Elemental analysis and forensic comparison of soils by laser-induced breakdown spectroscopy (LIBS) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS)

The elemental analysis of soil is useful in forensic and environmental sciences. Methods were developed and optimized for two laser-based multi-element analysis techniques: laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and laser-induced breakdown spectroscopy (LIBS). This work represents the first use of a 266 nm laser for forensic soil analysis by LIBS. Sample preparation methods were developed and optimized for a variety of sample types, including pellets for large bulk soil specimens (470 mg) and sediment-laden filters (47 mg), and tape-mounting for small transfer evidence specimens (10 mg). Analytical performance for sediment filter pellets and tape-mounted soils was similar to that achieved with bulk pellets. An inter-laboratory comparison exercise was designed to evaluate the performance of the LA-ICP-MS and LIBS methods, as well as for micro X-ray fluorescence (μXRF), across multiple laboratories. Limits of detection (LODs) were 0.01-23 ppm for LA-ICP-MS, 0.25-574 ppm for LIBS, 16-4400 ppm for μXRF, and well below the levels normally seen in soils. Good intra-laboratory precision (≤ 6 % relative standard deviation (RSD) for LA-ICP-MS; ≤ 8 % for μXRF; ≤ 17 % for LIBS) and inter-laboratory precision (≤ 19 % for LA-ICP-MS; ≤ 25 % for μXRF) were achieved for most elements, which is encouraging for a first inter-laboratory exercise. While LIBS generally has higher LODs and RSDs than LA-ICP-MS, both were capable of generating good quality multi-element data sufficient for discrimination purposes. Multivariate methods using principal components analysis (PCA) and linear discriminant analysis (LDA) were developed for discriminations of soils from different sources. Specimens from different sites that were indistinguishable by color alone were discriminated by elemental analysis. Correct classification rates of 94.5 % or better were achieved in a simulated forensic discrimination of three similar sites for both LIBS and LA-ICP-MS. Results for tape-mounted specimens were nearly identical to those achieved with pellets. Methods were tested on soils from USA, Canada and Tanzania. Within-site heterogeneity was site-specific. Elemental differences were greatest for specimens separated by large distances, even within the same lithology. Elemental profiles can be used to discriminate soils from different locations and narrow down locations even when mineralogy is similar.

The Performance and Service Life Prediction of High Performance Concrete in Sulfate and Acidic Environments

Concrete substructures are often subjected to environmental deterioration, such as sulfate and acid attack, which leads to severe damage and causes structure degradation or even failure. In order to improve the durability of concrete, the High Performance Concrete (HPC) has become widely used by partially replacing cement with pozzolanic materials. However, HPC degradation mechanisms in sulfate and acidic environments are not completely understood. It is therefore important to evaluate the performance of the HPC in such conditions and predict concrete service life by establishing degradation models. This study began with a review of available environmental data in the State of Florida. A total of seven bridges have been inspected. Concrete cores were taken from these bridge piles and were subjected for microstructural analysis using Scanning Electron Microscope (SEM). Ettringite is found to be the products of sulfate attack in sulfate and acidic condition. In order to quantitatively analyze concrete deterioration level, an image processing program is designed using Matlab to obtain quantitative data. Crack percentage (Acrack/Asurface) is used to evaluate concrete deterioration. Thereafter, correlation analysis was performed to find the correlation between five related variables and concrete deterioration. Environmental sulfate concentration and bridge age were found to be positively correlated, while environmental pH level was found to be negatively correlated. Besides environmental conditions, concrete property factor was also included in the equation. It was derived from laboratory testing data. Experimental tests were carried out implementing accelerated expansion test under controlled environment. Specimens of eight different mix designs were prepared. The effect of pozzolanic replacement rate was taken into consideration in the empirical equation. And the empirical equation was validated with existing bridges. Results show that the proposed equations compared well with field test results with a maximum deviation of ± 20%. Two examples showing how to use the proposed equations are provided to guide the practical implementation. In conclusion, the proposed approach of relating microcracks to deterioration is a better method than existing diffusion and sorption models since sulfate attack cause cracking in concrete. Imaging technique provided in this study can also be used to quantitatively analyze concrete samples.

Elemental Analysis and Forensic Comparison of Soils by Laser-Induced Breakdown Spectroscopy (LIBS) and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS)

The elemental analysis of soil is useful in forensic and environmental sciences. Methods were developed and optimized for two laser-based multi-element analysis techniques: laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and laser-induced breakdown spectroscopy (LIBS). This work represents the first use of a 266 nm laser for forensic soil analysis by LIBS. Sample preparation methods were developed and optimized for a variety of sample types, including pellets for large bulk soil specimens (470 mg) and sediment-laden filters (47 mg), and tape-mounting for small transfer evidence specimens (10 mg). Analytical performance for sediment filter pellets and tape-mounted soils was similar to that achieved with bulk pellets. An inter-laboratory comparison exercise was designed to evaluate the performance of the LA-ICP-MS and LIBS methods, as well as for micro X-ray fluorescence (μXRF), across multiple laboratories. Limits of detection (LODs) were 0.01-23 ppm for LA-ICP-MS, 0.25-574 ppm for LIBS, 16-4400 ppm for µXRF, and well below the levels normally seen in soils. Good intra-laboratory precision (≤ 6 % relative standard deviation (RSD) for LA-ICP-MS; ≤ 8 % for µXRF; ≤ 17 % for LIBS) and inter-laboratory precision (≤ 19 % for LA-ICP-MS; ≤ 25 % for µXRF) were achieved for most elements, which is encouraging for a first inter-laboratory exercise. While LIBS generally has higher LODs and RSDs than LA-ICP-MS, both were capable of generating good quality multi-element data sufficient for discrimination purposes. Multivariate methods using principal components analysis (PCA) and linear discriminant analysis (LDA) were developed for discriminations of soils from different sources. Specimens from different sites that were indistinguishable by color alone were discriminated by elemental analysis. Correct classification rates of 94.5 % or better were achieved in a simulated forensic discrimination of three similar sites for both LIBS and LA-ICP-MS. Results for tape-mounted specimens were nearly identical to those achieved with pellets. Methods were tested on soils from USA, Canada and Tanzania. Within-site heterogeneity was site-specific. Elemental differences were greatest for specimens separated by large distances, even within the same lithology. Elemental profiles can be used to discriminate soils from different locations and narrow down locations even when mineralogy is similar.

Aerodynamic load characteristics evaluation and tri-axial performance testing on fiber reinforced polymer connections and metal fasteners to promote hurricane damage mitigation

Damages during extreme wind events highlight the weaknesses of mechanical fasteners at the roof-to-wall connections in residential timber frame buildings. The allowable capacity of the metal fasteners is based on results of unidirectional component testing that do not simulate realistic tri-axial aerodynamic loading effects. The first objective of this research was to simulate hurricane effects and study hurricane-structure interaction at full-scale, facilitating better understanding of the combined impacts of wind, rain, and debris on inter-component connections at spatial and temporal scales. The second objective was to evaluate the performance of a non-intrusive roof-to-wall connection system using fiber reinforced polymer (FRP) materials and compare its load capacity to the capacity of an existing metal fastener under simulated aerodynamic loads. ^ The Wall of Wind (WoW) testing performed using FRP connections on a one-story gable-roof timber structure instrumented with a variety of sensors, was used to create a database on aerodynamic and aero-hydrodynamic loading on roof-to-wall connections tested under several parameters: angles of attack, wind-turbulence content, internal pressure conditions, with and without effects of rain. Based on the aerodynamic loading results obtained from WoW tests, sets of three force components (tri-axial mean loads) were combined into a series of resultant mean forces, which were used to test the FRP and metal connections in the structures laboratory up to failure. A new component testing system and test protocol were developed for testing fasteners under simulated triaxial loading as opposed to uni-axial loading. The tri-axial and uni-axial test results were compared for hurricane clips. Also, comparison was made between tri-axial load capacity of FRP and metal connections. ^ The research findings demonstrate that the FRP connection is a viable option for use in timber roof-to-wall connection system. Findings also confirm that current testing methods of mechanical fasteners tend to overestimate the actual load capacities of a connector. Additionally, the research also contributes to the development a new testing protocol for fasteners using tri-axial simultaneous loads based on the aerodynamic database obtained from the WoW testing. ^

Development of effective approaches to the large-scale aerodynamic testing of low-rise buildings

Low-rise buildings are often subjected to high wind loads during hurricanes that lead to severe damage and cause water intrusion. It is therefore important to estimate accurate wind pressures for design purposes to reduce losses. Wind loads on low-rise buildings can differ significantly depending upon the laboratory in which they were measured. The differences are due in large part to inadequate simulations of the low-frequency content of atmospheric velocity fluctuations in the laboratory and to the small scale of the models used for the measurements. A new partial turbulence simulation methodology was developed for simulating the effect of low-frequency flow fluctuations on low-rise buildings more effectively from the point of view of testing accuracy and repeatability than is currently the case. The methodology was validated by comparing aerodynamic pressure data for building models obtained in the open-jet 12-Fan Wall of Wind (WOW) facility against their counterparts in a boundary-layer wind tunnel. Field measurements of pressures on Texas Tech University building and Silsoe building were also used for validation purposes. The tests in partial simulation are freed of integral length scale constraints, meaning that model length scales in such testing are only limited by blockage considerations. Thus the partial simulation methodology can be used to produce aerodynamic data for low-rise buildings by using large-scale models in wind tunnels and WOW-like facilities. This is a major advantage, because large-scale models allow for accurate modeling of architectural details, testing at higher Reynolds number, using greater spatial resolution of the pressure taps in high pressure zones, and assessing the performance of aerodynamic devices to reduce wind effects. The technique eliminates a major cause of discrepancies among measurements conducted in different laboratories and can help to standardize flow simulations for testing residential homes as well as significantly improving testing accuracy and repeatability. Partial turbulence simulation was used in the WOW to determine the performance of discontinuous perforated parapets in mitigating roof pressures. The comparisons of pressures with and without parapets showed significant reductions in pressure coefficients in the zones with high suctions. This demonstrated the potential of such aerodynamic add-on devices to reduce uplift forces.

Large-Scale Testing to Study the Effects of Critical Parameters on the Aerodynamic Behavior of Long Span Bridges

Long-span bridges are flexible and therefore are sensitive to wind induced effects. One way to improve the stability of long span bridges against flutter is to use cross-sections that involve twin side-by-side decks. However, this can amplify responses due to vortex induced oscillations. Wind tunnel testing is a well-established practice to evaluate the stability of bridges against wind loads. In order to study the response of the prototype in laboratory, dynamic similarity requirements should be satisfied. One of the parameters that is normally violated in wind tunnel testing is Reynolds number. In this dissertation, the effects of Reynolds number on the aerodynamics of a double deck bridge were evaluated by measuring fluctuating forces on a motionless sectional model of a bridge at different wind speeds representing different Reynolds regimes. Also, the efficacy of vortex mitigation devices was evaluated at different Reynolds number regimes. One other parameter that is frequently ignored in wind tunnel studies is the correct simulation of turbulence characteristics. Due to the difficulties in simulating flow with large turbulence length scale on a sectional model, wind tunnel tests are often performed in smooth flow as a conservative approach. The validity of simplifying assumptions in calculation of buffeting loads, as the direct impact of turbulence, needs to be verified for twin deck bridges. The effects of turbulence characteristics were investigated by testing sectional models of a twin deck bridge under two different turbulent flow conditions. Not only the flow properties play an important role on the aerodynamic response of the bridge, but also the geometry of the cross section shape is expected to have significant effects. In this dissertation, the effects of deck details, such as width of the gap between the twin decks, and traffic barriers on the aerodynamic characteristics of a twin deck bridge were investigated, particularly on the vortex shedding forces with the aim of clarifying how these shape details can alter the wind induced responses. Finally, a summary of the issues that are involved in designing a dynamic test rig for high Reynolds number tests is given, using the studied cross section as an example.

Aerodynamic Load Characteristics Evaluation and Tri-Axial Performance Testing on Fiber Reinforced Polymer Connections and Metal Fasteners to Promote Hurricane Damage Mitigation

Damages during extreme wind events highlight the weaknesses of mechanical fasteners at the roof-to-wall connections in residential timber frame buildings. The allowable capacity of the metal fasteners is based on results of unidirectional component testing that do not simulate realistic tri-axial aerodynamic loading effects. The first objective of this research was to simulate hurricane effects and study hurricane-structure interaction at full-scale, facilitating better understanding of the combined impacts of wind, rain, and debris on inter-component connections at spatial and temporal scales. The second objective was to evaluate the performance of a non-intrusive roof-to-wall connection system using fiber reinforced polymer (FRP) materials and compare its load capacity to the capacity of an existing metal fastener under simulated aerodynamic loads. The Wall of Wind (WoW) testing performed using FRP connections on a one-story gable-roof timber structure instrumented with a variety of sensors, was used to create a database on aerodynamic and aero-hydrodynamic loading on roof-to-wall connections tested under several parameters: angles of attack, wind-turbulence content, internal pressure conditions, with and without effects of rain. Based on the aerodynamic loading results obtained from WoW tests, sets of three force components (tri-axial mean loads) were combined into a series of resultant mean forces, which were used to test the FRP and metal connections in the structures laboratory up to failure. A new component testing system and test protocol were developed for testing fasteners under simulated tri-axial loading as opposed to uni-axial loading. The tri-axial and uni-axial test results were compared for hurricane clips. Also, comparison was made between tri-axial load capacity of FRP and metal connections. The research findings demonstrate that the FRP connection is a viable option for use in timber roof-to-wall connection system. Findings also confirm that current testing methods of mechanical fasteners tend to overestimate the actual load capacities of a connector. Additionally, the research also contributes to the development a new testing protocol for fasteners using tri-axial simultaneous loads based on the aerodynamic database obtained from the WoW testing.