A comprehensive investigation of sensitive ecosystems in South Florida with the main goal of determining the identity, spatial distribution, and sources of both organic biocides and trace elements in different environmental compartments is reported. This study presents the development and validation of a fractionation and isolation method of twelve polar acidic herbicides commonly applied in the vicinity of the study areas, including e.g. 2,4-D, MCPA, dichlorprop, mecroprop, picloram in surface water. Solid phase extraction (SPE) was used to isolate the analytes from abiotic matrices containing large amounts of dissolved organic material. Atmospheric-pressure ionization (API) with electrospray ionization in negative mode (ESP-) in a Quadrupole Ion Trap mass spectrometer was used to perform the characterization of the herbicides of interest. The application of Laser Ablation-ICP-MS methodology in the analysis of soils and sediments is reported in this study. The analytical performance of the method was evaluated on certified standards and real soil and sediment samples. Residential soils were analyzed to evaluate feasibility of using the powerful technique as a routine and rapid method to monitor potential contaminated sites. Forty eight sediments were also collected from semi pristine areas in South Florida to conduct screening of baseline levels of bioavailable elements in support of risk evaluation. The LA-ICP-MS data were used to perform a statistical evaluation of the elemental composition as a tool for environmental forensics. A LA-ICP-MS protocol was also developed and optimized for the elemental analysis of a wide range of elements in polymeric filters containing atmospheric dust. A quantitative strategy based on internal and external standards allowed for a rapid determination of airborne trace elements in filters containing both contemporary African dust and local dust emissions. These distributions were used to qualitative and quantitative assess differences of composition and to establish provenance and fluxes to protected regional ecosystems such as coral reefs and national parks.

The need for elemental analysis of biological matrices such as bone, teeth, and plant matter for sourcing purposes has emerged within the forensic and geochemical laboratories. Trace elemental analyses for the comparison of aterials such as glass by inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS has been shown to offer a high degree of discrimination between different manufacturing sources. Unit resolution ICP-MS instruments may suffer from some polyatomic interferences including 40Ar16O+, 40Ar16O1H+, and 40Ca16O+ that affect iron measurement at trace levels. Iron is an important element in the analysis of glass and also of interest for the analysis of several biological matrices. A comparison of the nalytical performance of two different ICP-MS systems for iron analysis in glass for determining the method detection limits (MDLs), accuracy, and precision of the measurement is presented. Acid digestion and laser ablation methods are also compared. Iron polyatomic interferences were reduced or resolved by using dynamic reaction cell and high resolution ICP-MS. MDLs as low as 0.03 ìg g-1 and 0.14 ìg g-1 for laser ablation and solution based analyses respectively were achieved. The use of helium as a carrier gas demonstrated improvement in the detection limits of both iron isotopes (56Fe and 57Fe) in medium resolution for the HR-ICP-MS and with a dynamic reaction cell (DRC) coupled to a quadrupole ICP-MS system. The development and application of robust analytical methods for the quantification of trace elements in biological matrices has lead to a better understanding of the potential utility of these measurements in forensic chemical analyses. Standard reference materials (SRMs) were used in the development of an analytical method using HR-ICP-MS and LA-HR-ICP-MS that was subsequently applied on the analysis of real samples. Bone, teeth and ashed marijuana samples were analyzed with the developed method. Elemental analysis of bone samples from 12 different individuals provided discrimination between individuals, when femur and humerus bones were considered separately. Discrimination of 14 teeth samples based on elemental composition was achieved with the exception of one case where samples from the same individual were not associated with each other. The discrimination of 49 different ashed plant (cannabis)samples was achieved using the developed method.

Routine monitoring of environmental pollution demands simplicity and speed without sacrificing sensitivity or accuracy. The development and application of sensitive, fast and easy to implement analytical methodologies for detecting emerging and traditional water and airborne contaminants in South Florida is presented. A novel method was developed for quantification of the herbicide glyphosate based on lyophilization followed by derivatization and simultaneous detection by fluorescence and mass spectrometry. Samples were analyzed from water canals that will hydrate estuarine wetlands of Biscayne National Park, detecting inputs of glyphosate from both aquatic usage and agricultural runoff from farms. A second study describes a set of fast, automated LC-MS/MS protocols for the analysis of dioctyl sulfosuccinate (DOSS) and 2-butoxyethanol, two components of Corexit®. Around 1.8 million gallons of those dispersant formulations were used in the response efforts for the Gulf of Mexico oil spill in 2010. The methods presented here allow the trace-level detection of these compounds in seawater, crude oil and commercial dispersants formulations. In addition, two methodologies were developed for the analysis of well-known pollutants, namely Polycyclic Aromatic Hydrocarbons (PAHs) and airborne particulate matter (APM). PAHs are ubiquitous environmental contaminants and some are potent carcinogens. Traditional GC-MS analysis is labor-intensive and consumes large amounts of toxic solvents. My study provides an alternative automated SPE-LC-APPI-MS/MS analysis with minimal sample preparation and a lower solvent consumption. The system can inject, extract, clean, separate and detect 28 PAHs and 15 families of alkylated PAHs in 28 minutes. The methodology was tested with environmental samples from Miami. Airborne Particulate Matter is a mixture of particles of chemical and biological origin. Assessment of its elemental composition is critical for the protection of sensitive ecosystems and public health. The APM collected from Port Everglades between 2005 and 2010 was analyzed by ICP-MS after acid digestion of filters. The most abundant elements were Fe and Al, followed by Cu, V and Zn. Enrichment factors show that hazardous elements (Cd, Pb, As, Co, Ni and Cr) are introduced by anthropogenic activities. Data suggest that the major sources of APM were an electricity plant, road dust, industrial emissions and marine vessels.

This dissertation contributes to our understanding of the use of the Li-isotopic composition of seawater as a tracer of the earth system with a focus on the role of low-temperature hydrothermal systems within the lava section of the ocean crust. Experiments were conducted to study the exchange coefficient (D(Li/Ca)) and isotopic fractionation factor (α; 1000ln(α)=Δ) for lithium between inorganic calcite and an aqueous solution as a function of solution chemistry. These experiments show that, under the conditions used, D(Li/Ca) negatively correlates with solution H+/Ca2+ ratio (and the solution pH) and Δ positively correlates with solution pH. The change in D(Li/Ca) with solution chemistry is interpreted as indicating that Li is incorporated into calcite as LiHCO3, and hence depends on solution H+/Ca2+. A series of diffusion experiments were performed to test whether changes in pH led to changes in the aqueous Li speciation that would lead to changes in the relative diffusivity of the two Li-isotopes, but no such changes were observed. It is proposed that the change in Δ with changing solution pH may either reflect a kinetic or equilibrium isotope fractionation associated with changing solution chemistry. These results have important implications for interpreting the Li content of calcite that has undergone any diagenetic modification. The Li-content and isotopic composition of rocks altered by low-temperature, off-axis hydrothermal systems in the upper oceanic crust were studied to better understand the role of these systems in controlling the Li-isotopic composition of seawater. Results of a detailed study of DSDP Holes 417A, 417D and 418A from 119 Myr Western North Atlantic Ocean basin show that the Li content of the lavas decreases with depth in the upper ~30 m below sediments while the Li-isotopic composition increases from a low value and then does not show systematic variation in deeper sections. No evidence was found to support a role for a change in mineralogy of alteration products to explain the observed variation in Li composition of lavas. There is also no evidence for the modification of the composition of hydrothermal fluid due to a mixture with sediment pore-fluid. Simple one-dimensional fluid flow and fluid-rock reaction models also cannot explain the observed variation. Instead, a model of free-circulation of seawater through the upper few tens of meters of the lavas, and leakage of modified fluid into the deeper portion of the lava pile seems to explain the observed variations best. To investigate the role of low-temperature off-axis hydrothermal systems on the Li content and isotopic composition of seawater from the Cretaceous to modern era, five DSDP/ODP holes with crustal age spanning from 13.6 to 95 Myr were studied in combination with results from previous studies. Results suggest that the average amount of Li added to the upper oceanic crust decreases, while its average Li-isotopic composition increases, from the Cretaceous to the modern. The simplest explanation for these variations may be a decrease in Li concentration and an increase in Li-isotopic composition, of seawater over this time interval. / Graduate

The determination of uranium in samples of the enviroment was considered for liquadeted chemical toxicity of uranium and it is impossible to leave out a potential occurrence in drinking water. The purpose of this diploma thesis was the monitoring of preselected public water supplies in the South Moravia and post action analysis of those samples. That was all on the basis of the requierement of the Regional Hygiene Station. For determination of trace concentrations of uranium in drinking waters the method ICP-MS (Inductively Coupled Plasma with Mass Spectrometry) was chosen. All of the results were then summarized and evaluated. At the end are proposed feasible solutions and precautions for public water supplies operators.

The theoretical part of the thesis deals with the technology of fruit juices production and characteristics of the known varieties of elderberry. There are also summarized available information on the presence and properties of minerals in food. In the practical part of the thesis 17 different varieties of elderberry juice and commercially available juice sold as food supplements were analyzed using ICP-MS technique. The concentrations of 15 selected essential and toxic elements were determined in these juices.

Today is the food quality a discussed topic not only in the Czech Republic. In this work we focused on micronutrients and heavy metals in strawberries. Strawberries are very attractive fruit consumed by all age groups from children to seniors. These bring not only gustatory pleasure but also positive effects on human organism. Soft fruit structure could contribute to the accumulation of heavy metals, which can be dangerous in certain quantities in terms of acute toxicity or what is more likely in terms of chronic exposure. In the spring - autumn of 2011 samples from the home cultivation of strawberries in the Czech Republic were collected and also samples of fruits that are commonly available in supermarket chains in this period were purchased. The element analysis was performed by the mass spectrometry with inductively coupled plasma, which belongs to a very sensitive method of elements determination.

The work has been focused on the preconcentration techniques for determination of 9Be, 51V, 59Co, 60Ni, 89Y, 111Cd, 208Pb, 232Th and 238U on the modified sorbents, all measurements were performed on ICP-MS. The instrument setup was optimized. The solution of internal standard (200 µg•l-1) was used during all measurements. The internal standard were chosen as follows: 6Li for 9Be, 45Sc (51V), 72Ge (59Co, 60Ni, 89Y), 103Rh (111Cd), 209Bi (206Pb, 207Pb, 208Pb, 232Th and 238U). Another parameters such as influence of mineral acids (HCl, HNO3), surfactant (Septonex®, Zephyramin, Ajatin, Brij 35 and Sodium dodecyl sulphate) and organic reagents (Ammonium pyrrolidinedithiocarbamate, 8-Hydroxyquinoline-5-sulphonic acid, 1,2-Dihydroxyanthraquinone-3-sulphonic acid and 4-(2-Pyridylazo)resorcinol) and the effect of some matrix components on intensity of instrument signal determination was investigated. For preconcentration polar Silicagel and modified nonpolar Silicagels (Silicagel-C18, C8 nad Phenyl) were used. Another experimantal part was dedicated to preconcentration on nonpolar Amberlite XAD-16 and Strata SDB-L and intermediately polar sorbent Amberlite XAD-7. Recoveries of sorption process were observed in the presence of all testing types of surfactants in certified concentration 5•10-4 mol•l-1. Surfactants were always applied in the conditioning step. The suitable combinations of surfactant and organic reagent were tested for increasing of recoveries of analytes. Testing organic reagents were added in five times mass excess againts concentration of analytes, the concentration of the organic reagents was 900 µg•l-1. The organic reagent was always added to the solution for preconcentration before this solution was led on the sorbent. The composition and a necessary volume of elution mixture for quantitative elution were tested, too. Only one sorbent was chosen from each group of sorbents with similar properties. The chosen sorbent showed the best recoveries in majority of target analytes. The highest recoveries from silica-group was reached for Silicagel-C18, from nonpolar Amberlite was chosen Strata SDB-L and intermediately polar Amberlite XAD-7. The influence of some matrix components (anionts and cations) on recoveries of analytes was investigated for chosen sorbent. The optimized process was applied on real samples of nature water and industry water. In experimental part all analytes are marked as specific izotopes, which were measured by ICP-MS. Of course, all izotopes of analytes undergo preconcentration techniques.

Silver isotopes nowadays present a very fast evolving system. One of the field in which this isotopic system is used is archaeology where the silver isotopes are used as a tracer of monetary and power changes between geographical regions. Through statistical analysis of measured data and their comparison with so far published values can be estimated probability of common source area of metal used for coinage. On Celtic coin samples (180-70 BC) provided by the Institute of Archaeology of the CAS, Prague (A. Danielisová) the isotopic composition of silver was measured. Silver was separated from the matrix elements by a method which uses ascorbic acid to precipitate silver. However, the weights of samples commonly used for this method are generally distinctly higher than the amounts of the obtained fragments of Celtic coins. Regarding the differences in the method and low weights of fragments, tests with variable concentrations of ascorbic acid and amounts of silver were performed. The amounts of silver used for this method are commonly ~30x-70x higher. The results showed that this method effectively separates silver from matrix elements and is sufficient for higher concentrations of silver; with lower ones the yields are reduced. The separated silver was measured using MC-ICP-MS. The adjusted...

In the leading part of this work I presented general information on the kingdom of fungi and fungal ecology focused on marofungi (macromycetes). Furthermore, I reviewed the phenomenon of trace elements accumulation in macrofungal fruit-bodies, particularly focused on uranium and its biogeochemistry. In the experimental part, results of my own research are presented. I determined concentrations of uranium, thorium, silver and lead by use of HR- ICP-MS and ENAA. The macrofungal samples were collected 1/ in clean areas with diverse geological bedrock, 2/ in uranium-polluted area in vicinity of Příbram (Central Bohemia, Czech Republic). Furthermore, selected trace elements were determined also in underlying soils by use of the both analytical methods. For investigation of trace elements mobility, the BCR sequential extraction was applied.