

Miniaturized mass spectrometric ionization techniques for environmental analysis and bioanalysis

Miniaturized mass spectrometric ionization techniques for environmental analysis and bioanalysis Novel miniaturized mass spectrometric ionization techniques based on atmospheric pressure chemical ionization (APCI) and atmospheric pressure photoionization (APPI) were studied and evaluated in the analysis of environmental samples and biosamples. The three analytical systems investigated here were gas chromatography-microchip atmospheric pressure chemical ionization-mass spectrometry (GC-µAPCI-MS) and gas chromatography-microchip atmospheric pressure photoionization-mass spectrometry (GC-µAPPI-MS), where sample pretreatment and chromatographic separation precede ionization, and desorption atmospheric pressure photoionization-mass spectrometry (DAPPI-MS), where the samples are analyzed either as such or after minimal pretreatment. The gas chromatography-microchip atmospheric pressure ionization-mass spectrometry (GC-µAPI-MS) instrumentations were used in the analysis of polychlorinated biphenyls (PCBs) in negative ion mode and 2-quinolinone-derived selective androgen receptor modulators (SARMs) in positive ion mode. The analytical characteristics (i.e., limits of detection, linear ranges, and repeatabilities) of the methods were evaluated with PCB standards and SARMs in urine. All methods showed good analytical characteristics and potential for quantitative environmental analysis or bioanalysis. Desorption and ionization mechanisms in DAPPI were studied. Desorption was found to be a thermal process, with the efficiency strongly depending on thermal conductivity of the sampling surface. Probably the size and polarity of the analyte also play a role. In positive ion mode, the ionization is dependent on the ionization energy and proton affinity of the analyte and the spray solvent, while in negative ion mode the ionization mechanism is determined by the electron affinity and gas-phase acidity of the analyte and the spray solvent. DAPPI-MS was tested in the fast screening analysis of environmental, food, and forensic samples, and the results demonstrated the feasibility of DAPPI-MS for rapid screening analysis of authentic samples.

Chemical mass closure and source-specific composition of atmospheric particles

It has been known for decades that particles can cause adverse health effects as they are deposited within the respiratory system. Atmospheric aerosol particles influence climate by scattering solar radiation but aerosol particles act also as the nuclei around which cloud droplets form. The principal objectives of this thesis were to investigate the chemical composition and the sources of fine particles in different environments (traffic, urban background, remote) as well as during some specific air pollution situations. Quantifying the climate and health effects of atmospheric aerosols is not possible without detailed information of the aerosol chemical composition. Aerosol measurements were carried out at nine sites in six countries (Finland, Germany, Czech, Netherlands, Greece and Italy). Several different instruments were used in order to measure both the particulate matter (PM) mass and its chemical composition. In the off-line measurements the samples were collected first on a substrate or filter and gravimetric and chemical analysis were conducted in the laboratory. In the on-line measurements the sampling and analysis were either a combined procedure or performed successively within the same instrument. Results from the impactor samples were analyzed by the statistical methods. This thesis comprises also a work where a method for the determination carbonaceous matter size distribution by using a multistage impactor was developed. It was found that the chemistry of PM has usually strong spatial, temporal and size-dependent variability. In the Finnish sites most of the fine PM consisted of organic matter. However, in Greece sulfate dominated the fine PM and in Italy nitrate made the largest contribution to the fine PM. Regarding the size-dependent chemical composition, organic components were likely to be enriched in smaller particles than inorganic ions. Data analysis showed that organic carbon (OC) had four major sources in Helsinki. Secondary production was the major source in Helsinki during spring, summer and fall, whereas in winter biomass combustion dominated OC. The significant impact of biomass combustion on OC concentrations was also observed in the measurements performed in Central Europe. In this thesis aerosol samples were collected mainly by the conventional filter and impactor methods which suffered from the long integration time. However, by filter and impactor measurements chemical mass closure was achieved accurately, and a simple filter sampling was found to be useful in order to explain the sources of PM on the seasonal basis. The online instruments gave additional information related to the temporal variations of the sources and the atmospheric mixing conditions.

Dietary media for mass rearing of rusty grain beetle, Cryptolestes ferrugineus (Stephens) and flat grain beetle, Cryptolestes pusillus (Schonherr) (Coleoptera: Cucujidae)

We developed a suitable diet for mass rearing of Cryptolestes ferrugineus (Stephens) populations under laboratory conditions. Recently, this pest has developed strong level of resistance to phosphine in Australia, and therefore, a significant amount of research has been directed towards its management. In total, nineteen grain-based diets, containing rolled oats, various combinations of cracked grains and flours of wheat, sorghum, maize and barley were tested. Each diet contained a small proportion of wheat germ (4.5% w/w) and torula yeast (0.5% w/w). Experiments were conducted at fixed temperature and relative humidity regimes of 30 ± 2 °C and 70 ± 2%, respectively, and replicated three times. Adults (n = 40) of a laboratory strain of C. ferrugineus were introduced into each diet, removed after 14 days and total numbers of live adult progeny were recorded. The following diets resulted in highest live progeny production: barley flour (95%) (607.67 ± 11.21) = rolled oats (75%) + cracked sorghum (20%) (597.33 ± 33.79) ≥ wheat flour (47.5%) + barley flour (47.5%) (496.67 ± 52.93) > cracked sorghum (95%) (384.00 ± 60.66). The performance of these four diets was then tested with field-collected populations of C. ferrugineus and Cryptolestes pusillus (Schonherr). The diets based on rolled oats + cracked sorghum, wheat flour + barley flour, and barley flour alone consistently produced highest progeny numbers in field-collected populations of both species, with mean progeny numbers ranging from 359.9 to 478.5. The multiplication of C. pusillus was significantly higher than C. ferrugineus on all four diets. Our findings will help in mass rearing of healthy cultures of C. ferrugineus and C. pusillus that will greatly facilitate laboratory and field research and in particular, in developing management tactics for these species.

Impacts of level of utilisation by grazing on an Astrebla (Mitchell grass) grassland in north-western Queensland between 1984 and 2010. 1. Herbage mass and population dynamics of Astrebla spp

Managing large variations in herbage production, resulting from highly variable seasonal rainfall, provides a major challenge for the sustainable management of Astrebla (Mitchell grass) grasslands in Australia. A grazing study with sheep was conducted between 1984 and 2010 on an Astrebla grassland in northern Queensland to describe the effects of a range of levels of utilisation of the herbage at the end of the summer growing season (April–May in northern Australia) on the sustainability of these grasslands. In unreplicated paddocks, sheep numbers were adjusted annually to achieve 0, 10, 20, 30, 50 and 80% utilisation of the herbage mass at the end of the summer over the ensuing 12 months. Higher levels of utilisation reduced both total and Astrebla spp. herbage mass because of the effects of higher utilisation on Astrebla spp. and this effect was accentuated by drought. The tussock density of Astrebla spp. varied widely among years but with few treatment differences until 2005 when density was reduced at the 50% level of utilisation. A major change in density resulted from a large recruitment of Astrebla spp. in 1989 that influenced its density for the remainder of the study. Basal area of the tussocks fluctuated among years, with increases due to rainfall and decreases during droughts. Seasonal rainfall was more influential than level of utilisation in changes to the basal area of perennial grasses. Drought resulted in the death of Astrebla spp. tussocks and this effect was accentuated at higher levels of utilisation. A series of three grazing exclosures were used to examine the recovery of the density and basal area of Astrebla spp. after it had been reduced by 80% utilisation over the preceding 9 years. This recovery study indicated that, although grazing exclusion was useful in the recovery of Astrebla spp., above-average rainfall was the major factor driving increases in the basal area of perennial grasses. Spring values of the Southern Oscillation Index and associated rainfall probabilities were considered to have potential for understanding the dynamics of Astrebla spp. It was concluded that Astrebla grassland remained sustainable after 26 years when grazed at up to 30% utilisation, while, at 50% utilisation, they became unsustainable after 20 years. Results from this study emphasised the need to maintain the population of Astrebla spp. tussocks.

Tailoring polyolefin properties by metallocene catalysis

This doctoral thesis deals with the syntheses of olefin homo- and copolymers using different kind of metallocene catalyst. Ethene, propene, 1-hexene, 1-hexadecene, vinylcyclohexane and phenylnorbornene were homo- or copolymerized with the catalysts. The unbridged benzyl substituted zirconium dichloride catalysts (1-4), ansa- bridged acenaphtyl substituted zirconium dichloride catalysts, ( 5, 6), rac- and meso-ethylene-bis(1-indenyl)zirconium dichlorides, (rac- and meso-8), rac-ethylene-bis(1-indenyl)hafnium dichloride, ( 12), bis(9-fluorenyl)hafnium dichloride (14 ) enantiomerically pure (R)- phenylethyl[(9-fluorenyl-1-indenyl)]ZrCl2, (11), 14 and asymmetric dimethylsilyl[(3-benzylindenyl-(2-methylbenzen[e]indenyl)] zirconium dichloride, (13), were prepared in our laboratory. Dimethylsilyl-bis(1-indenyl)zirconium dichloride, (9), isopropylidene(9-fluorenyl-cyclopentadienyl)zirconium dichloride, (10), and were obtained commercially. The solid-state structures of the catalysts rac- and meso-1 were determined by X-ray crystallography. Computational methods were used for the structure optimization of the catalyst rac- and meso-1 in order to compare the theoretical calculations with the experimental results. Polymerization experiments were conducted in a highly purified autoclave system using low pressures (< 5 bar) of gaseous monomers. The experiments were designed to attain the optimal catalytic activity and a uniform copolymer composition. The prepared homo- and copolymers were characterized by the gel permeation chromatography, GPC, differential scanning calorimetry, DSC, nuclear magnetic resonance, NMR, and Fourier transform infrared spectrometry, FTIR . Molar mass (Mw, Mn), molar mass distribution (Mw/Mn), tacticity, comonomer content, melting temperature, glass transition temperature, and end group structures and content were determined. A special attention was paid on the correlation of the polymer properties with the catalyst structures and polymerization conditions. An intramolecular phenyl coordination was found in phenyl substituted benzyl zirconocenes 1-3 explaining the decreased activity of the catalysts. Novel copolymers poly(propene-co-phenylnorbornene) and poly(propene co-vinylcyclohexane), were synthesized and high molar mass poly(ethene-co-1-hexene) and poly(ethene-co-1-hexadecene) copolymers with elastic properties were prepared. Activation of a hafnocene catalyst was studied with UV-Vis spectrometry and activation process for the synthesis of ultra high molar mass poly(1-hexene) was found out.

Deriving optimal fishing effort for managing Australia's Moreton Bay multispecies trawl fishery with aggregated effort data

Deriving an estimate of optimal fishing effort or even an approximate estimate is very valuable for managing fisheries with multiple target species. The most challenging task associated with this is allocating effort to individual species when only the total effort is recorded. Spatial information on the distribution of each species within a fishery can be used to justify the allocations, but often such information is not available. To determine the long-term overall effort required to achieve maximum sustainable yield (MSY) and maximum economic yield (MEY), we consider three methods for allocating effort: (i) optimal allocation, which optimally allocates effort among target species; (ii) fixed proportions, which chooses proportions based on past catch data; and (iii) economic allocation, which splits effort based on the expected catch value of each species. Determining the overall fishing effort required to achieve these management objectives is a maximizing problem subject to constraints due to economic and social considerations. We illustrated the approaches using a case study of the Moreton Bay Prawn Trawl Fishery in Queensland (Australia). The results were consistent across the three methods. Importantly, our analysis demonstrated the optimal total effort was very sensitive to daily fishing costs—the effort ranged from 9500–11 500 to 6000–7000, 4000 and 2500 boat-days, using daily cost estimates of $0, $500, $750, and $950, respectively. The zero daily cost corresponds to the MSY, while a daily cost of $750 most closely represents the actual present fishing cost. Given the recent debate on which costs should be factored into the analyses for deriving MEY, our findings highlight the importance of including an appropriate cost function for practical management advice. The approaches developed here could be applied to other multispecies fisheries where only aggregated fishing effort data are recorded, as the literature on this type of modelling is sparse.