Respiratory parameters at varied altitudes in intermittent mining work.

OBJECTIVES: Workers in the mining industry in altitude are subjected to several risk factors, e.g., airborne silica and low barometric pressure. The aim of this study has been to assess the risks for this work category, evaluating single risk factors as airborne silica, altitude and work shift, and relating them with cardiovascular and ventilatory parameters. MATERIAL AND METHODS: Healthy miners employed in a mining company, Chile, working at varied altitudes, and subjected to unusual work shifts, were evaluated. Cardiovascular and respiratory parameters were investigated. Exposure to airborne silica was evaluated and compared to currently binding exposure limits. RESULTS: At varied altitudes and work shifts, alterations emerged in haemoglobin, ventilation and respiratory parameters, related to employment duration, due to compensatory mechanisms for hypoxia. Haemoglobin increased with altitude, saturation fell down under 90% in the highest mines. The multiple linear regression analysis showed a direct relationship, in the higher mine, between years of exposure to altitude and increased forced vital capacity percent (FVC%), and forced expiratory volume in 1 s (FEV1). An inverse relationship emerged between forced vital capacity (FVC) and years of exposure to airborne silica. In the workplace Mina Subterrànea (MT-3600), statistically significant inverse relationship emerged between the Tiffeneau index and body weight. CONCLUSIONS: The working conditions in the mining industry in altitude appeared to be potentially pathogenic; further investigations should be realized integrating risk assessment protocols even in consideration of their undeniable unconventionality. Int J Occup Med Environ Health 2018;31(2):129-138.

Bridging spatially segregated redox zones with a microbial electrochemical snorkel triggers biogeochemical cycles in oil-contaminated River Tyne (UK) sediments.

Marine sediments represent an important sink for a number of anthropogenic organic contaminants, including petroleum hydrocarbons following an accidental oil spill. Degradation of these compounds largely depends on the activity of sedimentary microbial communities linked to biogeochemical cycles, in which abundant elements such as iron and sulfur are shuttled between their oxidized and reduced forms. Here we show that introduction of a small electrically conductive graphite rod ("the electrochemical snorkel") into an oil-contaminated River Tyne (UK) sediment, so as to create an electrochemical connection between the anoxic contaminated sediment and the oxygenated overlying water, has a large impact on the rate of metabolic reactions taking place in the bulk sediment. The electrochemical snorkel accelerated sulfate reduction processes driven by organic contaminant oxidation and suppressed competitive methane-producing reactions. The application of a comprehensive suite of chemical, spectroscopic, biomolecular and thermodynamic analyses suggested that the snorkel served as a scavenger of toxic sulfide via a redox interaction with the iron cycle. Taken as a whole, the results of this work highlight a new strategy for controlling biological processes, such as bioremediation, through the manipulation of the electron flows in contaminated sediments.

Innovative analytical method for the determination of underivatized tributyltin and pentachlorophenol in seawater by gas chromatography-triple quadrupole mass spectrometry.

Tributyltin (TBT) and pentachlorophenol (PCP) are listed as priority substances that warrant monitoring in the European Water Framework Directive (WFD 2000/60/CE), since TBT and PCP were identified as environmental endocrine disruptors and exhibit considerable toxicity toward both aquatic organisms and mammals even at very low levels. This paper shows a novel approach to analyze underivatized tributyltin (TBT) and pentachlorophenol (PCP) in seawater based on capillary gas chromatography-triple quadrupole mass spectrometry. The optimized extraction method for TBT an PCP in water involved liquid-liquid microextraction with toluene. The reduced extract was added with a solvent mix, composed of methanol and trimethylsilyl derivatives of methanol (MeOTMS), that allowed good chromatographic resolution of underivatized TBT and PCP, interacting as a lubricant along the glass liner during the injection phase. The proposed method showed good linearity and repeatability (RSD%<20% at 0.05 ng L-1 for TBT and 0.2 µg L-1 for PCP). The overall recoveries were 74% and 106% for TBT and PCP, respectively. Very low quantification limits that met the strict statutory and regulatory demands were achieved: 0.002 ng L-1 for TBT and 0.050 µg L-1 for PCP.

On-line analysis of volatile chlorinated hydrocarbons in air by gas chromatography-mass spectrometry Improvements in preconcentration and injection steps.

An analytical system composed of a cryofocusing trap injector device coupled to a gas chromatograph with mass spectrometric detection (CTI-GC-MS) specific for the on-line analysis in air of volatile chlorinated hydrocarbons (VCHCs) (dichloromethane; chloroform; 1,1,1-trichloroethane; tetrachloromethane; 1,1,2-trichloroethylene; tetrachloroethylene) was developed. The cryofocusing trap injector was the result of appropriate low cost modifications to an original purge-and-trap device to make it suitable for direct air analysis even in the case of only slightly contaminated air samples, such as those from remote zones. The CTI device can rapidly and easily be rearranged into the purge-and-trap allowing water and air analysis with the same apparatus. Air samples, collected in stainless steel canisters, were introduced directly into the CTI-GC-MS system to realize cryo-concentration (at -120 degrees C), thermal desorption (at 200 degrees C) and for the subsequent analysis of volatiles. The operating phases and conditions were customised and optimized. Recovery efficiency was optimized in terms of moisture removal, cold trap temperature and sampling mass flow. The injection of entrapped volatiles was realized through a direct transfer with high chromatographic reliability (capillary column-capillary column). These improvements allowed obtaining limits of detection (LODs) at least one order of magnitude lower than current LODs for the investigated substances. The method was successfully employed on real samples: air from urban and rural areas and air from remote zones such as Antarctica.

Comparison of atmosphere/aquatic environment concentration ratio of volatile chlorinated hydrocarbons between temperate regions and Antarctica.

For the purpose of understanding the transport and deposition mechanisms and the air-water distribution of some volatile chlorinated hydrocarbons (VCHCs), their atmosphere/aquatic environment concentration ratio was evaluated. In addition, for the purpose of differentiating VCHC behaviour in a temperate climate from its behaviour in a polar climate, the atmosphere/aquatic environment concentration ratio evaluated in matrices from temperate zones was compared with the concentration ratio evaluated in Antarctic matrices. In order to perform air samplings also at rigid Antarctic temperatures, the sampling apparatus, consisting of a diaphragm pump and canisters, was suitably modified. Chloroform, 1,1,1-trichloroethane, tetrachloromethane, 1,1,2-trichloroethylene and tetrachloroethylene were measured in air, water and snow using specific techniques composed of a purpose-made cryofocusing-trap-injector (for air samples) and a modified purge-and-trap injector (for aqueous samples) coupled to a gas chromatograph with mass spectrometric detection operating in selected ion monitoring mode. The VCHCs were retrieved in all the investigated matrices, both Italian and Antarctic, with concentrations varying from tens to thousands of ng m(-3) in air and from digits to hundreds of ng kg(-1) in water and snow. The atmosphere/aquatic environment concentration ratios were always found to be lower than 1. In particular, the Italian air/water concentration ratios were smaller than the Antarctic ones, by reason of the higher atmospheric photochemical activity in temperate zones. On the other hand, the Antarctic air/snow concentration ratios proved to be largely in favour of snow with respect to the Italian ratios, thus corroborating the hypothesis of a more efficient VCHC deposition mechanism and accumulation on Antarctic snow.

Volatile chlorinated hydrocarbons in Antarctic superficial snow sampled during Italian ITASE expeditions.

In order to detect the presence of some volatile chlorinated hydrocarbons (VCHCs) and to understand their transport and deposition mechanism, superficial snow was sampled during two Italian ITASE (International Trans Antarctic Scientific Expedition) expeditions: the first traverse was carried out in 1998/1999 from Terra Nova Bay to Dome Concordia; the second traverse was carried out in 2001/2002 through Adélie, George V, Oates and Northern Victoria Lands. Some VCHCs (chloroform; 1,1,1-trichloroethane; tetrachloromethane; 1,1,2-trichloroethylene; tetrachloroethylene) were analysed using a highly sensitive and selective hyphenated technique composed of a purge-and-trap injector coupled to a gas chromatograph with a mass spectrometric detector (PTI-GC-MS) operating in SIM mode. Investigated VCHCs were present in all analysed snow samples with concentration levels of several units, tens, or sometimes hundreds of ng kg(-1). VCHC snow concentration levels remained approximately constant with changing distance from the coast and the comparison between fresh and aged snow did not show any substantial differences; on the basis of this evidence marine aerosol and dry deposition may be rejected as principal VCHC transport and deposition mechanism hypotheses. VCHC concentration levels in Antarctic snow samples were comparable to or greater than those found in snow from temperate zones.

Organocatalytic regioselective Michael additions of cyclic enones via asymmetric phase transfer catalysis.

Cyclohexanone and cycloheptanone can be enantioselectively functionalized in the 3-position with up to 92% ee and 87% ee, respectively, by the base-promoted dimerization of the corresponding enones using 3,4,5-tribenzyloxybenzyl cinchoninium bromide, as a new effective catalyst.

Improved analysis of volatile halogenated hydrocarbons in water by purge-and-trap with gas chromatography and mass spectrometric detection.

An analytical system composed of a purge-and-trap injection system coupled to gas chromatography with mass spectrometric detection (PTI-GC-MS) specific for the analysis of volatile chlorinated hydrocarbons (VCHCs) (chloroform; 1,1,1-trichloroethane; tetrachloromethane; 1,1,2-trichloroethylene; tetrachloroethylene) and trihalomethanes (THMs) (chloroform; bromodichloromethane; dibromochloromethane; bromoform) in water was optimised. Samples were purged and trapped in a cold trap (-100 degrees C) fed with liquid nitrogen (cryo-concentration). In order to make this method suitable also for only slightly contaminated waters, some modifications were made to PTI sample introduction, in order to avoid any air intake into the system. PTI, GC and MS conditions were optimised for halogenated compound analysis and limits of detection (LOD) were evaluated. The proposed method allows analysis of samples whose concentrations range from microg/L to ng/L. It is, therefore, applicable to drinking waters, in analyses required by law, and to slightly contaminated aqueous matrices, such as those found in remote areas, in environmental monitoring. Moreover, by changing cold trap temperature, even sparkling mineral waters can be analysed, thus avoiding CO2 interference during the cryo-concentration phase. Our method has been successfully used on real samples: tap water, mineral water and Antarctic snow.