Oxidative potential of particles in different occupational environments: a pilot study

The oxidative potential (OP) of particulate matter has been proposed as a toxicologically relevant metric. This concept is already frequently used for hazard characterization of ambient particles but it is still seldom applied in the occupational field. The objective of this study was to assess the OP in two different types of workplaces and to investigate the relationship between the OP and the physicochemical characteristics of the collected particles. At a toll station, at the entrance of a tunnel ('Tunnel' site), and at three different mechanical yards ('Depot' sites), we assessed particle mass (PM4 and PM2.5 and size distribution), number and surface area, organic and elemental carbon, polycyclic aromatic hydrocarbon (PAH), and four quinones as well as iron and copper concentration. The OP was determined directly on filters without extraction by using the dithiothreitol assay (DTT assay-OP(DTT)). The averaged mass concentration of respirable particles (PM4) at the Tunnel site was about twice the one at the Depot sites (173±103 and 90±36 µg m(-3), respectively), whereas the OP(DTT) was practically identical for all the sites (10.6±7.2 pmol DTT min(-1) μg(-1) at the Tunnel site; 10.4±4.6 pmol DTT min(-1) μg(-1) at the Depot sites). The OP(DTT) of PM4 was mostly present on the smallest PM2.5 fraction (OP(DTT) PM2.5: 10.2±8.1 pmol DTT min(-1) μg(-1); OP(DTT) PM4: 10.5±5.8 pmol DTT min(-1) μg(-1) for all sites), suggesting the presence of redox inactive components in the PM2.5-4 fraction. Although the reactivity was similar at the Tunnel and Depot sites irrespective of the metric chosen (OP(DTT) µg(-1) or OP(DTT) m(-3)), the chemicals associated with OP(DTT) were different between the two types of workplaces. The organic carbon, quinones, and/or metal content (Fe, Cu) were strongly associated with the DTT reactivity at the Tunnel site whereas only Fe and PAH were associated (positively and negatively, respectively) with this reactivity at the Depot sites. These results demonstrate the feasibility of measuring of the OP(DTT) in occupational environments and suggest that the particulate OP(DTT) is integrative of different physicochemical properties. This parameter could be a potentially useful exposure proxy for investigating particle exposure-related oxidative stress and its consequences. Further research is needed mostly to demonstrate the association of OP(DTT) with relevant oxidative endpoints in humans exposed to particles.

L'oxalate: un déchet organique peu soluble, avec conséquences [Oxalate: a poorly soluble organic waste with consequences].

Oxalate is a highly insoluble metabolic waste excreted by the kidneys. Disturbances of oxalate metabolism are encountered in enteric hyperoxaluria (secondary to malabsorption, gastric bypass or in case of insufficient Oxalobacter colonization), in hereditary hyperoxaluria and in intoxication (ethylene glycol, vitamin C). Hyperoxaluria causes a large spectrum of diseases, from isolated hyperoxaluria to kidney stones and nephrocalcinosis formation, eventually leading to kidney failure and systemic oxalosis with life-threatening deposits in vital organs. New causes of hyperoxaluria are arising recently, in particular after gastric bypass surgery, which requires regular and preemptive monitoring. The treatment of hyperoxaluria involves reduction in oxalate intake and increase in calcium intake. Optimal urine dilution and supplementation with inhibitors of kidney stone formation (citrate) are required. Some conditions may need vitamin B6 supplementation, and the addition of probiotics might be useful in the future. Primary care physicians should identify cases of recurrent calcium oxalate stones and severe hyperoxaluria. Further management of hyperoxaluria requires specialized care.

Fertilizing Methods and Nutrient Balance at the End of Traditional Organic Agriculture in the Mediterranean Bioregion: Catalonia (Spain) in the 1860s

By reconstructing the nutrient balance of a Catalan v illage circa 1861-65 we examine the sustainability of organic agricultural sy stems in the northwest Mediterranean bioregion prior to the green rev olution and the question of whether the nutrients extracted f rom the soil were replenished. With a population density of 59 inhabitants per square km, similar to other northern European rural areas at that time, and a lower liv estock density per cropland unit, this v illage experienced a manure shortage. The gap was f illed by other labour-intensiv e way s of transf erring nutrients f rom uncultiv ated areas into the cropland. Key elements in this agricultural sy stem were v iney ards because they hav e f ew nutrient requirements, and woodland and scrublands as sources of relev ant amounts of nutrients collected in sev eral ways.

A web-based tool to aid the identification of chemicals potentially posing a health risk through percutaneous exposure

Occupational hygiene practitioners typically assess the risk posed by occupational exposure by comparing exposure measurements to regulatory occupational exposure limits (OELs). In most jurisdictions, OELs are only available for exposure by the inhalation pathway. Skin notations are used to indicate substances for which dermal exposure may lead to health effects. However, these notations are either present or absent and provide no indication of acceptable levels of exposure. Furthermore, the methodology and framework for assigning skin notation differ widely across jurisdictions resulting in inconsistencies in the substances that carry notations. The UPERCUT tool was developed in response to these limitations. It helps occupational health stakeholders to assess the hazard associated with dermal exposure to chemicals. UPERCUT integrates dermal quantitative structure-activity relationships (QSARs) and toxicological data to provide users with a skin hazard index called the dermal hazard ratio (DHR) for the substance and scenario of interest. The DHR is the ratio between the estimated 'received' dose and the 'acceptable' dose. The 'received' dose is estimated using physico-chemical data and information on the exposure scenario provided by the user (body parts exposure and exposure duration), and the 'acceptable' dose is estimated using inhalation OELs and toxicological data. The uncertainty surrounding the DHR is estimated with Monte Carlo simulation. Additional information on the selected substances includes intrinsic skin permeation potential of the substance and the existence of skin notations. UPERCUT is the only available tool that estimates the absorbed dose and compares this to an acceptable dose. In the absence of dermal OELs it provides a systematic and simple approach for screening dermal exposure scenarios for 1686 substances.

Headspace needle-trap analysis of priority volatile organic compounds from aqueous samples: application to the analysis of natural and waste waters

Combining headspace (HS) sampling with a needle-trap device (NTD) to determine priority volatile organic compounds (VOCs) in water samples results in improved sensitivity and efficiency when compared to conventional static HS sampling. A 22 gauge stainless steel, 51-mm needle packed with Tenax TA and Carboxen 1000 particles is used as the NTD. Three different HS-NTD sampling methodologies are evaluated and all give limits of detection for the target VOCs in the ng L−1 range. Active (purge-and-trap) HS-NTD sampling is found to give the best sensitivity but requires exhaustive control of the sampling conditions. The use of the NTD to collect the headspace gas sample results in a combined adsorption/desorption mechanism. The testing of different temperatures for the HS thermostating reveals a greater desorption effect when the sample is allowed to diffuse, whether passively or actively, through the sorbent particles. The limits of detection obtained in the simplest sampling methodology, static HS-NTD (5 mL aqueous sample in 20 mL HS vials, thermostating at 50 °C for 30 min with agitation), are sufficiently low as to permit its application to the analysis of 18 priority VOCs in natural and waste waters. In all cases compounds were detected below regulated levels

LC-MS method development and comparison of sampling materials for the analysis of organic gunshot residues

This study aimed at comparing the efficiency of various sampling materials for the collection and subsequent analysis of organic gunshot residues (OGSR). To the best of our knowledge, it is the first time that sampling devices were investigated in detail for further quantitation of OGSR by LC-MS. Seven sampling materials, namely two "swab"-type and five "stub"-type collection materials, were tested. The investigation started with the development of a simple and robust LC-MS method able to separate and quantify molecules typically found in gunpowders, such as diphenylamine or ethylcentralite. The evaluation of sampling materials was then systematically carried out by first analysing blank extracts of the materials to check for potential interferences and determining matrix effects. Based on these results, the best four materials, namely cotton buds, polyester swabs, a tape from 3M and PTFE were compared in terms of collection efficiency during shooting experiments using a set of 9 mm Luger ammunition. It was found that the tape was capable of recovering the highest amounts of OGSR. As tape-lifting is the technique currently used in routine for inorganic GSR, OGSR analysis might be implemented without modifying IGSR sampling and analysis procedure.

Contribuições recentes da reação de hidroformilação na síntese de produtos farmacêuticos: parte II

The hydroformylation reaction represents one of the most important C1-chemistry area in the chemical industry. This catalytic process, which has been developed up to now mainly to the production of commodities chemicals, has shown a remarkable potential for the preparation of several categories of specialty chemicals and in particular pharmaceutical compounds. Arylpropanoic acids, various amines containing aryl groups, and intermediates for the preparation of vitamins, carbocyclic and heterocyclic compounds and many other classes of organic molecules endowed with pharmacological activity are currently accessible in good-to-high yields through hydroformylation of selected olefinic substrates. The asymmetric hydroformylation is going to reach the stage of maturity and hence to contribute in solving many troublesome synthetic problems connected with the preparation of pharmacologically active compounds with very high enantiomeric purity. The present survey emphasizes the usefulness of synthesis gas as a starting material in fine chemistry, which is expected to be important for industry.

High voltage discharge for degradation of organic contaminants in water

The pulsed dielectric barrier discharge (PDBD) and pulsed corona discharge (PCD) were compared for their efficiency to degrade phenol in water solution. Results show that PCD has higher efficiency than PDBD to degrade phenol. When initial pH of water solution was elevated, phenol degradation in the PCD reactor was significantly enhanced, although no considerable effect was seen in the PDBD reactor. The PCD reactor was also able to degrade lignin significantly, both in synthetically prepared solution and in pulp and paper mill wastewater. Water temperature did not affect phenol degradation; however, lignin was better oxidized at lower temperature.

Determinação de fósforo orgânico em águas de produção petrolífera por ICP- AES e ICP- MS após pré-concentração em coluna de sílica-C18

Results on the optimization of analytical methods for the determination of phosphorus in phosphino-polycarboxylate (PPCA), used frequently as scale inhibitor during oil production, by ICP-AES and ICP-MS are presented. Due to the complex matrix of production waters (brines) and their high concentration in inorganic phosphorus, the separation of organic phosphorus prior to its determination is necessary. In this work, minicolumns of silica immobilized C18 were used. Optimization of the separation step resulted in the following working conditions: (1) prewashing of the column with methanol (80% v/v); (2) use of a flow rate of 5 mL/min and 10 mL/min, respectively, for the preconditioning step and for percolation of the water sample; (3) final elution of organic phosphorus with 7 mL of buffer of H3BO3/NaOH (0.05 M, pH 9) with a flow rate of 1 mL/min. Sample detection limits (3s) for different combinations of nebulizers and spectrometric methods, based on 10 mL water aliquots, are: ICP-AES -Cross flow (47 mg/L) and Ultrasonic (18 mug/L); ICP-MS -Cross flow (1.2 mug/L), Cyclonic (0.7 mug/L) and Ultrasonic (0.5 mug/L). Typical recoveries of organic phosphorus are between 90 and 95% and the repeatability of the whole procedure is better than 10%. The developed methodology was applied successfully to samples from the oil-well NA 46, platform PNA 2, Campos basin, Brazil. Assessment of the PPCA inhibitor was possible at lower concentrations than achieved by current analytical methods, resulting in benefits such as reduced cost of chemicals, postponed oil production and lower environmental impacts.

One pot obtention of a tetrabutylammonium hydroxide solution for ironporphyrin-OH- interaction studies in organic solvents

In this work we report the obtention of a tetrabutylammonium hydroxide (TBAOH) solution in acetonitrile in a one pot process in order to study the interaction ironporphyrinOH- in non-aqueous systems. All the reactions were carried out under dry argon atmosphere to prevent the contamination of the solution with CO2, which leads to the formation of (TBA)2CO3.

Evaluation of potential breath biomarkers for active smoking: assessment of smoking habits

Different compounds have been reported as biomarkers of a smoking habit, but, to date, there is no appropriate biomarker for tobacco-related exposure because the proposed chemicals seem to be nonspecific or they are only appropriate for short-term exposure. Moreover, conventional sampling methodologies require an invasive method because blood or urine samples are required. The use of a microtrap system coupled to gas chromatography–mass spectrometry analysis has been found to be very effective for the noninvasive analysis of volatile organic compounds in breath samples. The levels of benzene, 2,5-dimethylfuran, toluene, o-xylene, and m- p-xylene have been analyzed in breath samples obtained from 204 volunteers (100 smokers, 104 nonsmokers; 147 females, 57 males; ages 16 to 53 years). 2,5-Dimethylfuran was always below the limit of detection (0.005 ppbv) in the nonsmoker population and always detected in smokers independently of the smoking habits. Benzene was only an effective biomarker for medium and heavy smokers, and its level was affected by smoking habits. Regarding the levels of xylenes and toluene, they were only different in heavy smokers and after short-term exposure. The results obtained suggest that 2,5-dimethylfuran is a specific breath biomarker of smoking status independently of the smoking habits (e.g., short- and long-term exposure, light and heavy consumption), and so this compound might be useful as a biomarker of smoking exposure

A Headspace needle-trap method for the analysis of volatile organic compounds in whole blood

Needle trap devices (NTDs) are a relatively new and promising tool for headspace (HS) analysis. In this study, a dynamic HS sampling procedure is evaluated for the determination of volatile organic compounds (VOCs) in whole blood samples. A full factorial design was used to evaluate the influence of the number of cycles and incubation time and it is demonstrated that the controlling factor in the process is the number of cycles. A mathematical model can be used to determine the most appropriate number of cycles required to adsorb a prefixed amount of VOCs present in the HS phase whenever quantitative adsorption is reached in each cycle. Matrix effect is of great importance when complex biological samples, such as blood, are analyzed. The evaluation of the salting out effect showed a significant improvement in the volatilization of VOCs to the HS in this type of matrices. Moreover, a 1:4 (blood:water) dilution is required to obtain quantitative recoveries of the target analytes when external calibration is used. The method developed gives detection limits in the 0.020–0.080 μg L−1 range (0.1–0.4 μg L−1 range for undiluted blood samples) with appropriate repeatability values (RSD < 15% at high level and <23% at LOQ level). Figure of merits of the method can be improved by using a smaller phase ratio (i.e., an increase in the blood volume and a decrease in the HS volume), which lead to lower detection limits, better repeatability values and greater sensibility. Twenty-eight blood samples have been evaluated with the proposed method and the results agree with those indicated in other studies. Benzene was the only target compound that gave significant differences between blood levels detected in volunteer non-smokers and smokers