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Silver nanoparticles (AgNPs) are widely used in a variety of industrial and consumer applications and the disposal AgNP-containing materials is a potential source of environmental contamination. This study investigated the reaction of AgNPs with synthetic birnessite (δ-MnO2), a naturally-occurring MnO2 soil mineral shown in previous studies to oxidize both organic and inorganic dissolved species. The AgNPs used in this study ranged in size from 5 to 25 nm with an average particle diameter of 15.6 nm. Batch and kinetic reactions of MnO2-treated AgNP suspensions were studied by detecting AgNP oxidation to Ag+ using a combination of UV-Vis and microwave plasma atomic emission (MP-AES) spectrometries. Synchrotron K-edge X-ray absorption spectroscopy (XANES and EXAFS) was used to investigate the Ag oxidation state and structural characteristics of the reaction products. Oxidation of AgNP by MnO2 was detected in batch reactions showing an initial fast oxidation of AgNP to Ag+ (0–10 min) followed by a slower reaction (> 10 min) where Ag+ was removed by adsorption on MnO2 surfaces. XANES results confirmed that total AgNP oxidation by MnO2 occurred after 48 h when the Mn:Ag mole ratio treatment exceeded 5:1. The final AgNP oxidation product determined by EXAFS was Ag+ ion bound as a AgO4 tetrahedral structure in MnO2 interlayer cation exchange sites with Ag-O and Ag-Mn inter-atomic distances of 2.28 (± 0.02) and 3.88 (± 0.09) A, respectively. This structure is in agreement with previous EXAFS studies of naturally-occurring Ag-bearing MnO2 mineral samples and represents one of many possible Ag+ binding sites on soil mineral surfaces.

Fuente TESIUNAM

We calculate Berry's phase when the driving field, to which a spin-1/2 is coupled adiabatically, rather than the familiar classical magnetic field, is a quantum vector operator, of noncommuting, in general, components, e.g., the angular momentum of another particle, or another spin. The geometric phase of the entire system, spin plus "quantum driving field", is first computed, and is then subdivided into the two subsystems, using the Schmidt decomposition of the total wave function -the resulting expression shows a marked, purely quantum effect, involving the commutator of the field components. We also compute the corresponding mean "classical" phase, involving a precessing magnetic field in the presence of noise, up to terms quadratic in the noise amplitude -the results are shown to be in excellent agreement with numerical simulations in the literature. Subtleties in the relation between the quantum and classical case are pointed out, while three concrete examples illustrate the scope and internal consistency of our treatment., Comment: 19 pages. Matches published version. PACS. 03.65.Vf, 03.65.-w

Drilling underbalanced is often expected to prevent formation damage, avoid lost circulation, and increase rate of penetration. However, it is also risky and may lead to borehole collapse due to lack of positive support provided by the borehole mud. Hence, its feasibility should be evaluated thoroughly through an accurate evaluation of in-situ stresses and a realistic estimation of formation rock mechanical properties. These two entities combined with the proposed borehole trajectory and mud weight design play an important role in avoiding borehole instability problems and achieving the field objectives. A study was conducted in San Joaquin field in Eastern Venezuela, to evaluate the feasibility of drilling underbalanced in highly depleted sands inter-layered with normally pressured shales. Data required for the study was obtained from five wells in the field (pressures, daily drilling reports, wireline logs, leak off tests and rock mechanical tests). A geo-stress model was developed, including pore pressure model, minimum and maximum horizontal stresses, and overburden stress. The in-situ horizontal stress directions were estimated from caliper logs, image logs and other field data. Formation rock mechanical properties were obtained using a program which utilizes the log data from the field and estimates the more representative static mechanical properties, which were then calibrated with the lab results. The combined geo-stress and mechanical properties models were calibrated with respect to drilling induced fractures and breakouts observed on the image logs. The calibrated models were used to estimate the required mud weights for drilling under various degrees of underbalance. Instabilities (breakouts) associated with each degree of underbalance were also quantified. The required mud weights to avoid shear and tensile failures, or the expected breakouts for a given mud weight, can be estimated from the generated contour plots for any borehole azimuth and inclination in the field. The results of the study were successfully implemented in the field, resulting in cost benefits of $1MM over five wells. Lost circulation was significantly avoided, and improvements in drilling rate as well as savings in rig days were achieved. The outcome of the study is expected to provide guidelines for underbalanced drilling for future wells in the area.