Optimization of the Ion Source-Mass Spectrometry Parameters in Non-Steroidal Anti-Inflammatory and Analgesic Pharmaceuticals Analysis by a Design of Experiments Approach

The flow rates of drying and nebulizing gas, heat block and desolvation line temperatures and interface voltage are potential electrospray ionization parameters as they may enhance sensitivity of the mass spectrometer. The conditions that give higher sensitivity of 13 pharmaceuticals were explored. First, Plackett-Burman design was implemented to screen significant factors, and it was concluded that interface voltage and nebulizing gas flow were the only factors that influence the intensity signal for all pharmaceuticals. This fractionated factorial design was projected to set a full 2(2) factorial design with center points. The lack-of-fit test proved to be significant. Then, a central composite face-centered design was conducted. Finally, a stepwise multiple linear regression and subsequently an optimization problem solving were carried out. Two main drug clusters were found concerning the signal intensities of all runs of the augmented factorial design. p-Aminophenol, salicylic acid, and nimesulide constitute one cluster as a result of showing much higher sensitivity than the remaining drugs. The other cluster is more homogeneous with some sub-clusters comprising one pharmaceutical and its respective metabolite. It was observed that instrumental signal increased when both significant factors increased with maximum signal occurring when both codified factors are set at level +1. It was also found that, for most of the pharmaceuticals, interface voltage influences the intensity of the instrument more than the nebulizing gas flowrate. The only exceptions refer to nimesulide where the relative importance of the factors is reversed and still salicylic acid where both factors equally influence the instrumental signal. Graphical Abstract ᅟ.

Vitamin D status in the first-trimester: effects of Vitamin D deficiency on pregnancy outcomes.

Objective: To assess serum levels of 25-hydroxyvitamin D [25(OH)D] in the first trimester and to determine the factors affecting deficiency levels and its association with pregnancy outcomes. Methods: Serum 25(OH)D concentrations were measured at 11-14 weeks’ gestation in 229 singleton pregnancies using liquid chromatography-tandem mass spectrometry. Results: The median serum 25(OH)D concentration was 10.8 ng/mL and 45.9% of women had severe vitamin D deficiency with concentrations of <10 ng/mL. Logistic regression analysis revealed that covered dressing style, lack of multivitamin intake, season of blood sampling (November-April) were factors associated with 25(OH)D deficiency. There was a negative correlation between 25(OH)D levels and gestational age at sampling. Low 25(OH)D levels were not associated with adverse pregnancy outcomes. Higher rate of cesarean section (CS) was noted in women with 25(OH)D ≥10 ng/mL compared to those with 25(OH)D < 10mg/ml ( p= 0.01). Conclusion: A high prevalence of vitamin D deficiency was observed in early pregnancy which was related to dress code, use of multi-vitamins and season at sampling. Low 25(OH)D levels were not related with adverse pregnancy outcomes. Women with severe vitamin D deficiency were more likely to deliver vaginally.

Radiogenic isotopes in the Mediterranean Sea: water mass exchange and precessional variability during the Messinian

During the late Miocene, exchange between the Mediterranean Sea and Atlantic Ocean changed dramatically, culminating in the Messinian Salinity Crisis (MSC). Understanding Mediterranean-Atlantic exchange at that time could answer the enigmatic question of how so much salt built up within the Mediterranean, while furthering the development of a framework for future studies attempting to understand how changes may have impacted global thermohaline circulation. Due to their association with specific water masses at different scales, radiogenic Sr, Pb, and Nd isotope records were generated from various archives contained within marine deposits to endeavour to understand better late Miocene Mediterranean-Atlantic exchange. The archives used include foraminiferal calcite (Sr), fish teeth and bone (Nd), dispersed authigenic ferromanganese oxyhydroxides (Nd, Pb), and a ferromanganese crust (Pb). The primary focus is on sediments preserved at one end of the Betic corridor, a gateway that once connected the Mediterranean to the Atlantic through southern Spain, although other locations are investigated. The Betic gateway terminated within several marginal sub-basins before entering the Western Mediterranean; one of these is the Sorbas Basin, a well-studied location whose sediments have been astronomically tuned at high temporal resolution, providing the necessary age control for sub-precessional resolution records. Since the climatic history of the Mediterranean is strongly controlled by precessional changes in regional climate, the aim was to produce records at high (sub-precessional) temporal resolution, to be able to observe clearly any precessional cyclicity driven by regional climate which could be superimposed over longer trends. This goal was achieved for all records except the ferromanganese crust record. The 87Sr/86Sr isotope record (Ch. 3) shows precessional frequency excursions away from the global seawater curve. As precessional frequency oscillations are unexpected for this setting, a numerical box model was used to determine the mechanisms causing the excursions. To enable parameterisation of model variables, regional Sr characteristics, data from general circulation model HadCM3L, and new benthic foraminiferal assemblage data are employed. The model results imply that the Sorbas Basin likely had a positive hydrologic budget in the late Miocene, very different to that of today. Moreover, the model indicates that the mechanism controlling the Sr isotope ratio of Sorbas Basin seawater was not restriction, but a lack of density-driven exchange with the Mediterranean. Beyond improving our understanding of how marginal Mediterranean sub-basins may evolve different isotope signatures, these results have implications for astronomical tuning and stratigraphy in the region, findings which are crucial considering the geological and climatic history of the late Miocene Mediterranean is based entirely on marginal deposits. An improved estimate for the Nd isotope signature of late Miocene Mediterranean Outflow (MO) was determined by comparing Nd isotope signatures preserved in the deeper Alborán Sea at ODP Site 978 with literature data as well as the signature preserved in the Sorbas Basin (Ch. 4; -9.34 to -9.92 ± 0.37 εNd(t)). It was also inferred that it is unlikely that Nd isotopes can be used reliably to track changes in circulation within the shallow settings characteristic of the Mediterranean-Atlantic connections; this is significant in light of a recent publication documenting corridor closure using Nd isotopes. Both conclusions will prove useful for future studies attempting to understand changes in Mediterranean-Atlantic exchange. Excursions to high values, with precessional frequency, are also observed in the radiogenic Pb isotope record for the Sorbas Basin (Ch. 5). Widening the scope to include locations further away from the gateways, records were produced for late Miocene sections on Sicily and Northern Italy, and similar precessional frequency cyclicity was observed in the Pb isotope records for these sites as well. Comparing these records to proxies for Saharan dust and available whole rock data indicates that, while further analysis is necessary to draw strong conclusions, enhanced dust production during insolation minima may be driving the observed signal. These records also have implications for astronomical tuning; peaks in Pb isotope records driven by Saharan dust may be easier to connect directly to the insolation cycle, providing improved astronomical tuning points. Finally, a Pb isotope record derived using in-situ laser ablation performed on ferromanganese crust 3514-6 from the Lion Seamount, located west of Gibraltar within the MO plume, has provided evidence that plume depth shifted during the Pliocene. The record also suggests that Pb isotopes may not be a suitable proxy for changes in late Miocene Mediterranean-Atlantic exchange, since the Pb isotope signatures of regional water masses are too similar. To develop this record, the first published instance of laser ablation derived 230Thexcess measurements are combined with 10Be dating.

First metabolomic approach of the epiphytic bacteria-marine diatom Haslea ostrearia relationships

The marine diatom Haslea ostrearia [1] produces a water-soluble blue-pigment named marennine [2] of economic interest. But the lack of knowledge of the ecological conditions, under which this microalga develops in its natural ecosystem, more especially bacteria H. ostrearia interactions, prevents any optimization of its culture in well-controlled conditions. The structure of the bacterial community was analyzed by PCR-TTGE before and after the isolation of H. ostrearia cells recovered from 4 localities, to distinguish the relative part of the biotope and the biocenose and eventually to describe the temporal dynamic of the structure of the bacterial community at two time-scales. The differences in genetic fingerprints, more especially high between two H. ostrearia isolates (HO-R and HO-BM) showed also the highest differences in the bacterial structure [3] as the result of specific metabolomics profiles. The non-targeted metabolomic investigation showed that these profiles were more distinct in case of bacteria-alga associations than for the H. ostrearia monoculture Here we present a Q-TOF LC/MS metabolomic fingerprinting approach [3]: - to investigate differential metabolites of axenic versus non axenic H. ostrearia cultures. - to focus on the specific metabolites of a bacterial surrounding associated with the activation or inhibition of the microalga growing. The Agilent suite of data processing software makes feature finding, statistical analysis, and identification easier. This enables rapid transformation of complex raw data into biologically relevant metabolite information.

Development of the gas chromatograph – mass spectrometer to investigate volatile species in the lunar soil for the Luna-Resurs mission

Since the analysis of the lunar rocks and soil samples, brought to Earth by the Apollo missions, it is believed that the Moon has a waterless nature and also other volatile species are strongly depleted. Advancement in analysis techniques helped to identify water and other volatile species in lunar volcanic glasses. Additionally, recent lunar space missions detected water and volatile organic compounds in the region of the lunar poles where permanently shadowed craters are existing. All known lunar soil samples available on Earth come from the lunar near side, close to the equator. To verify the most recent measurement results and to enhance the knowledge of the geological history of the Moon it is of high interest to perform in situ measurements on the lunar poles. For this reason the Russian space agency, Roskosmos, developed aprogram for the scientific exploration of the lunar poles. The Gas Analysis Package (GAP) is part of the selected scientific payload aboard the Luna-Resurs Lander. This instrument uses pyrolytic cells and will apply laser spectroscopy, gas chromatography and mass spectrometry to detect and analyze volatile components trapped in the lunar soil. An existing ion optical design of a compact reflectron type time-of-flight mass spectrometer, originally built for the MEAP/P-BACE balloon mission, was chosen as a part of the GAP instrument. The scope of this thesis is the development of the interface between gas chromatography (GC) and this Neutral Gas Mass Spectrometer (NGMS) to perform coupled GC-MS measurements. In the first part of this thesis the interfacing concept was developed and verified by coupling the NGMS prototype to gas chromatography. The second part of this thesis is devoted to the development of the NGMS flight version.

Development of new analytical procedures of isotope geochemistry by mass spectrometry. Application to the study of high-pressure metamorphic rocks from the Iberian Massif

319 p.

Influence of autogenous shrinkage on mass transport properties of concrete

La retracción autógena en el hormigón es el cambio volumétrico una vez iniciado su proceso de fraguado. Se desarrolla a edades muy tempranas debido a la retracción química y a la autodesecación. Éstos causan microfisuras en hormigones de alta resistencia y permiten el ingreso de agentes nocivos como dióxido de carbono, cloruros y sulfatos que deterioran al hormigón. A pesar de haber estudios de la retracción autógena, existe incertidumbre sobre su influencia en la durabilidad del hormigón. Por ello, el motivo del presente estudio es cuantificar y analizar el efecto de la retracción autógena en el hormigón usando tres pruebas de transporte: difusión de oxígeno, permeabilidad de oxígeno y absorción de agua. Dos métodos, para tres diferentes aglutinantes, fueron usados para determinar la mezcla control que produce menor retracción: utilizando SRA y realizando el curado en un cuarto de niebla. Posteriormente, los resultados de las pruebas de transporte entre la mezcla de control seleccionada y mezclas altamente afectadas por retracción autógena fueron comparados para diferentes aglutinantes. Resultados revelaron que muestras con SRA presentan menores retracciones autógenas y se sugiere que estas muestras sean consideradas de control. Se demostró que la retracción autógena afecta significativamente los coeficientes de transporte los cuales en un punto de vista de servicio pueden reducir la vida útil de cualquier estructura realizada con hormigón de alta resistencia. Esta investigación además confirmó que la mayor deformación autógena ocurre durante las dos primeras semanas; por lo tanto, se debe tomar cuidado suficiente en el curado.

Removal of BrO3 − from drinking water samples using newly developed agricultural waste-based activated carbon and its determination by ultra-performance liquid chromatography-mass spectrometry

Activated carbon was prepared from date pits via chemical activation with H3PO4. The effects of activating agent concentration and activation temperature on the yield and surface area were studied. The optimal activated carbon was prepared at 450 °C using 55 % H3PO4. The prepared activated carbon was characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric-differential thermal analysis, and Brunauer, Emmett, and Teller (BET) surface area. The prepared date pit-based activated carbon (DAC) was used for the removal of bromate (BrO3 −). The concentration of BrO3 − was determined by ultra-performance liquid chromatography-mass tandem spectrometry (UPLC-MS/MS). The experimental equilibrium data for BrO3 − adsorption onto DAC was well fitted to the Langmuir isotherm model and showed maximum monolayer adsorption capacity of 25.64 mg g−1. The adsorption kinetics of BrO3 − adsorption was very well represented by the pseudo-first-order equation. The analytical application of DAC for the analysis of real water samples was studied with very promising results.

Identification of metabolites of kurarinone from Sophora flavescens Ait in rat urine by ultra-performance liquid chromatography with linear ion trap orbitrap mass spectrometry

Purpose: To study the in vivo metabolism of kurarinone, a lavandulyl flavanone which is a major constituent of Kushen and a marker compound with many biological activities, using ultra-performance liquid chromatography coupled with linear ion trap Orbitrap mass spectrometry (UPLC-LTQ-Orbitrap- MS). Methods: Six male Sprague-Dawley rats were randomly divided into two groups. First, kurarinone was suspended in 0.5 % carboxymethylcellulose sodium (CMC-Na) aqueous solution, and was given to rats (n = 3, 2 mL for each rat) orally at 50 mg/kg. A 2 mL aliquot of 0.5 % CMC-Na aqueous solution was administered to the rats in the control group. Next, urine samples were collected over 0-24 h after the oral administrations and all urine samples were pretreated by a solid phase extraction (SPE) method. Finally, all samples were analyzed by a UPLC-LTQ-Orbitrap mass spectrometry coupled with an electrospray ionization source (ESI) that was operated in the negative ionization mode. Results: A total of 11 metabolites, including the parent drug and 10 phase II metabolites in rat urine, were first detected and interpreted based on accurate mass measurement, fragment ions, and chromatographic retention times. The results were based on the assumption that kurarinone glucuronidation was the dominant metabolite that was excreted in rat urine. Conclusion: The results from this work indicate that kurarinone in vivo is typically transformed to nontoxic glucuronidation metabolites, and these findings may help to characterize the metabolic profile of kurarinone.

CHARACTERIZING THE FIRST HISTORIC ERUPTION OF NABRO, ERITREA: INSIGHTS FROM THERMAL AND UV REMOTE SENSING

June 2011 saw the first historic eruption of Nabro volcano, one of an ongoing sequence of eruptions in the Afar-Red Sea region since 2005. It halted air travel in northern Africa, contaminated food and water sources, and displaced thousands from their homes. Due to its remote location, little was known about this event in terms of the quantity of erupted products and the timing and mechanisms of their emplacement. Geographic isolation, previous quiescence and regional civil unrest meant that this volcano was effectively unmonitored at the time of eruption, and opportunities for field study are limited. Using free, publicly available satellite data, I examined rates of lava effusion and SO2 emission in order to quantify the amount of erupted products and understand the temporal evolution of the eruption, as well as explore what information can be gleaned about eruption mechanisms using remote sensing data. These data revealed a bimodal eruption, beginning with explosive activity marked by high SO2 emission totalling 1824 - 2299 KT, and extensive ash fall of 270 - 440 km2. This gave way to a period of rapid effusion, producing a ~17 km long lava flow, and a volume of ~22.1 x 106 m3. Mass balance between the SO2 and lava flows reveals no sulfur 'excess', suggesting that nearly all of the degassed magma was extruded. The 2011 eruption of Nabro lasted nearly 6 weeks, and may be considered the second largest historic eruption in Africa. Work such as this highlights the importance of satellite remote sensing for studying and monitoring volcanoes, particularly those in remote regions that may be otherwise inaccessible.

IMPROVED SENSITIVITY OF RESONANT MASS SENSOR BASED ON MICRO TILTING PLATE AND MICRO CANTILEVER

Vapor sensors have been used for many years. Their applications range from detection of toxic gases and dangerous chemicals in industrial environments, the monitoring of landmines and other explosives, to the monitoring of atmospheric conditions. Microelectrical mechanical systems (MEMS) fabrication technologies provide a way to fabricate sensitive devices. One type of MEMS vapor sensors is based on mass changing detection and the sensors have a functional chemical coating for absorbing the chemical vapor of interest. The principle of the resonant mass sensor is that the resonant frequency will experience a large change due to a small mass of gas vapor change. This thesis is trying to build analytical micro-cantilever and micro-tilting plate models, which can make optimization more efficient. Several objectives need to be accomplished: (1) Build an analytical model of MEMS resonant mass sensor based on micro-tilting plate with the effects of air damping. (2) Perform design optimization of micro-tilting plate with a hole in the center. (3) Build an analytical model of MEMS resonant mass sensor based on micro-cantilever with the effects of air damping. (4) Perform design optimization of micro-cantilever by COMSOL. Analytical models of micro-tilting plate with a hole in the center are compared with a COMSOL simulation model and show good agreement. The analytical models have been used to do design optimization that maximizes sensitivity. The micro-cantilever analytical model does not show good agreement with a COMSOL simulation model. To further investigate, the air damping pressures at several points on the micro-cantilever have been compared between analytical model and COMSOL model. The analytical model is inadequate for two reasons. First, the model’s boundary condition assumption is not realistic. Second, the deflection shape of the cantilever changes with the hole size, and the model does not account for this. Design optimization of micro-cantilever is done by COMSOL.

Assessment of the Occurrence and Potential Risks of Pharmaceuticals and their Metabolites in Fish and Water Using Liquid Chromatography Mass Spectrometry

A comprehensive method for the analysis of 11 target pharmaceuticals representing multiple therapeutic classes was developed for biological tissues (fish) and water. Water samples were extracted using solid phase extraction (SPE), while fish tissue homogenates were extracted using accelerated solvent extraction (ASE) followed by mixed-mode cation exchange SPE cleanup and analyzed by liquid chromatography tandem mass spectrometry (LC-MS/MS). Among the 11 target pharmaceuticals analyzed, trimethoprim, caffeine, sulfamethoxazole, diphenhydramine, diltiazem, carbamazepine, erythromycin and fluoxetine were consistently detected in reclaimed water. On the other hand, caffeine, diphenhydramine and carbamazepine were consistently detected in fish and surface water samples. In order to understand the uptake and depuration of pharmaceuticals as well as bioconcentration factors (BCFs) under the worst-case conditions, mosquito fish were exposed to reclaimed water under static-renewal for 7 days, followed by a 14-day depuration phase in clean water. Characterization of the exposure media revealed the presence of 26 pharmaceuticals while 5 pharmaceuticals including caffeine, diphenhydramine, diltiazem, carbamazepine, and ibuprofen were present in the organisms as early as 5 h from the start of the exposure. Liquid chromatography ultra-high resolution Orbitrap mass spectrometry was explored as a tool to identify and quantify phase II pharmaceutical metabolites in reclaimed water. The resulting data confirmed the presence of acetyl-sulfamethoxazole and sulfamethoxazole glucuronide in reclaimed water. To my knowledge, this is the first known report of sulfamethoxazole glucuronide surviving intact through wastewater treatment plants and occurring in environmental water samples. Finally, five bioaccumulative pharmaceuticals including caffeine, carbamazepine, diltiazem, diphenhydramine and ibuprofen detected in reclaimed water were investigated regarding the acute and chronic risks to aquatic organisms. The results indicated a low potential risk of carbamazepine even under the worst case exposure scenario. Given the dilution factors that affect environmental releases, the risk of exposure to carbamazepine will be even more reduced.

The Great Escape: A Modern Charismatic Movement within the Presbyterian Church

The present thesis examines the relationship between Youth Conference Ministries (YCM) and the Presbyterian Church. YCM is a charismatic organization that organizes youth retreats for students in middle school and high school, with the goal of charismatically educating the youth of America. The focus of this thesis is on the Great Escape Southwind, a middle school retreat that caters to the southern portion of United States. My thesis first traces the biblical and historical underpinnings of charismatic Christianity. Next it provides an ethnographic case study of the Great Escape, focusing on its ability to foster spiritual growth of students through an enthusiastic response to the Holy Spirit. Finally it examines the relationship between YCM and the Presbyteries that populate its retreats. Overall this thesis shows how YCM provides a charismatic service to the local Presbyterian Churches, allowing for its adolescent parishioners to remain enthusiastically active as they progress towards adulthood.

Assessment of the Occurrence and Potential Risks of Antibiotics and their Metabolites in South Florida Waters Using Liquid Chromatography Tandem Mass Spectrometry

An automated on-line SPE-LC-MS/MS method was developed for the quantitation of multiple classes of antibiotics in environmental waters. High sensitivity in the low ng/L range was accomplished by using large volume injections with 10-mL of sample. Positive confirmation of analytes was achieved using two selected reaction monitoring (SRM) transitions per antibiotic and quantitation was performed using an internal standard approach. Samples were extracted using online solid phase extraction, then using column switching technique; extracted samples were immediately passed through liquid chromatography and analyzed by tandem mass spectrometry. The total run time per each sample was 20 min. The statistically calculated method detection limits for various environmental samples were between 1.2 and 63 ng/L. Furthermore, the method was validated in terms of precision, accuracy and linearity. The developed analytical methodology was used to measure the occurrence of antibiotics in reclaimed waters (n=56), surface waters (n=53), ground waters (n=8) and drinking waters (n=54) collected from different parts of South Florida. In reclaimed waters, the most frequently detected antibiotics were nalidixic acid, erythromycin, clarithromycin, azithromycin trimethoprim, sulfamethoxazole and ofloxacin (19.3-604.9 ng/L). Detection of antibiotics in reclaimed waters indicates that they can’t be completely removed by conventional wastewater treatment process. Furthermore, the average mass loads of antibiotics released into the local environment through reclaimed water were estimated as 0.248 Kg/day. Among the surface waters samples, Miami River (reaching up to 580 ng/L) and Black Creek canal (up to 124 ng/L) showed highest concentrations of antibiotics. No traces of antibiotics were found in ground waters. On the other hand, erythromycin (monitored as anhydro erythromycin) was detected in 82% of the drinking water samples (n.d-66 ng/L). The developed approach is suitable for both research and monitoring applications. Major metabolites of antibiotics in reclaimed wates were identified and quantified using high resolution benchtop Q-Exactive orbitrap mass spectrometer. A phase I metabolite of erythromycin was tentatively identified in full scan based on accurate mass measurement. Using extracted ion chromatogram (XIC), high resolution data-dependent MS/MS spectra and metabolic profiling software the metabolite was identified as desmethyl anhydro erythromycin with molecular formula C36H63NO12 and m/z 702.4423. The molar concentration of the metabolite to erythromycin was in the order of 13 %. To my knowledge, this is the first known report on this metabolite in reclaimed water. Another compound acetyl-sulfamethoxazole, a phase II metabolite of sulfamethoxazole was also identified in reclaimed water and mole fraction of the metabolite represent 36 %, of the cumulative sulfamethoxazole concentration. The results were illustrating the importance to include metabolites also in the routine analysis to obtain a mass balance for better understanding of the occurrence, fate and distribution of antibiotics in the environment. Finally, all the antibiotics detected in reclaimed and surface waters were investigated to assess the potential risk to the aquatic organisms. The surface water antibiotic concentrations that represented the real time exposure conditions revealed that the macrolide antibiotics, erythromycin, clarithromycin and tylosin along with quinolone antibiotic, ciprofloxacin were suspected to induce high toxicity to aquatic biota. Preliminary results showing that, among the antibiotic groups tested, macrolides posed the highest ecological threat, and therefore, they may need to be further evaluated with, long-term exposure studies considering bioaccumulation factors and more number of species selected. Overall, the occurrence of antibiotics in aquatic environment is posing an ecological health concern.

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.