Development of measurement and modeling techniques to quantify atmospheric deposition of persistent, bioaccumulative and toxic chemicals in the Great Lakes

Measurement and modeling techniques were developed to improve over-water gaseous air-water exchange measurements for persistent bioaccumulative and toxic chemicals (PBTs). Analytical methods were applied to atmospheric measurements of hexachlorobenzene (HCB), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs). Additionally, the sampling and analytical methods are well suited to study semivolatile organic compounds (SOCs) in air with applications related to secondary organic aerosol formation, urban, and indoor air quality. A novel gas-phase cleanup method is described for use with thermal desorption methods for analysis of atmospheric SOCs using multicapillary denuders. The cleanup selectively removed hydrogen-bonding chemicals from samples, including much of the background matrix of oxidized organic compounds in ambient air, and thereby improved precision and method detection limits for nonpolar analytes. A model is presented that predicts gas collection efficiency and particle collection artifact for SOCs in multicapillary denuders using polydimethylsiloxane (PDMS) sorbent. An approach is presented to estimate the equilibrium PDMS-gas partition coefficient (Kpdms) from an Abraham solvation parameter model for any SOC. A high flow rate (300 L min-1) multicapillary denuder was designed for measurement of trace atmospheric SOCs. Overall method precision and detection limits were determined using field duplicates and compared to the conventional high-volume sampler method. The high-flow denuder is an alternative to high-volume or passive samplers when separation of gas and particle-associated SOCs upstream of a filter and short sample collection time are advantageous. A Lagrangian internal boundary layer transport exchange (IBLTE) Model is described. The model predicts the near-surface variation in several quantities with fetch in coastal, offshore flow: 1) modification in potential temperature and gas mixing ratio, 2) surface fluxes of sensible heat, water vapor, and trace gases using the NOAA COARE Bulk Algorithm and Gas Transfer Model, 3) vertical gradients in potential temperature and mixing ratio. The model was applied to interpret micrometeorological measurements of air-water exchange flux of HCB and several PCB congeners in Lake Superior. The IBLTE Model can be applied to any scalar, including water vapor, carbon dioxide, dimethyl sulfide, and other scalar quantities of interest with respect to hydrology, climate, and ecosystem science.

Paléoécologie d’une tourbière à pergélisol en dégradation du sud des Territoires du Nord-Ouest : implications pour le cycle du carbone

Les tourbières ont contribué à refroidir le climat terrestre pendant l’Holocène en accumulant un réservoir de carbone important. Dans la forêt boréale canadienne, les sols gelés en permanence (pergélisols) sont répandus et ceux-ci sont principalement localisés dans les tourbières où ils forment des plateaux surélevés. Le dégel du pergélisol, causé entre autres par le réchauffement atmosphérique ou d’autres perturbations, provoque l’effondrement des plateaux et la saturation en eau du sol ce qui modifie entre autres le couvert végétal et le cycle du carbone. Les modélisations suggèrent que les latitudes nordiques seront les plus affectées par le réchauffement climatique alors qu’on y observe déjà un recul du couvert du pergélisol. Il est primordial de comprendre comment le dégel du pergélisol affecte la fonction de puits de carbone des tourbières puisque des rétroactions sur le climat sont possibles si une grande quantité de gaz à effet de serre est émise ou séquestrée. J’utilise une chronoséquence représentant le temps depuis le dégel d’un plateau de pergélisol des Territoires du Nord-Ouest pour comprendre les facteurs influençant l’aggradation et la dégradation du pergélisol dans les tourbières et évaluer l’effet du dégel sur l’accumulation de carbone et la préservation du carbone déjà accumulé. Les taux d’accumulation de carbone associés à la présence de pergélisol dans le passé et au présent sont lents, et la tourbe est moins décomposée dans les secteurs ayant été affectés plus longtemps par le pergélisol. En somme, le pergélisol réduit l’accumulation de carbone en surface mais permet une meilleure préservation du carbone déjà accumulé.

Contribution to the diffuse radiation modelling in Évora, Portugal

Solar radiation data is crucial for the design of energy systems based on the solar resource. Since diffuse radiation measurements are not always available in the archive data series, either due to the inexistence of measuring equipment, shading device misplacement or missing data, models to generate these data are needed. In this work, one year of hourly and daily horizontal solar global and diffuse irradiation measurements in Évora are used to establish a new relation between the diffuse radiation and the clearness index. The proposed model includes a fitting parameter, which was adjusted through a simple optimization procedure to minimize the Least Square Error as compared to measurements. A comparison against several other fitting models presented in the literature was also carried out using the Root Mean Square Error as statistical indicator, and it was found that the present model is more accurate than the previous fitting models for the diffuse radiation data in Évora.

The influence of particles recycling on the geochemistry of sediments in a large tropical dam lake in the Amazonian region, Brazil

The influence of particles recycling on the geochemistry of sediments in a large tropical dam lake in the Amazonian region, Brazil. Article in Journal of South American Earth Sciences 72 · December 2016 DOI: 10.1016/j.jsames.2016.09.012 1st Rita Fonseca 16.85 · Universidade de Évora 2nd Catarina Pinho 3rd Manuela Oliveira 22.6 · Universidade de Évora Abstract As a result of over-erosion of soils, the fine particles, which contain the majority of nutrients, are easily washed away from soils, which become deficient in a host of components, accumulating in lakes. On one hand, the accumulation of nutrients-rich sediments are a problem, as they affect the quality of the overlying water and decrease the water storage capacity of the system; on the other hand, sediments may constitute an important resource, as they are often extremely rich in organic and inorganic nutrients in readily available forms. In the framework of an extensive work on the use of rock related materials to enhance the fertility of impoverish soils, this study aimed to evaluate the role on the nutrients cycle, of particles recycling processes from the watershed to the bottom of a large dam reservoir, at a wet tropical region under high weathering conditions. The study focus on the mineralogical transformations that clay particles undergo from the soils of the drainage basin to their final deposition within the reservoir and their influence in terms of the geochemical characteristics of sediments. We studied the bottom sediments that accumulate in two distinct seasonal periods in Tucuruí reservoir, located in the Amazonian Basin, Brazil, and soils from its drainage basin. The surface layers of sediments in twenty sampling points with variable depths, are representative of the different morphological sections of the reservoir. Nineteen soil samples, representing the main soil classes, were collected near the margins of the reservoir. Sediments and soils were subjected to the same array of physical, mineralogical and geochemical analyses: (1) texture, (2) characterization and semi-quantification of the clay fraction mineralogy and (3) geochemical analysis of the total concentration of major elements, organic compounds (organic C and nitrogen), soluble fractions of nutrients (P and K), exchangeable fractions (cation exchange capacity, exchangeable bases and acidity) and pH(H2O).

Peripherally η1-Platinated Organometallic Porphyrins as Building Blocks for Multiporphyrin Arrays

The modification of peripherally metalated meso-η1-platiniometalloporphyrins, such as trans-[PtBr(NiDAPP)(PPh3)2] (H2DAPP = 5-phenyl-10,20-bis(3‘,5‘-di-tert-butylphenyl)porphyrin), leads to the analogous platinum(II) nitrato and triflato electrophiles in almost quantitative yields. Self-assembly reactions of these meso-platinioporphyrin tectons with pyridine, 4,4‘-bipyridine, or various meso-4-pyridylporphyrins in chloroform generate new multicomponent organometallic porphyrin arrays containing up to five porphyrin units. These new types of supramolecular arrays are formed exclusively in high yields and are stable in solution or in the solid state for extended periods. They were characterized by multinuclear NMR and UV−visible spectroscopy as well as high-resolution electrospray ionization mass spectrometry.

Brucite Microbialites in Living Coral Skeletons: Indicators of Extreme Microenvironments in Shallow-Marine Settings

Brucite [Mg(OH)2] microbialites occur in vacated interseptal spaces of living scleractinian coral colonies (Acropora, Pocillopora, Porites) from subtidal and intertidal settings in the Great Barrier Reef, Australia, and subtidal Montastraea from the Florida Keys, United States. Brucite encrusts microbial filaments of endobionts (i.e., fungi, green algae, cyanobacteria) growing under organic biofilms; the brucite distribution is patchy both within interseptal spaces and within coralla. Although brucite is undersaturated in seawater, its precipitation was apparently induced in the corals by lowered pCO2 and increased pH within microenvironments protected by microbial biofilms. The occurrence of brucite in shallow-marine settings highlights the importance of microenvironments in the formation and early diagenesis of marine carbonates. Significantly, the brucite precipitates discovered in microenvironments in these corals show that early diagenetic products do not necessarily reflect ambient seawater chemistry. Errors in environmental interpretation may arise where unidentified precipitates occur in microenvironments in skeletal carbonates that are subsequently utilized as geochemical seawater proxies.

Sexual selection in a tropical fruit fly : role of a plant derived chemical in mate choice

The specific mechanisms by which selective pressures affect individuals are often difficult to resolve. In tephritid fruit flies, males respond strongly and positively to certain plant derived chemicals. Sexual selection by female choice has been hypothesized as the mechanism driving this behaviour in certain species, as females preferentially mate with males that have fed on these chemicals. This hypothesis is, to date, based on studies of only very few species and its generality is largely untested. We tested the hypothesis on different spatial scales (small cage and seminatural field-cage) using the monophagous fruit fly, Bactrocera cacuminata. This species is known to respond to methyl eugenol (ME), a chemical found in many plant species and one upon which previous studies have focused. Contrary to expectation, no obvious female choice was apparent in selecting ME-fed males over unfed males as measured by the number of matings achieved over time, copulation duration, or time of copulation initiation. However, the number of matings achieved by ME-fed males was significantly greater than unfed males 16 and 32 days after exposure to ME in small cages (but not in a field-cage). This delayed advantage suggests that ME may not influence the pheromone system of B. cacuminata but may have other consequences, acting on some other fitness consequence (e.g., enhancement of physiology or survival) of male exposure to these chemicals. We discuss the ecological and evolutionary implications of our findings to explore alternate hypotheses to explain the patterns of response of dacine fruit flies to specific plant-derived chemicals.

A three species model to simulate application of hyperbaric oxygen therapy to chronic wounds

Chronic wounds are a significant socioeconomic problem for governments worldwide. Approximately 15% of people who suffer from diabetes will experience a lower-limb ulcer at some stage of their lives, and 24% of these wounds will ultimately result in amputation of the lower limb. Hyperbaric Oxygen Therapy (HBOT) has been shown to aid the healing of chronic wounds; however, the causal reasons for the improved healing remain unclear and hence current HBOT protocols remain empirical. Here we develop a three-species mathematical model of wound healing that is used to simulate the application of hyperbaric oxygen therapy in the treatment of wounds. Based on our modelling, we predict that intermittent HBOT will assist chronic wound healing while normobaric oxygen is ineffective in treating such wounds. Furthermore, treatment should continue until healing is complete, and HBOT will not stimulate healing under all circumstances, leading us to conclude that finding the right protocol for an individual patient is crucial if HBOT is to be effective. We provide constraints that depend on the model parameters for the range of HBOT protocols that will stimulate healing. More specifically, we predict that patients with a poor arterial supply of oxygen, high consumption of oxygen by the wound tissue, chronically hypoxic wounds, and/or a dysfunctional endothelial cell response to oxygen are at risk of nonresponsiveness to HBOT. The work of this paper can, in some way, highlight which patients are most likely to respond well to HBOT (for example, those with a good arterial supply), and thus has the potential to assist in improving both the success rate and hence the costeffectiveness of this therapy.