Spectroscopic analysis of terrestrial analogues for the interpretation of surface composition of rocky bodies in the solar system. Effects of mineral mixing and particle size. Applications to moon, mars and implications for mercury.

Among the Solar System’s bodies, Moon, Mercury and Mars are at present, or have been in the recent years, object of space missions aimed, among other topics, also at improving our knowledge about surface composition. Between the techniques to detect planet’s mineralogical composition, both from remote and close range platforms, visible and near-infrared reflectance (VNIR) spectroscopy is a powerful tool, because crystal field absorption bands are related to particular transitional metals in well-defined crystal structures, e.g., Fe2+ in M1 and M2 sites of olivine or pyroxene (Burns, 1993). Thanks to the improvements in the spectrometers onboard the recent missions, a more detailed interpretation of the planetary surfaces can now be delineated. However, quantitative interpretation of planetary surface mineralogy could not always be a simple task. In fact, several factors such as the mineral chemistry, the presence of different minerals that absorb in a narrow spectral range, the regolith with a variable particle size range, the space weathering, the atmosphere composition etc., act in unpredictable ways on the reflectance spectra on a planetary surface (Serventi et al., 2014). One method for the interpretation of reflectance spectra of unknown materials involves the study of a number of spectra acquired in the laboratory under different conditions, such as different mineral abundances or different particle sizes, in order to derive empirical trends. This is the methodology that has been followed in this PhD thesis: the single factors previously listed have been analyzed, creating, in the laboratory, a set of terrestrial analogues with well-defined composition and size. The aim of this work is to provide new tools and criteria to improve the knowledge of the composition of planetary surfaces. In particular, mixtures composed with different content and chemistry of plagioclase and mafic minerals have been spectroscopically analyzed at different particle sizes and with different mineral relative percentages. The reflectance spectra of each mixture have been analyzed both qualitatively (using the software ORIGIN®) and quantitatively applying the Modified Gaussian Model (MGM, Sunshine et al., 1990) algorithm. In particular, the spectral parameter variations of each absorption band have been evaluated versus the volumetric FeO% content in the PL phase and versus the PL modal abundance. This delineated calibration curves of composition vs. spectral parameters and allow implementation of spectral libraries. Furthermore, the trends derived from terrestrial analogues here analyzed and from analogues in the literature have been applied for the interpretation of hyperspectral images of both plagioclase-rich (Moon) and plagioclase-poor (Mars) bodies.

Accumulation and fate of mercury in an Everglades aquatic food web

This project examined the pathways of mercury (Hg) bioaccumulation and its relation to trophic position and hydroperiod in the Everglades. I described fish-diet differences across habitats and seasons by analyzing stomach contents of 4,000 fishes of 32 native and introduced species. Major foods included periphyton, detritus/algal conglomerate, small invertebrates, aquatic insects, decapods, and fishes. Florida gar, largemouth bass, pike killifish, and bowfin were at the top of the piscine food web. Using prey volumes, I quantitatively classified the fishes into trophic groups of herbivores, omnivores, and carnivores. Stable-isotope analysis of fishes and invertebrates gave an independent and similar assessment of trophic placement. Trophic patterns were similar to those from tropical communities. I tested for correlations of trophic position and total mercury. Over 4,000 fish, 620 invertebrate, and 46 plant samples were analyzed for mercury with an atomic-fluorescence spectrometer. Mercury varied within and among taxa. Invertebrates ranged from 25–200 ng g −1 ww. Small-bodied fishes varied from 78–>400 ng g −1 ww. Large predatory fishes were highest, reaching a maximum of 1,515 ng−1 ww. Hg concentrations in both fishes and invertebrates were positively correlated with trophic position. I examined the effects of season and hydroperiod on mercury in wild and caged mosquitofish at three pairs of marshes. Nine monthly collections of wild mosquitofish were analyzed. Hydroperiod-within-site significantly affected concentrations but it interacted with sampling period. To control for wild-fish dispersal, and to measure in situ uptake and growth, I placed captive-reared, neonate mosquitofish with mercury levels from 7–14 ng g−1 ww into field cages in the six study marshes in six trials. Uptake rates ranged from 0.25–3.61 ng g−1 ww d −1. As with the wild fish, hydroperiod-within-site was a significant main effect that also interacted with sampling period. Survival exceeded 80%. Growth varied with season and hydroperiod, with greatest growth in short-hydroperiod marshes. The results suggest that dietary bioaccumulation determined mercury levels in Everglades aquatic animals, and that, although hydroperiod affected mercury uptake, its effect varied with season. ^

The effects of a family-based educational intervention on the prevention of lead poisoning in children

The effects of lead exposure may endure through one's lifetime and can negatively effect educational performance. While the link between the cause and effects of lead poisoning has been identified, the application of lead health education as the mechanism of disease prevention has not. The purpose of this study was to examine whether caregiver participation in a family-based educational intervention can result in decreased lead exposure in low socioeconomic children. ^ Participants (n = 50) were caregivers of children 12 to 36 months of age. They were randomly selected from an urban clinic and randomly assigned to either a treatment or control group. The experimental design of this study involved two clinic visits. Parents in the treatment group were given the educational intervention during the first clinic visit while those in the control group were given the intervention during the second clinic visit. The intervention was reinforced with a lead education brochure coupled with a video on childhood lead poisoning. One instrument was used to test parental knowledge of lead poisoning both pre- and post-intervention. Blood lead levels in pediatric participants were tested using two blood lead screens approximately three to four months apart determined by well-child check-up schedules. ^ Findings from the analysis of variance showed the interaction between the change in blood lead level between the children's first and second clinic visits and the treatment level. This demonstrated a significant interaction between the differences of first and second clinic visits blood lead levels and the presence or absence of the educational intervention. ^ The findings from an analysis of covariance support that caregivers in the treatment group have significantly higher scores on the second clinic visit scores on the CLKT than the caregivers in the control group. These data suggest that the educational treatment is effective in increasing the knowledge of caregivers about the dangers of lead poisoning and the strategies for lead poisoning prevention. ^ Conclusions indicate that the education of adult caregivers can affect blood lead levels of children, the educational treatment increased the knowledge of caregivers, caregivers were able to carry out procedures taught, and caregivers retained knowledge over time. ^

Human impacts on pig frog (Rana grylio) populations in south Florida wetlands: Harvest, water management and mercury contamination

This study investigated how harvest and water management affected the ecology of the Pig Frog, Rana grylio. It also examined how mercury levels in leg muscle tissue vary spatially across the Everglades. Rana grylio is an intermediate link in the Everglades food web. Although common, this inconspicuous species can be affected by three forms of anthropogenic disturbance: harvest, water management and mercury contamination. This frog is harvested both commercially and recreationally for its legs, is aquatic and thus may be susceptible to water management practices, and can transfer mercury throughout the Everglades food web. ^ This two-year study took place in three major regions: Everglades National Park (ENP), Water Conservation Areas 3A (A), and Water Conservation Area 3B (B). The study categorized the three sites by their relative harvest level and hydroperiod. During the spring of 2001, areas of the Everglades dried completely. On a regional and local scale Pig Frog abundance was highest in Site A, the longest hydroperiod, heavily harvested site, followed by ENP and B. More frogs were found along survey transects and in capture-recapture plots before the dry-down than after the dry-down in Sites ENP and B. Individual growth patterns were similar across all sites, suggesting differences in body size may be due to selective harvest. Frogs from Site A, the flooded and harvested site, had no differences in survival rates between adults and juveniles. Site B populations shifted from a juvenile to adult dominated population after the dry-down. Dry-downs appeared to affect survival rates more than harvest. ^ Total mercury in frog leg tissue was highest in protected areas of Everglades National Park with a maximum concentration of 2.3 mg/kg wet mass where harvesting is prohibited. Similar spatial patterns in mercury levels were found among pig frogs and other wildlife throughout parts of the Everglades. Pig Frogs may be transferring substantial levels of mercury to other wildlife species in ENP. ^ In summary, although it was found that abundance and survival were reduced by dry-down, lack of adult size classes in Site A, suggest harvest also plays a role in regulating population structure. ^