Analysis of mercury species present during coal combustion by thermal desorption

Mercury in coal and its emissions from coal-fired boilers is a topic of primary environmental concern in the United States and Europe. The predominant forms of mercury in coal-fired flue gas are elemental (Hg⁰) and oxidized (Hg²⁺, primarily as HgCl₂). Because Hg²⁺ is more condensable and far more water soluble than Hg⁰, the wide variability in mercury speciation in coal-fired flue gases undermines the total mercury removal efficiency of most mercury emission control technologies. It is important therefore to have an understanding of the behaviour of mercury during coal combustion and the mechanisms of mercury oxidation along the flue gas path. In this study, a temperature programmed decomposition technique was applied in order to acquire an understanding of the mode of decomposition of mercury species during coal combustion. A series of mercury model compounds were used for qualitative calibration. The temperature appearance range of the main mercury species can be arranged in increasing order as HgCl₂ < HgS < HgO < HgSO₄. Different fly ashes with certified and reference values for mercury concentration were used to evaluate the method. This study has shown that the thermal decomposition test is a newly developed efficient method for identifying and quantifying mercury species from coal combustion products.     

Quantifying phthalate metabolites in human meconium and semen using automated off-line solid-phase extraction coupled with on-line SPE and isotope-dilution high-performance liquid chromatography--tandem mass spectrometry

We developed an analytical method using off-line solid-phase extraction (SPE) coupled with on-line SPE and isotope-dilution high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) to determine the concentrations of phthalate metabolites in human meconium and in semen. First, we used off-line SPE to remove interfering proteins and other biomolecules from the samples. Then, we preconcentrated the phthalate metabolites in the extract using on-line SPE before measuring them by HPLC-MS/MS. For most of the analytes, the limits of detection ranged between 0.2 and 0.7 ng/g for meconium and between 0.3 and 0.7 ng/mL for semen. The recovery after off-line SPE varied for most analytes between 65 and 99% at concentrations ranging from 3.0 to 30.0 ng/mL in semen and between 67 and 103% at concentrations ranging from 2.0 to 10.0 ng/mL in meconium. Precision measured by the relative standard deviation ranged from 3.2 to 19.1% for intraday and from 3.9 to 18.6% for interday. We validated this novel approach--which is applicable to other biological matrixes, including serum and breast milk--on spiked samples and on five meconium samples and one pooled semen sample from people with no known occupational exposure to phthalates.     

Ductile PLA nanocomposites with improved thermal stability

Polylactide (PLA) is used as a biomedical material because it is biodegradable, but the vast majority of biodegradable polymers in clinical use are composed of rather stiff materials that are unsuitable for use in numerous applications because they exhibit limited extendibility, weak mechanical strength, and poor thermal stability. We modified PLA with 2-methacryloyloxyethyl isocyanate (MOI) to prepare ductile PLA materials. By utilizing a novel sol–gel process, PLA nanocomposites were further prepared with improved mechanical properties and thermal stability. The 10% thermal decomposition temperature for PLA modified with 5% MOI and 5–10% silica was 21–32 °C higher than that of original pristine PLA. Elongation at break increased by 4–13 times when compared to neat PLA while the tensile strength was maintained at 30–40 MPa. These synthesized PLA nanocomposites can be applied as biomaterials with improved mechanical and thermal properties.     

Alcohol expectancies regarding sex, aggression, and sexual vulnerability: Reliability and validity assessment.

This study was designed to validate the Alcohol Expectancies Regarding Sex, Aggression, and Sexual Vulnerability Questionnaire. This instrument includes alcohol expectancies in 4 domains (aggression, sexual affect, sexual drive, and vulnerability to sexual coercion) for 3 targets (self, women, and men). Confirmatory factor analyses with 715 undergraduates supported the hypothesized factor structure for the entire sample, as well as for gender and ethnic subgroups. Each of the subscales had high internal consistency reliability, moderate test-retest reliability, and good discriminant validity. Multivariate analyses of variance supported the hypothesis that participants' alcohol expectancies for other people conformed to gender role stereotypes. Participants saw themselves as being less influenced by alcohol than were others. Implications for sexual assault prevention programs are discussed. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Mercury content in Chilean fish and estimated intake levels.

The intake of fish products is a major public health concern due to possible methyl mercury exposure, which is especially toxic to the human nervous system. This pilot study (n = 46) was designed to determine mercury concentrations in fish products for national consumption (Chilean jack mackerel, hake, Chilean mussel, tuna) and for export (salmon, Patagonian toothfish, swordfish, southern hake), and to estimate the exposure of the general population. The fish products were collected from markets in Talcahuano, Puerto Montt and Santiago. Samples were analyzed at the National Environmental Center by cold vapor atomic absorption spectrophotometry. Mercury levels in swordfish and one canned tuna sample exceeded levels prescribed by national and international standards. The remaining two export products (Patagonian toothfish, also known as Chilean sea bass, and salmon) complied with international limits, which are more demanding than Chilean regulations. Theoretical estimates of mercury intake varied from 0.08 to 3.8 microg kg(-1) bw day(-1) for high fish consumers, exceeding the provisional tolerable intake for tuna, Chilean seabass, Chilean jack mackerel and swordfish. This group appears to be at the greatest risk from mercury contamination among the Chilean population.     

Silicon etch with chromium ions generated by a filtered or non-filtered cathodic arc discharge

The pre-treatment of substrate surfaces prior to deposition is important for the adhesion of physical vapour deposition coatings. This work investigates Si surfaces after the bombardment by energetic Cr ions which are created in cathodic arc discharges. The effect of the pre-treatment is analysed by X-ray diffraction, Rutherford backscattering spectroscopy, scanning electron microscopy and in-depth X-ray photoemission spectroscopy and compared for Cr vapour produced from a filtered and non-filtered cathodic arc discharge. Cr coverage as a function of ion energy was also predicted by TRIDYN Monte Carlo calculations. Discrepancies between measured and simulated values in the transition regime between layer growth and surface removal can be explained by the chemical reactions between Cr ions and the Si substrate or between the substrate surface and the residual gases. Simulations help to find optimum and more stable parameters for specific film and substrate combinations faster than trial-and-error procedure.     

Freeze drying optimization of polymeric nanoparticles for ocular flurbiprofen delivery: effect of protectant agents and critical process parameters on long-term stability

Context: The stabilization of flurbiprofen loaded poly-?-caprolactone nanoparticles (FB-P?CL-NPs) for ocular delivery under accurate freeze-drying (FD) process provides the basis for a large-scale production and its commercial development.

Objective: Optimization of the FD to improve long-term stability of ocular administration’s FB-P?CL-NPs.

Methods: FB-P?CL-NPs were prepared by solvent displacement method with poloxamer 188 (P188) as stabilizer. Freezing and primary drying (PD) were studied and optimized through freeze-thawing test and FD microscopy. Design of experiments was used to accurate secondary drying (SD) conditions and components concentration. Formulations were selected according to desired physicochemical properties. Furthermore, differential scanning calorimetry (DSC) and X-ray diffraction (XRD) were used to study interactions components.

Results: Optimized FB-P?CL-NPs, stabilized with 3.5% (w/w) P188 and protected with 8% (w/w) poly(ethylene glycol), was submitted to precooling at +10?°C for 1?h, freezing at ?50?°C for 4?h, PD at +5?°C and 0.140 mbar for 24?h and a SD at +45?°C during 10?h. These conditions showed 188.4?±?1.3?nm, 0.087?±?0.014, 85.5?±?1.4%, 0.61?±?0.12%, ?16.4?±?0.1?mV and 325?±?7 mOsm/kg of average size, polydispersity index, entrapment efficiency, residual moisture, surface charge and osmolality, respectively. It performed a long-term stability >12 months. DSC and XRD spectra confirmed adequate chemical interaction between formulation components and showed a semi-crystalline state after FD.

Conclusions: An optimal freeze dried ocular formulation was achieved. Evidently, the successful design of this promising colloidal system resulted from rational cooperation between a good formulation and the right conditions in the FD process.     

Flexible estimation of wage distributions in the presence of covariates

An estimator of conditional wage distributions based on a piecewise-linear specification of the conditional hazard function is proposed. Under a minimal set of assumptions, the estimator is flexible enough to capture almost any underlying relationship, and is not affected by the curse of dimensionality. It also allows us to derive estimates of the conditional Lorenz curves and Gini indices. The methodology is used to investigate the wage trends in Spain in 1994-1999. The estimation results provide evidence that there has been strong decreases in both the returns to schooling and the inequality indices for workers with low levels of experience; these decreases may partly be explained by the “overeducation” phenomenon, which intensified in this period.