DEVELOPMENT AND APPLICATION OF SHORT-TERM MUTAGENICITY AND CYTOTOXICITY BIOASSAYS FOR INTEGRATED HEALTH ASSESSMENT STUDIES OF COAL FLY ASH EMISSIONS

Two respirable coal fly ash samples ((LESSTHEQ) 3(mu)m), one from a pressurized fluidized-bed combustion miniplant and one from a conventional combustion power plant, were investigated for physical properties, chemical composition and biological activity. Electron microscopy illustrated irregularity in fluidized-bed combustion fly ash and sphericity in conventional combustion fly ash. Elemental analysis of these samples showed differences in trace elements. Both fly ash samples were toxic in rabbit alveolar macrophage and Chinese hamster ovary cell systems in vitro. The macrophages were more sensitive to toxicity of fly ash than the ovary cells. For measuring the cytotoxicity of fly ash, the most sensitive parameters were adenosine triphosphate in the alveolar macrophage system and viability index in the hamster ovary system. Intact fluidized-bed combustion fly-ash particles showed mutagenicity only in strains TA98 and TA1538 without metabolic activation in the Ames Salmonella assay. No mutagenicity was detected in bioassay of conventional combustion fly ash particles. Solvent extraction yielded more mass from fluidized-bed combustion fly ash than from conventional combustion fly ash. The extracts of fluidized-bed combustion fly ash showed higher mutagenic activity than conventional combustion fly ash. These samples contained direct-acting, frameshift mutagens.^ Fly ash samples collected from the same fluidized-bed source by cyclones, a fabric filter, and a electrostatic precipitator at various temperatures were compared for particle size, toxicity, and mutagenicity. Results demonstrated that the biological activity of coal fly ash were affected by the collection site, device, and temperature.^ Coal fly ash vapor-coated with 1-nitropyrene was developed as a model system to study the bioavailability and recovery of nitroaromatic compounds in fly ash. The effects of vapor deposition on toxicity and mutagenicity of fly ash were examined. The nitropyrene coating did not significantly alter the ash's cytotoxicity. Nitropyrene was bioavailable in the biological media, and a significant percentage was not recovered after the coated fly ash was cultured with alveolar macrophages. 1-Nitropyrene loss increased as the number of macrophages was increased, suggesting that the macrophages are capable of metabolizing or binding 1-nitropyrene present in coal fly ash. ^

Stable isotope ratios and chemistry on corals from the Caribbean Sea

Instrumental climate data are limited in length and only available with low spatial coverage before the middle of the 20th century. This is too short to reliably determine and interpret decadal and longer scale climate variability and to understand the underlying mechanisms with sufficient accuracy. A proper knowledge of past variability of the climate system is needed to assess the anthropogenic impact on climate and ecosystems, and also important with regard to long-range climate forecasting. Highly-resolved records of past climate variations that extend beyond pre-industrial times can significantly help to understand long-term climate changes and trends. Indirect information on past environmental and climatic conditions can be deduced from climate-sensitive proxies. Large colonies of massive growing tropical reef corals have been proven to sensitively monitor changes in ambient seawater. Rapid skeletal growth, typically ranging between several millimeters to centimeters per year, allows the development of proxy records at sub-seasonal resolution. Stable oxygen isotopic composition and trace elemental ratios incorporated in the aragonitic coral skeleton can reveal a detailed history of past environmental conditions, e.g., sea surface temperature (SST). In general, coral-based reconstructions from the tropical Atlantic region have lagged behind the extensive work published using coral records from the Indian and Pacific Oceans. Difficulties in the analysis of previously utilized coral archives from the Atlantic, typically corals of the genera Montastrea and Siderastrea, have so far exacerbated the production of long-term high-resolution proxy records. The objective of this study is the evaluation of massive fast-growing corals of the species Diploria strigosa as a new marine archive for climate reconstructions from the tropical Atlantic region. For this purpose, coral records from two study sites in the eastern Caribbean Sea (Guadeloupe, Lesser Antilles; and Archipelago Los Roques, Venezuela) were examined. At Guadeloupe, a century-long monthly resolved multi-proxy coral record was generated. Results present the first d18O (Sr/Ca)-SST calibration equations for the Atlantic braincoral Diploria strigosa, that are robust and consistent with previously published values using other coral species from different regions. Both proxies reflect local variability of SST on a sub-seasonal scale, which is a precondition for studying seasonally phase-locked climate variations, as well as track variability on a larger spatial scale (i.e., in the Caribbean and tropical North Atlantic). Coral Sr/Ca reliably records local annual to interannual temperature variations and is higher correlated to in-situ air temperature than to grid-SST. The warming calculated from coral Sr/Ca is concurrent with the strong surface temperature increase at the study site during the past decades. Proxy data show a close relationship to major climate signals from the tropical Pacific and North Atlantic (the El Niño Southern Oscillation (ENSO) and the North Atlantic Oscillation (NAO)) affecting the seasonal cycle of SST in the North Tropical Atlantic (NTA). Coral oxygen isotopes are also influenced by seawater d18O (d18Osw) which is linked to the hydrological cycle, and capture large-scale climate variability in the NTA region better than Sr/Ca. Results from a quantitative comparison between extreme events in the two most prominent modes of external forcing, namely the ENSO and NAO, and respective events recorded in seasonal coral d18O imply that SST variability at the study site is highly linked to Pacific and North Atlantic variability, by this means supporting the assumptions of observational- and model-based studies which suggest a strong impact of ENSO and NAO forcings onto the NTA region through a modulation of trade wind strength in winter. Results from different spectral analysis tools suggest that interannual climate variability recorded by the coral proxies is II largely dictated by Pacific ENSO forcing, whereas at decadal and longer timescales the influence of the NAO is dominan. tThe Archipelago Los Roques is situated in the southeastern Caribbean Sea, north of the Venezuelan coast. Year-to-year variations in monthly resolved coral d18O of a nearcentury- long Diploria strigosa record are significantly correlated with SST and show pronounced multidecadal variations. About half of the variance in coral d18O can be explained by variations in seawater d18O, which can be estimated by calculating the d18Oresidual via subtracting the SST component from measured coral d18O. The d18Oresidual and a regional precipitation index are highly correlated at low frequencies, suggesting that d18Osw variations are primarily atmospheric-driven. Warmer SSTs at Los Roques broadly coincide with higher precipitation in the southeastern Caribbean at multidecadal time scales, effectively strengthening the climate signal in the coral d18O record. The Los Roques coral d18O record displays a strong and statistically significant relationship to different indices of hurricane activity during the peak of the Atlantic hurricane season in boreal summer and is a particularly good indicator of decadal-multidecadal swings in the latter indices. In general, the detection of long-term changes and trends in Atlantic hurricane activity is hampered due to the limited length of the reliable instrumental record and the known inhomogeneity in the observational databases which result from changes in observing practice and technology over the years. The results suggest that coral-derived proxy data from Los Roques can be used to infer changes in past hurricane activity on timescales that extend well beyond the reliable record. In addition, the coral record exhibits a clear negative trend superimposed on the decadal to multidecadal cycles, indicating a significant warming and freshening of surface waters in the genesis region of tropical cyclones during the past decades. The presented coral d18O time series provides the first and, so far, longest continuous coral-based record of hurricane activity. It appears that the combination of both signals (SST and d18Osw) in coral d18O leads to an amplification of large-scale climate signals in the record, and makes coral d18O even a better proxy for hurricane activity than SST alone. Atlantic hurricane activity naturally exhibits strong multidecadal variations that are associated with the Atlantic Multidecadal Oscillation (AMO), the major mode of lowfrequency variability in the North Atlantic Ocean. However, the mechanisms underlying this multidecadal variability remain controversial, primarily because of the limited instrumental record. The Los Roques coral d18O displays strong multidecadal variability with a period of approximately 60 years that is closely related to the AMO, making the Archipelago Los Roques a very sensitive location for studying low-frequency climate variability in the Atlantic Ocean. In summary, the coral records presented in this thesis capture different key climate variables in the north tropical Atlantic region very well, indicating that fast-growing Diploria strigosa corals represent a promising marine archive for further proxy-based reconstructions of past climate variability on a range of time scales.

Geochemistry of ODP Leg 129 igneous rocks

This report presents all the available major and trace elemental analyses and Sr, Nd, and Pb isotopic compositions of basaltic rocks recovered from Ocean Drilling Program Sites 800, 801, and 802 during Leg 129 (Table 1). Its main purpose is to provide other investigators a complete summary of geochemical data for Leg 129 basement basalts that they can use for later work. Detailed discussions of the data are presented elsewhere in the volume by Floyd and Castillo (Site 801 geochemistry and petrogenesis, dataset: doi:10.1594/PANGAEA.779154) Floyd et al. (Sites 800 and 802 geochemistry and petrography, dataset: doi:10.1594/PANGAEA.779129), Alt et al. (Site 801 alteration, dataset: doi:10.1594/PANGAEA.779207), and Castillo et al. (Sr, Nd, and Pb isotope geochemistry of Leg 129 basalts, dataset: doi:10.1594/PANGAEA.779191).

(Table 1) Geochemistry of ODP Hole 130-807C carbonates across the K/T boundary

Paleontological, stable isotopic, trace elemental abundance, and magnetostratigraphic studies have been performed on limestones spanning the Cretaceous/Tertiary boundary transition at Ocean Drilling Program (ODP) Hole 807C. Paleontological evidence exists for considerable resedimentation, which we attribute to the fact that Hole 807C is located in a basement graben. Age estimates based on planktonic foraminiferal biostratigraphy, as well as magnetostratigraphy, indicate that sedimentation rates could have been on the order of 12-14 m/m.y. This is significantly higher than those documented in other important Deep Sea Drilling Project (DSDP) and ODP Cretaceous/Tertiary boundary sections using the same age control points (e.g., DSDP Hole 577 and ODP Hole 690B), although not as high as those documented from DSDP Hole 524. The expanded nature of this succession has resulted in the Cretaceous/Tertiary boundary d13C decrease occurring over approximately a 9-m interval. Ir analysis of these sediments do not show a single large anomaly, as has been found in other Cretaceous/Tertiary boundary sections, but trivial background levels instead. Ce data support the hypothesis that this section has been expanded by secondary sedimentological processes.

Foraminiferal trace element ratios from South Atlantic sediments

The rate of uranium accumulation in oceanic sediments from seawater is controlled by bottom water oxygen concentrations and organic carbon fluxes-two parameters that are linked to deep ocean storage of CO2. To investigate glacial-interglacial changes in what is known as authigenic U, we have developed a rapid method for its determination as a simple addition to a procedure for foraminiferal trace element analysis. Foraminiferal calcite acts as a low U substrate (U/Ca < 15 nmol/mol) upon which authigenic U accumulates in reducing sediments. We measured a downcore record of foraminiferal U/Ca from ODP Site 1090 in the South Atlantic and found that U/Ca ratios increase by 70-320 nmol/mol during glacial intervals. There is a significant correlation between U/Ca records of benthic and planktonic foraminiferal species and between U/Ca and bulk sediment authigenic U. These results indicate that elevated U/Ca ratios are attributable to the accumulation of authigenic U coatings in sediments. Foraminiferal Mn/Ca ratios were lower during the glacial intervals, suggesting that the observed U accumulation on the shells is not directly linked to U incorporation into secondary manganese phases. Thus, foraminiferal U/Ca ratios may provide useful information on past changes in sediment redox conditions.

Major and trace elements and interelement ratios at DSDP Leg 81 Holes

Fifty-two samples of basalt from the four holes drilled on the Leg 81 transect across the Rockall margin were analyzed by X-ray fluorescence for Rb, Sr, Y, Zr, and Nb. On the basis of these results 13 samples were chosen for major and supplementary trace-element analysis. The results show no progressive change in the character of the volcanism, from Hole 555 in the continental domain through Holes 552 and 553A in the dipping reflector sequence to Hole 554A on the outer high. Two distinct magma types are present, apparently reflecting heterogeneity of the underlying mantle, but both types are present in both Holes 553A and 555, while Hole 552 and Hole 554 are each composed of a single type. Both magma types have a clear ocean-floor basalt signature when examined by discrimination diagrams, as does the basalt from Deep Sea Drilling Project Site 112, which formed at the same time as the Leg 81 basalts slightly farther south along the spreading center. In contrast, the basalts of East Greenland, formed at the same time, are more enriched in incompatible elements and have a within-plate geochemical signature, as is found in some basalts of Iceland today. Clearly the present distinction in geochemistry between the basalts of Iceland and those erupting well south on the Reykjanes Ridge was already established when continental splitting took place.

Inorganic and organic geochemistry and sediment descriptions at DSDP Hole 93-603B

About one hundred samples of sediments and rocks recovered in Hole 603B were analyzed for type, abundance, and isotopic composition of organic matter, using a combination of Rock-Eval pyrolysis, C-H-N-S elemental analysis, and isotope-ratio mass spectrometry. Concentrations of major, minor, and trace inorganic elements were determined with a combination of X-ray fluorescence and induction-coupled plasma spectrometry. The oldest strata recovered in Hole 603B (lithologic Unit V) consist of interbedded light-colored limestones and marlstones, and black calcareous claystones of Neocomian age. The inorganic and organic geochemical results suggest a very terrigenous aspect to the black claystones. The organic geochemical results indicate that the limestones and marlstones contain a mixture of highly degraded marine and terrestrial organic matter. Comparison of the Neocomian carbonates at Site 603 with those on the other side of the North Atlantic, off Northwest Africa at Site 367, shows that the organic matter at Site 367 contains more marine organic matter, as indicated by higher pyrolysis hydrogen indices and lighter values of d13C. Comparison of inorganic geochemical results for the carbonate lithologies at Site 603 with those for carbonate lithologies at Site 367 suggests that the Site 603 carbonates may contain clastic material from both North American and African sources. The black claystones at Site 603, on the other hand, probably were derived almost entirely from North American clastic sources. Lithologic Unit IV overlying the Neocomian carbonates, consists of interbedded red, green, and black claystones. The black claystones at Site 603 contain more than ten times the organic carbon concentration of the interbedded green claystones. The average concentration of organic carbon in the black claystones (2.8%), however, is low relative to most mid-Cretaceous black claystones and shales in the Atlantic, particularly those found off Northwest Africa. The geochemical data all suggest that the organic matter in the black claystones is more abundant but generally more degraded than the organic matter in the green claystones, and that it was derived mainly from terrestrial sources and deposited in oxygenated bottom waters. The increased percentage of black claystone beds in the upper Cenomanian section, and the presence of more hydrogen-rich organic matter in this part of the section, probably resulted from the increased production and accumulation of marine organic matter that is represented worldwide near the Cenomanian/Turonian boundary in deep-sea and land sections. A few upper Cenomanian black claystone samples that have hydrogen indices > 150 also contain particularly high concentrations of V and Zn. Most samples of black claystone, however, are not particularly metal-rich compared with other black claystones and shales. Compared with red claystones from lithologic Unit IV, the green and black claystones are enriched in many trace transition elements, especially V, Zn, Cu, Co, and Pb. The main difference between the "carbonaceous" claystones of lithologic Unit IV and "variegated" or "multicolored" claystones of the overlying Upper Cretaceous to lower Tertiary Unit III is the absence of black claystone beds. As observed at several other sites (105 and 386), the multicolored claystones at Site 603 are somewhat enriched in several trace transition elements-especially Cu, Ni, and Cr-relative to most deep-sea clays. The multicolored claystones are not enriched in Fe and Mn, and therefore are not "metalliferous" sediments in the sense of those found at several locations in the eastern Pacific. The source of the slightly elevated concentrations of transition metals in the multicolored claystones probably is upward advection and diffusion of metals from the black claystones of the underlying Hatteras Formation. The red, orange, and green claystone beds of lithologic Unit II (Eocene), like those of Unit III, really represent a continuation of deposition of multicolored claystone that began after the deposition of the Neocomian carbonates. The color of the few black beds that occur within this unit results from high concentrations of manganese oxide rather than high concentrations of organic matter.

Fe-Mn crusts from the Atlantic Ocean

Mineral and chemical compositions of a set of crust samples collected from the North, Central and South Atlantic were examined by means of analytical electron microscopy and ICP-MS, chemical, and microchemical elemental analysis. Vernadite, asbolane, and goethite are dominant mineral phases of the crusts, ferrihydrite is minor, hematite and feroxyhyte are rare. The samples show wide variability in major and trace element contents; however, their characteristic geochemical signatures indicate hydrogenous origin. A comparison between compositions of oceanic hydrogenous and hydrothermal crusts and metalliferous hydrothermal sediments from different ocean areas suggests that the geochemical approach may be insufficient in some cases and fail to identify hydrothermal input in ferromanganese crusts of mixed composition.

Water chemistry controls on minor elemental concentrations and strontium isotopic compositions of freshwater biogenic carbonate in northeastern Washington streams

Tracking the movement of migratory freshwater fish is essential to those invested in rebuilding declining fish populations. Using strontium isotopic signatures to match calcified fish tissues to streams where fish spawn is a useful method of tracking migratory fish where physical tracking methods such as radio, acoustic, or external tags, have proven unsuccessful. In this study, we develop tools to practice this method of tracking fish in Lake Roosevelt and its upstream tributaries in Washington State by analyzing the elemental concentrations and 87Sr/86Sr ratios of water samples, and mussel shell samples. This study evaluates whether mussel shells act as an appropriate proxy for water chemistry by comparing the 87Sr/86Sr isotope ratios of water samples to the 87Sr/86Sr isotope ratios of mussel shells sampled from the same, or nearby, locations. We compare concentrations of Ba, Ca, Cd, Cu, Fe, Mg, Pb, Sr, and U in the water and mussel shell samples to determine the feasibility of using mussel shells as a proxy for water chemistry. If it is determined that the concentrations of these elements in mussel shells reflect that of the surrounding water composition, the elemental composition of mussel shells can be compared to that of calcified tissues in fish, such as otoliths, to infer the location of the natal stream. We report analyses of water and mussel shell samples collected from Lake Roosevelt, Sanpoil River, Spokane River, Colville River, Kettle River, Pend Oreille River, Kootenay River, and Columbia River in Washington State. Each of these rivers is a tributary to Lake Roosevelt, and each flows through different geologic units. We hypothesize that the differences in the rock units of each stream’s watershed are reflected in the elemental concentrations and strontium isotopic ratios of water in each stream and in the lake. We also hypothesize that the composition of the mussel shells will match the composition of the water samples, therefore allowing us to use the mussel shells as a proxy for local water chemistry. Additionally, we hypothesize that the composition of the mussel shells will vary by location, and that we will be able to then infer where a fish is from by matching the composition of the fish in question to the mussels we have analyzed. We found that 87Sr/86Sr values for water and mussel hinge samples collected from tributaries east of Lake Roosevelt are significantly higher than the 87Sr/86Sr values for samples collected from tributaries west of Lake Roosevelt with averages of 0.7235 and 0.7089, respectively. The average 87Sr/86Sr ratios for water and mussel hinge samples collected within Lake Roosevelt is 0.7158, which is between the averages for samples collected east and west of the lake. Generally, older rocks are exposed on the east side of the lake, and younger rocks on the west side of the lake, so our 87Sr/86Sr values support the hypothesis that geologic units are a primary control on water chemistry, and that tributary compositions mix to form an average weighed by flow in Lake Roosevelt. The 87Sr/86Sr values for water and mussel shell samples collected from the same locations have a strong, positive linear correlation, suggesting that mussel shell 87Sr/86Sr ratios reflect the 87Sr/86Sr ratios of the ambient water. With these data, we can distinguish between different streams and the lake, but cannot distinguish between samples from within the same stream or within Lake Roosevelt. The Sr:Ca and Fe:Ca ratios of water samples show positive correlations with mussel shell compositions, with R2 values of 0.82 and 0.52, respectively. Ratios of Mg, Ba, Cu, Cd, Pb, and U to Ca showed little or no positive correlation between water and mussel shell samples. The elemental concentration data collected for this study do not demonstrate whether a correlation between elemental ratios in water samples and elemental ratios in mussel shell samples collected from the same location exists. Positive Sr:Ca and Fe:Ca correlations for water versus mussel shell samples indicate that perhaps for some elements, the composition of mussel shells are representative of the composition of ambient water. Using elemental concentration ratios to complement 87Sr/86Sr isotopic data may enhance our ability to identify correlations between water and mussel shell samples, and ultimately between mussel shell and otolith samples. The hinge part of a mussel shell may be used as a proxy for local water composition because the mussel shell composition reflects that of the local ambient water. The hinge of the mussel has the same composition as the whole mussel shell. We measured variation of 87Sr/86Sr ratios in the water among different streams and Lake Roosevelt. The 87Sr/86Sr values for samples collected in tributaries east of Lake Roosevelt, which erode older rocks, are higher for mussel shell and water samples than the average 87Sr/86Sr values for mussel shell and water samples collected in tributaries west of Lake Roosevelt, which flow through younger rocks.

Potential of Sr isotopic analysis in ceramic provenance studies: Characterisation of Chinese stonewares

We compare the trace element and Sr isotopic compositions of stoneware bodies made in Yaozhou and Jizhou to characterise these Chinese archaeological ceramics and examine the potential of Sr isotopes in provenance studies. Element concentrations determined by ICP-MS achieve distinct characterisation for Jizhou samples due to their restricted variation, yet had limited success with Yaozhou wares because of their large variability. In contrast, Sr-87/Sr-86 ratios in Yaozhou samples have a very small variation and are all significantly lower than those of Jizhou samples, which show a large variation and cannot be well characterised with Sr isotopes. Geochemical interpretation reveals that Sr-87/Sr-86 ratios will have greater potential to characterise ceramics made of low Rb/Sr materials such as kaolin clay, yet will show larger variations in ceramics made of high Rb/Sr materials such as porcelain stone. (c) 2005 Elsevier B.V. All rights reserved.

Development and evaluation of an ion induced x-ray emission system for the analysis of light and medium weight elements

The present work describes the development of a proton induced X-ray emission (PIXE) analysis system, especially designed and builtfor routine quantitative multi-elemental analysis of a large number of samples. The historical and general developments of the analytical technique and the physical processes involved are discussed. The philosophy, design, constructional details and evaluation of a versatile vacuum chamber, an automatic multi-sample changer, an on-demand beam pulsing system and ion beam current monitoring facility are described.The system calibration using thin standard foils of Si, P, S,Cl, K, Ca, Ti, V, Fe, Cu, Ga, Ge, Rb, Y and Mo was undertaken at proton beam energies of 1 to 3 MeV in steps of 0.5 MeV energy and compared with theoretical calculations. An independent calibration check using bovine liver Standard Reference Material was performed.  The minimum detectable limits have been experimentally determined at detector positions of 90° and 135° with respect to the incident beam for the above range of proton energies as a function of atomic number Z. The system has detection limits of typically 10- 7 to 10- 9 g for elements 14elemental concentrations. In conclusion the findings of this work are discussed with suggestions for further work .

The analysis of organic matter in oil-shales

The organic matter in five oil shales (three from the Kimmeridge Clay sequence, one from the Oxford Clay sequence and one from the Julia Creek deposits in Australia) has been isolated by acid demineralisation, separated into kerogens and bitumens by solvent extraction and then characterised in some detail by chromatographic, spectroscopic and degradative techniques. Kerogens cannot be characterised as easily as bitumens because of their insolubility, and hence before any detailed molecular information can be obtained from them they must be degraded into lower molecular weight, more soluble components. Unfortunately, the determination of kerogen structures has all too often involved degradations that were far too harsh and which lead to destruction of much of the structural information. For this reason a number of milder more selective degradative procedures have been tested and used to probe the structure of kerogens. These are: 1. Lithium aluminium hydride reduction. - This procedure is commonly used to remove pyrite from kerogens and it may also increase their solubility by reduction of labile functional groups. Although reduction of the kerogens was confirmed, increases in solubility were correlated with pyrite content and not kerogen reduction. 2. O-methylation in the presence of a phase transfer catalyst. - By the removal of hydrogen bond interactions via O-methylation, it was possible to determine the contribution of such secondary interactions to the insolubility of the kerogens. Problems were encountered with the use of the phase transfer catalyst. 3. Stepwise alkaline potassium permanganate oxidation. - Significant kerogen dissolution was achieved using this procedure but uncontrolled oxidation of initial oxidation products proved to be a problem. A comparison with the peroxytrifluoroaceticacid oxidation of these kerogens was made. 4. Peroxytrifluoroacetic acid oxidation. - This was used because it preferentially degrades aromatic rings whilst leaving any benzylic positions intact. Considerable conversion of the kerogens into soluble products was achieved with this procedure. At all stages of degradation the products were fully characterised where possible using a variety of techniques including elemental analysis, solution state 1H and 13C nuclear magnetic resonance, solid state 13C nuclear magnetic resonance, gel-permeationchromatography, gas chromatography-mass spectroscopy, fourier transform infra-red spectroscopy and some ultra violet-visible spectroscopy.

The use of hyphenated spectrometric techniques for the environmental forensic assessment of non-traditional pollutants and degradates in the greater Florida Everglades

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. ^

Evaluation of the evidential value of the elemental composition of glass, ink and paper by laser-based microspectrochemical methods

Elemental analysis can become an important piece of evidence to assist the solution of a case. The work presented in this dissertation aims to evaluate the evidential value of the elemental composition of three particular matrices: ink, paper and glass. In the first part of this study, the analytical performance of LIBS and LA-ICP-MS methods was evaluated for paper, writing inks and printing inks. A total of 350 ink specimens were examined including black and blue gel inks, ballpoint inks, inkjets and toners originating from several manufacturing sources and/or batches. The paper collection set consisted of over 200 paper specimens originating from 20 different paper sources produced by 10 different plants. Micro-homogeneity studies show smaller variation of elemental compositions within a single source (i.e., sheet, pen or cartridge) than the observed variation between different sources (i.e., brands, types, batches). Significant and detectable differences in the elemental profile of the inks and paper were observed between samples originating from different sources (discrimination of 87–100% of samples, depending on the sample set under investigation and the method applied). These results support the use of elemental analysis, using LA-ICP-MS and LIBS, for the examination of documents and provide additional discrimination to the currently used techniques in document examination. In the second part of this study, a direct comparison between four analytical methods (µ-XRF, solution-ICP-MS, LA-ICP-MS and LIBS) was conducted for glass analyses using interlaboratory studies. The data provided by 21 participants were used to assess the performance of the analytical methods in associating glass samples from the same source and differentiating different sources, as well as the use of different match criteria (confidence interval (±6s, ±5s, ±4s, ±3s, ±2s), modified confidence interval, t-test (sequential univariate, p=0.05 and p=0.01), t-test with Bonferroni correction (for multivariate comparisons), range overlap, and Hotelling's T2 tests. Error rates (Type 1 and Type 2) are reported for the use of each of these match criteria and depend on the heterogeneity of the glass sources, the repeatability between analytical measurements, and the number of elements that were measured. The study provided recommendations for analytical performance-based parameters for µ-XRF and LA-ICP-MS as well as the best performing match criteria for both analytical techniques, which can be applied now by forensic glass examiners.