Susanna Insogna

Sensitive profiling of biogenic amines in human urine by capillary electrophoresis with field amplified sample injection.

In order to monitor biogenic amines in human urine, a method based on field-amplified sample injection combined with capillary electrophoresis and direct UV absorption detection was developed. Dopamine, tyramine, tryptamine, serotonin and epinephrine were effectively separated and identified in human urine samples, and detection limits were 0.072, 0.010, 0.027, 0.010 and 0.120 µmol/L, respectively. Detection limits comparable to laser-induced fluorescence detection or solid phase extraction combined with capillary electrophoresis were achieved. Parameters affecting electrophoretic system detection sensitivity were investigated. Optimal separation conditions were obtained using as background electrolyte a pH 6.5 mixture of 2-(morpholino)ethanesulfonic acid 20 mmol/L and 30 mmol/L phosphate buffer, containing 0.05% hydroxypropylcellulose and 10% v/v methanol. Injections of the sample solution were performed by applying a voltage of 12 kV for 50 s. Recovery and accuracy ranged between 89.4 and 94.9%, and 89 and 112%, respectively. The method was successfully applied on actual urine samples (from a healthy volunteer): target bioamine content was consistent with endogenous levels reported in the literature. The proposed method is simple, fast and inexpensive and can be conveniently employed in work-related stress studies. The affordability and noninvasive sampling of the method allow epidemiological studies on large number of exposed persons to be performed.

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.

Remote Zones Air Quality. Persistent Organic Pollutants: Sources, Sampling and Analysis

Concern about air quality has been rising since the Industrial Revolution and the so-called “Second Industrial Revolution” characterized by internal combustion engine, electrical technology and above all synthesis of new chemicals. Since then humankind has been facing the consequences of its thoughtless release of pollutants in atmosphere, consequences as reducing smog, acid rains and photochemical smog. Notwithstanding the seriousness of single episodes, these were local, or at most regional, phenomena. Nowadays, the variety of pollutants and the extent of pollution are greater than even in history, and air pollution problems are reaching up to global scale. In the last decades, it was established that manmade chemicals, such as polychlorinated biphenyls, chlorofluorocarbons and volatile chlorinated hydrocarbons, were present even in the remotest zones of the Earth, according to their volatility and half-life. This evidence stimulated the scientific community to monitor air quality of remote zones, areas considered a short time ago as uncontaminated. This chapter deals with different sampling and analysis techniques for persistent organic pollutants (POPs) in the atmosphere of remote zones. Features, sources and environmental fate of POPs are presented in the first section. The second section focuses on logistic and experimental difficulties connected to surveys in remote zones. The third section focuses on recent developments and improvements concerning sampling and analytical methods for POPs in air. The most significant findings on the presence of POPs in remote zones are shown in the last section.

Indoor Air Quality. Volatile Organic Compounds: Sources, Sampling and Analysis

Since the 70s, research has found in Europe and in the United States that individuals spend between 70 and 90% of their time indoors. Health studies have found that exposures to a variety of air pollutants indoors can be substantially higher than outdoors, even in urban environment. Volatile Organic Compounds (VOCs) are often considered among the more important indoor pollutants, because of by their continue emission from many sources and their diffusion properties. With the aim to evaluate the occupants’ discomfort and health effects and in order to develop guidelines and standards, Indoor Air Quality (IAQ) assessment and control is an essential step. IAQ assessment will complain: • Sources: Identification and characterization of sources, as emissions from materials, products or activities, is best done under laboratory conditions; so it is possible measuring rates of emissions (especially chemicals such as VOCs). Exposure characterization is the second level of source identification; after the measurement of contaminants’ concentrations in controlled environment, characterised by known sources, adsorbing and absorbing surfaces, these data can be used in validation of current exposure models. • Sampling methods: In order to determine concentrations of VOCs and exposures of building occupants via inhalation, field studies can be carried out by sampling methods (and analysis) in accordance with existing official methods (EC, NIOSH, OSHA, ACGIH, etc.). This way may be expensive and cumbersome; in addition, it can be not exhaustive in predicting the discomfort and health impact. A greater number of perspectives are offered by using some “descriptors” that can be more adequate in characterizing anthropogenic pollution. Specific sampling methods may be reserved for contaminants with specific toxic effects (e.g., formaldehyde, benzene, monomers, etc.). Measurements of specific contaminants’ can be necessary for sources that cause high room concentrations for relatively short periods (e.g., in case of freshly applied coatings on walls, etc.). Currently, diffusion (passive) samplers are mainly used in order to evaluate long term exposures (days to weeks and more) • Analysis and data meaning: existing analytical methods are validated and generally show adequate limits of detection (LODs) and limits of quantification (LOQs) even in measuring subtoxic contaminants’ concentrations. Analytical methods for the more

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.

Trends of volatile chlorinated hydrocarbons and trihalomethanes in Antarctica

In order to understand behaviour and environmental fate of manmade chemicals in remote and cold areas, during the XXVII Italian Expedition carried out in Antarctica throughout the austral summer 2011/2012, superficial snow and lake water were sampled along the Ross Seas South coast and their content of some low-molecular weight volatile halogenated hydrocarbons was evaluated. In consideration of their important role in stratospheric ozone chemistry, some volatile chlorinated hydrocarbons (VCHCs) and trihalomethanes (THMs) were investigated. The analyses were realised with a dedicated system composed by a purge-and-trap injector coupled to a gas chromatograph with a mass spectrometer (PTI-GC-MS) operating in SIM mode. The investigated VCHCs (chloroform; 1,1,1-trichloroethane; tetrachloromethane; trichloroethylene and tetrachloroethylene) were present in all analysed samples, and concentration levels ranged from units to hundreds of ng L−1 according to considered matrix. For the first time, THMs (bromoform; dibromochloromethane; bromodichloromethane), were measured in Antarctic lake waters and freshly deposited snow; their concentration levels ranged from units to tens of ng L−1. In order to assess eventual temporal variations, VCHC content in aqueous Antarctic matrices was compared with levels occurring in the past Italian Antarctic expeditions: for some banned substances, a decrease in concentration was observed, probably due to worldwide use restrictions. Finally, current Antarctic and Italian VCHC and THM levels in snow and lake water samples were compared and were found to be quite similar, differing at most by one order of magnitude, corroborating the hypothesis of an accumulation of halogenated compounds in Antarctic aqueous matrices.