Gotas suspensas: uma proposta para amostragem e análise de gases traços da atmosfera

In the present paper, we report on the analytical use of a dynamic droplet based gas collection and an analysis system. A droplet formed at the tip of a tube represents a sampling approach that provides an indefinitely renewable surface and uses very little reagent. Sample gas flows past the droplet at a low flow rate. After the gas was sampled , the analysis can be carried out by different methodologies. The feasibility of the sensor is demonstrated by continuos determination of gaseous as: NO2, Cl2 and SO2.

Gotas suspensas: uma proposta para amostragem e análise de gases traços da atmosfera

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Study on the use of oxidant scrubbers for elimination of interferences due to nitrogen dioxide in analysis of atmospheric dimethylsulfide

Neste trabalho foi avaliado o desempenho de filtros para dióxido de nitrogênio, buscando evitar perdas durante a amostragem de sulfetos orgânicos, provocadas por oxidantes atmosféricos. Diferentes compostos e misturas foram usadas para recobrir superfícies sólidas empregadas na preparação destes filtros. Um sistema automatizado de análise em fluxo foi utilizado para comparar a eficiência de retenção de dióxido de nitrogênio pelos filtros. Entre os materiais testados na preparação dos filtros, as melhores escolhas foram papel ou lã de vidro impregnados com a mistura de sulfato de ferro (II), ácido sulfúrico e ácido pirogalico e ainda os filtros feitos de papel impregnados com trietanolamina. Os resultados obtidos em laboratório com mistura de gás padrão de dimetilsulfeto e experimentos em campo confirmaram a qualidade dos filtros e indicaram que eles podem ser utilizados para evitar a oxidação de sulfetos orgânicos durante a sua amostragem.

Investigation of Postmortem Gases: A Forensic Imaging and Analytical Chemistry Approach

Background: Distinguishing postmortem gas accumulations in the body due to natural decomposition and other phenomena such as gas embolism can prove a difficult task using purely Multi-Detector Computed Tomography (MDCT). The Radiological Alteration Index (RAI) was created with the intention to be able to identify bodies undergoing the putrefaction process based on the quantity of gas detected within the body. The flaw in this approach is the inability to absolutely determine putrefaction as the origin of gas volumes in cases of moderate alteration. The aim of the current study is to identify percentage compositions of O2, N2, CO2 and the presence of gases such as H2 and H2S within these sampling sites in order to resolve this complication. Materials and methods: All cases investigated in our University Center of Legal Medicine are undergoing a Post-Mortem Computed Tomography (PMCT)-scan before external examination or autopsy as a routine investigation. In the obtained images, areas of gas were characterized as 0, I, II or III based on the amount of gas present according to the RAI (1). The criteria for these characterizations were dependent of the site of gas, for example thoracic and abdominal cavities were graded as I (1 - 3cm gas), II (3 - 5cm gas) and III (>5cm gas). Cases showing gaseous sites with grade II or III were selected for this study. The sampling was performed under CT-guidance to target the regions to be punctured. Luer-lock PTFE syringes equipped with a three-way valve and needles were used to sample the gas directly (2). Gaseous samples were then analysed using gas chromatography coupled to a thermal conductivity detector (GC-TCD). The components present in the samples were expressed as a percentage of the overall gas present. Results: Up to now, we have investigated more than 40 cases using our standardized procedure for sampling and analysis of gas. O2, N2 and CO2 were present in most samples. The following distributions were found to correlate to gas origins of gas embolism/scuba diving accidents, trauma and putrefaction: ? Putrefaction → O2 = 1 - 5%; CO2 > 15%; N2 = 10 - 70%; H2 / H2S / CH4 variable presence ? Gas embolism/Scuba diving accidents → O2 and N2= varying percentages; CO2 > 20% ? Trauma → O2 = small percentage; CO2 < 15%; N2 > 65% H2 and H2S indicated levels of putrefaction along with methane which can also gauge environmental conditions or conditions of body storage/burial. Many cases showing large RAI values (advanced alteration) did reveal a radiological diagnosis which was in concordance with the interpretation of the gas composition. However, in certain cases (gas embolism, scuba divers) radiological interpretation was not possible and only chemical gas analysis was found to lead to the correct diagnosis, meaning that it provided complementary information to the radiological diagnosis. Conclusion: Investigation of postmortem gases is a useful tool to determine origin of gas generation which can aid the diagnosis of the cause of death. Levels of gas can provide information on stage of putrefaction and help to perform essential medico-legal diagnosis such as vital gas embolism.

Estimating arterial blood gases with the EABC® System (“Earlobe Arterialized Blood Collector”) in critically ill patients. A validation study.

The Earlobe Arterialized Blood Collector® is a minimally invasive system able to perform arterialized capillary blood gas analysis from the earlobe (EL). A prospective validation study was performed in 55 critical ill patients. Sampling failure rate was high (53.6%). Risk factors were age > 65 years, diabetes, vasoactive drug therapy and noradrenaline (NA) doses above 0.22 μg / kg / min. Multivariate analysis showed age > 65 years was the only factor independently associated with failure. Concordance analysis with arterial blood gases and Bland-Altman agreement evaluation were insufficient for validating the new system for all gasometrical variables.

Characterizing sampling bias in the trace gas climatologies of the SPARC Data Initiative

Monthly zonal mean climatologies of atmospheric measurements from satellite instruments can have biases due to the nonuniform sampling of the atmosphere by the instruments. We characterize potential sampling biases in stratospheric trace gas climatologies of the Stratospheric Processes and Their Role in Climate (SPARC) Data Initiative using chemical fields from a chemistry climate model simulation and sampling patterns from 16 satellite-borne instruments. The exercise is performed for the long-lived stratospheric trace gases O3 and H2O. Monthly sampling biases for O3 exceed 10% for many instruments in the high-latitude stratosphere and in the upper troposphere/lower stratosphere, while annual mean sampling biases reach values of up to 20% in the same regions for some instruments. Sampling biases for H2O are generally smaller than for O3, although still notable in the upper troposphere/lower stratosphere and Southern Hemisphere high latitudes. The most important mechanism leading to monthly sampling bias is nonuniform temporal sampling, i.e., the fact that for many instruments, monthly means are produced from measurements which span less than the full month in question. Similarly, annual mean sampling biases are well explained by nonuniformity in the month-to-month sampling by different instruments. Nonuniform sampling in latitude and longitude are shown to also lead to nonnegligible sampling biases, which are most relevant for climatologies which are otherwise free of biases due to nonuniform temporal sampling.

Climatology and variability of trace gases in extratropical double-tropopause regions from MLS, HIRDLS, and ACE-FTS measurements

Upper tropospheric and lower stratospheric measurements from the Aura Microwave Limb Sounder (MLS), the Aura High Resolution Dynamics Limb Sounder (HIRDLS), and the Atmospheric Chemistry Experiment-Fourier transform spectrometer (ACE-FTS) are used to present the first global climatological comparison of extratropical, nonpolar trace gas distributions in double-tropopause (DT) and single-tropopause (ST) regions. Stratospheric tracers, O3, HNO3, and HCl, have lower mixing ratios ∼2–8 km above the primary (lowermost) tropopause in DT than in ST regions in all seasons, with maximum Northern Hemisphere (NH) differences near 50% in winter and 30% in summer. Southern Hemisphere winter differences are somewhat smaller, but summer differences are similar in the two hemispheres. H2O in DT regions of both hemispheres shows strong negative anomalies in November through February and positive anomalies in July through October, reflecting the strong seasonal cycle in H2O near the tropical tropopause. CO and other tropospheric tracers examined have higher DT than ST values 2–7 km above the primary tropopause, with the largest differences in winter. Large DT-ST differences extend to high NH latitudes in fall and winter, with longitudinal maxima in regions associated with enhanced wave activity and subtropical jet variations. Results for O3 and HNO3 agree closely between MLS and HIRDLS, and differences from ACE-FTS are consistent with its sparse and irregular midlatitude sampling. Consistent signatures in climatological trace gas fields provide strong evidence that transport from the tropical upper troposphere into the layer between double tropopauses is an important pathway for stratosphere-troposphere exchange.

Emissão de gases de efeito estufa e estoque de carbono no solo em função do manejo e correção de acidez

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Emissão de gases do efeito estufa e estoque de carbono no sistema solo-planta em área com aplicação superficial de calcário e gesso em experimento de longa duração

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Quantifying the OH radical by global scale NMHC measurements from the NOAA - ESRL cooperative flask sampling network

Summary PhD Thesis Jan Pollmann: This thesis focuses on global scale measurements of light reactive non-methane hydrocarbon (NMHC), in the volatility range from ethane to toluene with a special focus on ethane, propane, isobutane, butane, isopentane and pentane. Even though they only occur at the ppt level (nmol mol-1) in the remote troposphere these species can yield insight into key atmospheric processes. An analytical method was developed and subsequently evaluated to analyze NMHC from the NOAA – ERSL cooperative air sampling network. Potential analytical interferences through other atmospheric trace gases (water vapor and ozone) were carefully examined. The analytical parameters accuracy and precision were analyzed in detail. It was proven that more than 90% of the data points meet the Global Atmospheric Watch (GAW) data quality objective. Trace gas measurements from 28 measurement stations were used to derive the global atmospheric distribution profile for 4 NMHC (ethane, propane, isobutane, butane). A close comparison of the derived ethane data with previously published reports showed that northern hemispheric ethane background mixing ratio declined by approximately 30% since 1990. No such change was observed for southern hemispheric ethane. The NMHC data and trace gas data supplied by NOAA ESRL were used to estimate local diurnal averaged hydroxyl radical (OH) mixing ratios by variability analysis. Comparison of the variability derived OH with directly measured OH and modeled OH mixing ratios were found in good agreement outside the tropics. Tropical OH was on average two times higher than predicted by the model. Variability analysis was used to assess the effect of chlorine radicals on atmospheric oxidation chemistry. It was found that Cl is probably not of significant relevance on a global scale.

Continuous geochemical monitoring by mass-spectometer in the Campi Flegrei geothermal area. An application at Pisciarelli-Solfatara (diffuse and fumarolic gases) and at the mud gases during drilling of the CFDDP pilot hole

During this work has been developed an innovative methodology for continuous and in situ gas monitoring (24/24 h) of fumarolic and soil diffusive emissions applied to the geothermal and volcanic area of Pisciarelli near Agnano inside the Campi Flegrei caldera (CFc). In literature there are only scattered and in discrete data of the geochemical gas composition of fumarole at Campi Flegrei; it is only since the early ’80 that exist a systematic record of fumaroles with discrete sampling at Solfatara (Bocca Grande and Bocca Nuova fumaroles) and since 1999, even at the degassing areas of Pisciarelli. This type of sampling has resulted in a time series of geochemical analysis with discontinuous periods of time set (in average 2-3 measurements per month) completely inadequate for the purposes of Civil Defence in such high volcanic risk and densely populated areas. For this purpose, and to remedy this lack of data, during this study was introduced a new methodology of continuous and in situ sampling able to continuously detect data related and from its soil diffusive degassing. Due to its high sampling density (about one measurement per minute therefore producing 1440 data daily) and numerous species detected (CO2, Ar, 36Ar, CH4, He, H2S, N2, O2) allowing a good statistic record and the reconstruction of the gas composition evolution of the investigated area. This methodology is based on continuous sampling of fumaroles gases and soil degassing using an extraction line, which after undergoing a series of condensation processes of the water vapour content - better described hereinafter - is analyzed through using a quadrupole mass spectrometer

Pressure core barrel characteristics and composition of gases at DSDP Site 76-533

A pressure core barrel (PCB), developed by the Deep Sea Drilling Project, was used successfully to recover, at in situ pressure, sediments of the Blake Outer Ridge, offshore the southeastern United States. The PCB is a unique, wire-line tool, 10.4 m long, capable of recovering 5.8 m of core (5.8 cm in diameter), maintained at or below in situ pressures of 34.4 million Pascals (MPa), and 1.8 m of unpressurized core (5.8 cm in diameter). All excess internal pressure above the operating pressure of 34.4 MPa is automatically vented off as the barrel is retrieved. The PCB was deployed five times at DSDP Site 533 where geophysical evidence suggests the presence of gas hydrates in the upper 600 m of sediment. Three cores were obtained holding average in situ pressures of 30 MPa. Two other cores did not maintain in situ pressures. Three of the five cores were intermittently degassed at varying intervals of time, and portions of the vented gas were collected for analysis. Pressure decline followed paths indicative of gas hydrates and/or dissolved gas. The released gas was dominantly methane (usually greater than 90%), along with higher molecular-weight hydrocarbon gases and carbon dioxide. During degassing the ratio of methane to ethane did not vary significantly. On the other hand, concentrations of higher molecular-weight hydrocarbon gases increased, as did carbon dioxide concentrations. The results from the PCB experiments provide tentative but equivocal evidence for the presence of .gas hydrates at Site 533. The amount of gas hydrate indicated is small. Nevertheless, this work represents the first successful study of marine gas hydrates utilizing the PCB.