Identification of metabolites and thermal transformation products of quinolones in raw cow milk by liquid chromatography coupled to high resolution mass spectrometry.

The presence of residues of antibiotics, metabolites, and thermal transformation products (TPs), produced during thermal treatment to eliminate pathogenic microorganisms in milk, could represent a risk for people. Cow"s milk samples spiked with enrofloxacin (ENR), ciprofloxacin (CIP), difloxacin (DIF), and sarafloxacin (SAR) and milk samples from cows medicated with ENR were submitted to several thermal treatments. The milk samples were analyzed by liquid chromatography-mass spectrometry (LC-MS) to find and identify TPs and metabolites. In this work, 27 TPs of 4 quinolones and 24 metabolites of ENR were found. Some of these compounds had been reported previously, but others were characterized for the first time, including lactose-conjugated CIP, the formamidation reaction for CIP and SAR, and hydroxylation or ketone formation to produce three different isomers for all quinolones studied.

Capillary thermal desorption unit for near real-time analysis of VOCs at sub-trace levels. Application to the analysis of environmental air contamination and breath samples

A capillary microtrap thermal desorption module is developed for near real-time analysis of volatile organic compounds (VOCs) at sub-ppbv levels in air samples. The device allows the direct injection of the thermally desorbed VOCs into a chromatographic column. It does not use a second cryotrap to focalize the adsorbed compounds before entering the separation column so reducing the formation of artifacts. The connection of the microtrap to a GC–MS allows the quantitative determination of VOCs in less than 40 min with detection limits of between 5 and 10 pptv (25 °C and 760 mmHg), which correspond to 19–43 ng m−3, using sampling volumes of 775 cm3. The microtrap is applied to the analysis of environmental air contamination in different laboratories of our faculty. The results obtained indicate that most volatile compounds are easily diffused through the air and that they also may contaminate the surrounding areas when the habitual safety precautions (e.g., working under fume hoods) are used during the manipulation of solvents. The application of the microtrap to the analysis of VOCs in breath samples suggest that 2,5-dimethylfuran may be a strong indicator of a person's smoking status

Ultra-trace monitoring of copper in environmental and biological samples by inductively coupled plasma atomic emission spectrometry after separation and preconcentration by using octadecyl silica membrane disks modified by a new schiff's base

Ultra-trace amounts of Cu(II) were separated and preconcentrated by solid phase extraction on octadecyl-bonded silica membrane disks modified with a new Schiff,s base (Bis- (2-Hydroxyacetophenone) -2,2-dimethyl-1,3-propanediimine) (SBTD) followed by elution and inductively coupled plasma atomic emission spectrometric detection. The method was applied as a separation and detection method for copper(II) in environmental and biological samples. Extraction efficiency and the influence of sample matrix, flow rate, pH, and type and minimum amount of stripping acid were investigated. The concentration factor and detection limit of the proposed method are 500 and 12.5 pg mL-1, respectively.

Flow analysis by using solenoid valves for As(III) determination in natural waters by an on-line separation and pre-concentration system coupled to a tungsten coil atomizer

A flow system coupled to a tungsten coil atomizer in an atomic absorption spectrometer (TCA-AAS) was developed for As(III) determination in waters, by extraction with sodium diethyldithiocarbamate (NaDDTC) as complexing agent, and by sorption of the As(III)-DDTC complex in a micro-column filled with 5 mg C18 reversed phase (10 µL dry sorbent), followed by elution with ethanol. A complete pre-concentration/elution cycle took 208 s, with 30 s sample load time (1.7 mL) and 4 s elution time (71 µL). The interface and software for the synchronous control of two peristaltic pumps (RUN/ STOP), an autosampler arm, seven solenoid valves, one injection valve, the electrothermal atomizer and the spectrometer Read function were constructed. The system was characterized and validated by analytical recovery studies performed both in synthetic solutions and in natural waters. Using a 30 s pre-concentration period, the working curve was linear between 0.25 and 6.0 µg L-1 (r = 0.9976), the retention efficiency was 94±1% (6.0 µg L-1), and the pre-concentration coefficient was 28.9. The characteristic mass was 58 pg, the mean repeatability (expressed as the variation coefficient) was 3.4% (n=5), the detection limit was 0.058 µg L-1 (4.1 pg in 71 µL of eluate injected into the coil), and the mean analytical recovery in natural waters was 92.6 ± 9.5 % (n=15). The procedure is simple, economic, less prone to sample loss and contamination and the useful lifetime of the micro-column was between 200-300 pre-concentration cycles.

Case-Crossover Analysis of Air Pollution Health Effects: A Systematic Review of Methodology and Application

Case-crossover is one of the most used designs for analyzing the health-related effects of air pollution. Nevertheless, no one has reviewed its application and methodology in this context. Objective: We conducted a systematic review of case-crossover (CCO) designs used to study the relationship between air pollution and morbidity and mortality, from the standpoint of methodology and application.Data sources and extraction: A search was made of the MEDLINE and EMBASE databases.Reports were classified as methodologic or applied. From the latter, the following information was extracted: author, study location, year, type of population (general or patients), dependent variable(s), independent variable(s), type of CCO design, and whether effect modification was analyzed for variables at the individual level. Data synthesis: The review covered 105 reports that fulfilled the inclusion criteria. Of these, 24 addressed methodological aspects, and the remainder involved the design’s application. In the methodological reports, the designs that yielded the best results in simulation were symmetric bidirectional CCO and time-stratified CCO. Furthermore, we observed an increase across time in the use of certain CCO designs, mainly symmetric bidirectional and time-stratified CCO. The dependent variables most frequently analyzed were those relating to hospital morbidity; the pollutants most often studied were those linked to particulate matter. Among the CCO-application reports, 13.6% studied effect modification for variables at the individual level.Conclusions: The use of CCO designs has undergone considerable growth; the most widely used designs were those that yielded better results in simulation studies: symmetric bidirectional and time-stratified CCO. However, the advantages of CCO as a method of analysis of variables at the individual level are put to little use

Association between Long-Term Exposure to Traffic-Related Air Pollution and Subclinical Atherosclerosis: The REGICOR Study

Background: Epidemiological evidence of the effects of long-term exposure to air pollu tion on the chronic processes of athero genesis is limited. Objective: We investigated the association of long-term exposure to traffic-related air pollu tion with subclinical atherosclerosis, measured by carotid intima media thickness (IMT) and ankle–brachial index (ABI). Methods: We performed a cross-sectional analysis using data collected during the reexamination (2007–2010) of 2,780 participants in the REGICOR (Registre Gironí del Cor: the Gerona Heart Register) study, a population-based prospective cohort in Girona, Spain. Long-term exposure across residences was calculated as the last 10 years’ time-weighted average of residential nitrogen dioxide (NO2) estimates (based on a local-scale land-use regression model), traffic intensity in the nearest street, and traffic intensity in a 100 m buffer. Associations with IMT and ABI were estimated using linear regression and multinomial logistic regression, respectively, controlling for sex, age, smoking status, education, marital status, and several other potential confounders or intermediates. Results: Exposure contrasts between the 5th and 95th percentiles for NO2 (25 μg/m), traffic intensity in the nearest street (15,000 vehicles/day), and traffic load within 100 m (7,200,000 vehicle-m/day) were associated with differences of 0.56% (95% CI: –1.5, 2.6%), 2.32% (95% CI: 0.48, 4.17%), and 1.91% (95% CI: –0.24, 4.06) percent difference in IMT, respectively. Exposures were positively associated with an ABI of > 1.3, but not an ABI of < 0.9. Stronger associations were observed among those with a high level of education and in men ≥ 60 years of age. Conclusions: Long-term traffic-related exposures were associated with subclinical markers of atherosclerosis. Prospective studies are needed to confirm associations and further examine differences among population subgroups.key words: ankle–brachial index, average daily traffic, cardiovascular disease, exposure assessment, exposure to tailpipe emissions, intima media thickness, land use regression model, Mediterranean diet, nitrogen dioxide

A novel method for fast enrichment and monitoring of hexavalent and trivalent chromium at the ppt level with modified silica MCM-41 and its determination by inductively coupled plasma optical emission spectrometry

Chromium(III) at the ng L-1 level was extracted using partially silylated MCM-41 modified by a tetraazamacrocyclic compound (TAMC) and determined by inductively coupled plasma optical emision spectrometry (ICP OES). The extraction time and efficiency, pH and flow rate, type and minimum amount of stripping acid, and break- through volume were investigated. The method's enrichment factor and detection limit are 300 and 45.5 pg mL-1, respectively. The maximum capacity of the 10 mg of modified silylated MCM-41 was found to be 400.5±4.7 µg for Cr(III). The method was applied to the determination of Cr(III) and Cr(VI) in the wastewater of the chromium electroplating industry and in environmental and biological samples (black tea, hot and black pepper).

Hybrid LC Filter for Power Electronic Drives: Theory and Implementation

Power electronic converter drives use, for the sake of high efficiency, pulse-width modulation that results in sequences of high-voltage high-frequency steep-edged pulses. Such a signal contains a set of high harmonics not required for control purposes. Harmonics cause reflections in the cable between the motor and the inverter leading to faster winding insulation ageing. Bearing failures and problems with electromagnetic compatibility may also result. Electrical du/dt filters provide an effective solution to problems caused by pulse-width modulation, thereby increasing the performance and service life of the electrical machines. It is shown that RLC filters effectively decrease the reflection phenomena in the cable. Improved (simple, but effective) solutions are found for both differential- and common-mode signals; these solutions use a galvanic connection between the RLC filter star point and the converter DC link. Foil chokes and film capacitors are among the most widely used components in high-power applications. In actual applications they can be placed in different parts of the cabinet. This fact complicates the arrangement of the cabinet and decreases the reliability of the system. In addition, the inductances of connection wires may prevent filtration at high frequencies. This thesis introduces a new hybrid LC filter that uses a natural capacitance between the turns of the foil choke based on integration of an auxiliary layer into it. The main idea of the hybrid LC filter results from the fact that both the foil choke and the film capacitors have the same roll structure. Moreover, the capacitance between the turns (“intra capacitance”) of the foil inductors is the reason for the deterioration of their properties at high frequencies. It is shown that the proposed filter has a natural cancellation of the intra capacitance. A hybrid LC filter may contain two or more foil layers isolated from each other and coiled on a core. The core material can be iron or even air as in the filter considered in this work. One of the foils, called the main foil, can be placed between the inverter and the motor cable. Other ones, called auxiliary foils, may be connected in star to create differential-mode noise paths, and then coupled to the DC link midpoint to guarantee a traveling path, especially for the common-mode currents. This way, there is a remarkable capacitance between the main foil and the auxiliary foil. Investigations showed that such a system can be described by a simple equivalent LC filter in a wide range of frequencies. Because of its simple hybrid construction, the proposed LC filter can be a cost-effective and competitive solution for modern power drives. In the thesis, the application field of the proposed filter is considered and determined. The basics of hybrid LC filter design are developed further. High-frequency behaviour of the proposed filter is analysed by simulations. Finally, the thesis presents experimental data proving that the hybrid LC filter can be used for du/dt of PWM pulses and reduction of common-mode currents.

Study of a vapor-compression air-conditioning system for jetliners

Most modern passenger aeroplanes use air cycle cooling. A high-speed air cycle is a reliable and light option, but not very efficient. This thesis presents research work done to design a novel vapour cooling cycle for aeroplanes. Due to advancements in high-speed permanent magnet motors, the vapour cycle is seen as a competitive option for the air cycle in aeroplanes. The aerospace industry places tighter demands on the weight, reliability and environmental effects of the machinery than those met by conventional chillers, and thus modifications to conventional design are needed. The thesis is divided into four parts: the initial screening of the working fluid, 1-D design and performance values of the compressor, 1-D off-design value predictions of the compressor and the 3-D design of the compressor. The R245fa was selected as the working fluid based the study. The off-design range of the compressor was predicted to be wide and suitable for the application. The air-conditioning system developed is considerably smaller than previous designs using centrifugal compressors.

Consumer valuation of energy-saving features of residential air conditioners with hedonic and choice models

The promotion of energy-efficient appliances is necessary to reduce the energetic and environmental burden of the household sector. However, many studies have reported that a typical consumer underestimates the benefits of energy-saving investment on the purchase of household electric appliances. To analyze this energy-efficiency gap problem, many scholars have estimated implicit discount rates that consumers use for energy-consuming durables. Although both hedonic and choice models have been used in previous studies, a comparison between two models has not yet been done. This study uses point of sale data about Japanese residential air conditioners and estimates implicit discounts rates with both hedonic and choice models. Both models demonstrate that a typical consumer underinvests in energy efficiency. Although choice models estimate a lower implicit discount rate than hedonic models, the latter models estimate the values of other product characteristics more consistently than choice models.

Assessment of air quality in Viana do Castelo, Portugal, in the scope of the polis programme

The present paper constitutes a synthesis of the results gotten during the five campaigns of air quality measurement in the years of 2003 and 2004 carried out in the Portuguese city of Viana do Castelo to characterise the reference situation and to accompany the Polis Programme, an urban re-qualification and environmental valorisation plan. The main objective of the monitoring programme consisted of the evaluation of atmospheric pollutants whose levels were susceptible of enhancement in the course of the urbanistic public works. The presented results refer to measurements performed in two distinct places of this city, comprising various consecutive days of acquisition that include, at least, one day of weekend.

Determination of etoricoxib in human plasma using automated on-line solid-phase extraction coupled with LC-APCI/MS/MS

A liquid chromatography-tandem mass spectrometry method with atmospheric pressure chemical ionization (LC-APCI/MS/MS) was validated for the determination of etoricoxib in human plasma using antipyrin as internal standard, followed by on-line solid-phase extraction. The method was performed on a Luna C18 column and the mobile phase consisted of acetonitrile:water (95:5, v/v)/ammonium acetate (pH 4.0; 10 mM), run at a flow rate of 0.6 mL/min. The method was linear in the range of 1-5000 ng/mL (r²>0.99). The lower limit of quantitation was 1 ng/mL. The recoveries were within 93.72-96.18%. Moreover, method validation demonstrated acceptable results for the precision, accuracy and stability studies.

Photometric procedure for quantitative analysis of Aflatoxin B1 in peanuts by thin-layer chromatography using charge coupled device detector

A photometric procedure was developed for determination of aflatoxin B1 in peanuts by TLC-CCD technique. The quantification and detection limit were 1.2 μg kg-1 and 0.4 ng per spot, respectively, with mean recovery of 98%. The CCD camera is sufficiently sensitive to detect small changes in spots fluorescence intensity and the results for performance confirmed the efficiency of the method. Another important property of CCD detector is its linearity for a wide range of luminous stimulus determined by analysis of five-point calibration curves using the intensity of AFB1 fluorescence versus AFB1 concentration (0.8 to 4.8 ng per spot). The method was applied to the analysis of thirty nine peanut samples and aflatoxin B1 levels ranged from 16 to 115 μg kg-1. The TLC-CCD and the photometric procedure developed in this study demonstrated to be a simple and efficient tool for quantitative analyses of AFB1 in peanut samples.

Air pollution and emergency admissions for cardiorespiratory diseases in Lisbon (Portugal)

Daily records of hospital admissions due to cardiorespiratory diseases and levels of PM10, SO2, CO, NO, NO2, and O3 were collected from 1999-2004 to evaluate the relationship between air pollution and morbidity in Lisbon. Generalised additive Poisson regression models were adopted, controlling for temperature, humidity, and both short and long-term seasonality. Significant positive associations, lagged by 1 or 2 days, were found between markers of traffic-related pollution (CO and NO2) and cardiocirculatory diseases in all age groups. Increased childhood emergency admissions for respiratory illness were significantly correlated with the 1-day lagged SO2 levels coming from industrial activities.