Metabolism of profenofos to 4-bromo-2-chlorophenol, a specific and sensitive exposure biomarker.

Profenofos is a direct acting phosphorothioate organophosphorus (OP) pesticide capable of inhibiting β-esterases such as acetylcholinesterase, butyrylcholinesterase, and carboxylesterase. Profenofos is known to be detoxified to the biologically inactive metabolite, 4-bromo-2-chlorophenol (BCP); however, limited data are available regarding the use of urinary BCP as an exposure biomarker in humans. A pilot study conducted in Egyptian agriculture workers, demonstrated that urinary BCP levels prior to application (3.3-30.0 μg/g creatinine) were elevated to 34.5-3,566 μg/g creatinine during the time workers were applying profenofos to cotton fields. Subsequently, the in vitro enzymatic formation of BCP was examined using pooled human liver microsomes and recombinant human cytochrome P-450s (CYPs) incubated with profenofos. Of the nine human CYPs studied, only CYPs 3A4, 2B6, and 2C19 were able to metabolize profenofos to BCP. Kinetic studies indicated that CYP 2C19 has the lowest Km, 0.516 μM followed by 2B6 (Km=1.02 μM) and 3A4 (Km=18.9μM). The Vmax for BCP formation was 47.9, 25.1, and 19.2 nmol/min/nmol CYP for CYP2B6, 2C19, and 3A4, respectively. Intrinsic clearance (Vmax/Km) values of 48.8, 46.9, and 1.02 ml/min/nmol CYP 2C19, 2B6, and 3A4, respectively, indicate that CYP2C19 and CYP2B6 are primarily responsible for the detoxification of profenofos. These findings support the use of urinary BCP as a biomarker of exposure to profenofos in humans and suggest polymorphisms in CYP 2C19 and CYP 2B6 as potential biomarkers of susceptibility

Leelanau County Inland Lakes Project

Master of ScienceLandscape ArchitectureUniversity of Michiganhttp://deepblue.lib.umich.edu/bitstream/2027.42/114606/2/39015043175614.pd

Distributions of Pigments and Primary Production in a Gulf-Stream Meander

An investigation was made of physical effects of Gulf Stream meandering on the vertical and horizontal distributions of photosynthetic pigments and primary production. Cruises were conducted in the vicinity of a meander east of 73-degrees-W and north of 37-degrees-N from September 21 to October 5 (leg 1) and October 12-21, 1988 (leg 2), on the R/V Cape Hatteras. Relationships of photosynthesis (normalized to chlorophyll) to irradiance (P-1) did not show large horizontal variation, and water column composite P-I curves from leg 1 and leg 2 were similar. Therefore a single P-I curve derived from pooled data was used to model distributions of primary production. Distributions of photosynthetic pigments were characterized on the basis of in vivo fluorescence profiles and empirical relationships with extracted pigment concentrations. Subsurface irradiance was described using a spectral irradiance model. Cross sections of the Gulf Stream revealed consistently higher pigment concentrations and primary production on the slope water side. Along-stream variations in pigment distributions and primary production were apparently related to density structure influenced by meander circulation. Such variations were less pronounced during leg 2. which came after a transition from a well-defined meander interacting with a warm-core ring (leg 1) to a more linear stream (leg 2). Higher water-column-integrated primary production during leg 2 was attributed to mixing-induced nutrient injection and redistribution of chlorophyll in the photic zone

Radiative Energy Budget Studies Using Observations from the Earth Radiation Budget Experiment (ERBE)

Our research activities under this NASA grant have focused on two broad topics associated with the Earth Radiation Budget Experiment (ERBE): (1) the role of clouds and the surface in modifying the radiative balance; and (2) the spatial and temporal variability of the earth's radiation budget. Each of these broad topics is discussed separately in the text that follows. The major points of the thesis are summarized in section 3 of this report. Other dissertation focuses on deriving the radiation budget over the TOGA COARE region

Capacitive Sensing of Intercalated H2O Molecules Using Graphene

Understanding the interactions of ambient molecules with graphene and adjacent dielectrics is of fundamental importance for a range of graphene-based devices, particularly sensors, where such interactions could influence the operation of the device. It is well-known that water can be trapped underneath graphene and its host substrate, however, the electrical effect of water beneath graphene and the dynamics of how it changes with different ambient conditions has not been quantified. Here, using a metal-oxide-graphene variable-capacitor (varactor) structure, we show that graphene can be used to capacitively sense the intercalation of water between graphene and HfO2 and that this process is reversible on a fast time scale. Atomic force microscopy is used to confirm the intercalation and quantify the displacement of graphene as a function of humidity. Density functional theory simulations are used to quantify the displacement of graphene induced by intercalated water and also explain the observed Dirac point shifts as being due to the combined effect of water and oxygen on the carrier concentration in the graphene. Finally, molecular dynamics simulations indicate that a likely mechanism for the intercalation involves adsorption and lateral diffusion of water molecules beneath the graphene.Comment: E.J.O. and R.M. made an equal contribution to this wor

Mechanisms of deformation-induced trace element migration in zircon resolved by atom probe and correlative microscopy

The widespread use of zircon in geochemical and geochronological studies of crustal rocks is underpinned by an understanding of the processes that may modify its composition. Deformation during tectonic and impact related strain is known to modify zircon trace element compositions, but the mechanisms by which this occurs remain unresolved. Here we combine electron backscatter diffraction, transmission Kikuchi diffraction and atom probe microscopy to investigate trace element migration associated with a ~20 nm wide, 2° low-angle subgrain boundary formed in zircon during a single, high-strain rate, deformation associated with a bolide impact. The low-angle boundary shows elevated concentrations of both substitutional (Y) and interstitial (Al, Mg and Be) ions. The observed compositional variations reflect a dynamic process associated with the recovery of shock-induced vacancies and dislocations into lower energy low-angle boundaries. Y segregation is linked to the migration and localisation of oxygen vacancies, whilst the interstitial ions migrate in association with dislocations. These data represent the direct nanoscale observation of geologically-instantaneous, trace element migration associated with crystal plasticity of zircon and provide a framework for further understanding mass transfer processes in zircon