Hydrogen sulfide measurements in air by passive/diffusive samplers and high-frequency analyzer: A critical comparison

In this study, hydrogen sulfide (H₂S) measurements in air carried out using (a) passive/diffusive samplers (Radiello^® traps) and (b) a high-frequency (60 s) real-time analyzer (Thermo^® 450i) were compared in order to evaluate advantages and limitations of the two techniques. Four different sites in urban environments (Florence, Italy) and two volcanic areas characterized by intense degassing of H₂S-rich fluids (Campi Flegrei and Vulcano Island, Italy) were selected for such measurements. The concentrations of H₂S generally varied over 5 orders of magnitude (from 10⁻¹–10³ μg/m³), the H₂S values measured with the Radiello^® traps (H₂S_R) being significantly higher than the average values measured by the Thermo^® 450i during the trap exposure (H₂S_Ta), especially when H₂S was <30 μg/m³. To test the reproducibility of the Radiello^® traps, 8 passive/diffusive samplers were contemporaneously deployed within an 0.2 m² area in an H₂S-contaminated site at Mt. Amiata (Tuscany, Italy), revealing that the precision of the H₂S_R values was ±49%. This large uncertainty, whose cause was not recognizable, is to be added to that related to the environmental conditions (wind speed and direction, humidity, temperature), which are known to strongly affect passive measurements. The Thermo^® 450i analyzer measurements highlighted the occurrence of short-term temporal variations of the H₂S concentrations, with peak values (up to 5732 μg/m³) potentially harmful to the human health. The Radiello^® traps were not able to detect such temporal variability due to their large exposure time. The disagreement between the H₂S_R and H₂S_Ta values poses severe concerns for the selection of an appropriate methodological approach aimed to provide an accurate measurement of this highly toxic air pollutant in compliance with the WHO air quality guidelines. Although passive samplers may offer the opportunity to carry out low-cost preliminary surveys, the use of the high-frequency H₂S analyzer is preferred when an accurate assessment of air quality is required. In fact, the latter provides precise real-time measurements for a reliable estimation of the effective exposure to hazardous H₂S concentrations, giving insights into the mechanisms regulating the dispersion of this air pollutant in relation to the meteorological parameters.     

Isometamorphic variations in the reflectance and fluorescence of vitrinite—a key to depositional environment

Petrographic investigations of serial ply samples from five high- to medium-volatile bituminous coal seams from Australia (4) and Canada (1) reveal substantial in-seam variations in the reflectance and monochromatic microfluorescence intensities of the maceral subgroup telovitrinite. The variations consist of one case of reflectance enhancement and fluorescence suppression, and four cases of reflectance suppression and fluorescence enhancement. The single case of reflectance enhancement and fluorescence suppression is due to the oxidation of the vitrinite nuclei at the sequence boundary between the Bayswater and Upper Wynn seams in New South Wales. The four cases of reflectance suppression and fluorescence enhancement result from the syn- and epigenetic absorption by the vitrinite nuclei of hydrogen donated by, presumably, anaerobic bacteria-generated lipids. Two of the coals are marine-influenced: the Liskeard Seam from the Bowen Basin by combined syngenetic and epigenetic effects, and the Greta Seam from the Sydney Basin mainly by epigenetic contact with sea water. For both coals, the results are strong vitrinite reflectance suppression and fluorescence enhancement. The remaining two coals, the Bulli Seam from the Sydney Basin and a coal seam from the Gates Formation in British Columbia, show moderate epigenetic effects on the optical properties of telovitrinite by fresh-water. In the Bulli Seam which was studied in two adjacent localities, the reflectance suppression and fluorescence enhancement of telovitrinite are stronger under sandstone roof than under shale roof. In some cases, the epigenetic effects are superimposed on syngenetic telovitrinite reflectance and fluorescence variations resulting from the cogeneration and mixing of different telovitrinite precursors, for example, autochthonous roots and hypautochthonous or allochthonous shoots. A measure of the degree of dispersal and mixing is the coefficient of variation of telovitrinite reflectance and/or fluorescence. This coefficient correlates well with detrital minerals and dispersed macerals, e.g., inertodetrinite and, to a lesser extent, sporinite. Some comments are made on slitted so-called pseudovitrinite which is regarded as a telovitrinite that was subjected to very weak post-coalification desiccation and possibly oxidation without losing much of its thermoplastic properties.     

Intercomparison of measurements of stratospheric hydrogen fluoride

Observations of the vertical profile of hydrogen fluoride (HF) vapor in the stratosphere and of the vertical column amounts of HF above certain altitudes were made using a variety of spectroscopic instruments in the 1982 and 1983 Balloon Intercomparison Campaigns. Both emission instruments working in the far infrared spectral region and absorption instruments using solar occultation in the 2.5m region were employed. No systematic differences were seen in results from the two spectral regions. A mean profile from 20–45 km is presented, with uncertainties ranging from 20% to 50%. Total columns measured from ground and from 12 km are consistent with the profile if the mixing ratio for HF is small in the tropophere and low stratosphere.     

氢——预报地震的灵敏元素

1976年唐山7.8级地震之后,到1991年底,首都圈地区先后发生了宁河6.9级、大同6.1级等6次5级以上中强地震和一系列3.5级以上中小地震,每次中强地震和部分中小地震前后,北京地区水化监测井网均能监测到地下热水中氢气含量明显的异常上升变化,其幅度达正常背景值的几倍、十几倍、几十倍甚至更高,震后均逐渐恢复正常,这表明地下氢气是反应地下应力应变灵敏的地球化学组分,也是地震预报很有希望的前兆手段之一     

硫化氢临震突跳异常

分析研究十四年来距乌鲁木齐350km范围内发生的Ms≥4.0级地震资料,总结硫化氢临震突跳异常特征及异常型态类型,确定硫化氢临震突跳与地震的内在联系。认为硫化氢突跳性前兆是中强地震短临预报标志之一,它与地震三要素的对应关系,可作为发震时间的定性判据,根据映震效果推断硫化氢是地震前兆灵敏组份之一。本文试图从硫化氢水地球化学环境、氧化还原反应及微生物影响等方面对硫化氢临震突跳异常作粗浅解释。     

The first and second order moments of the polarization profiles of hydrogen lines

The main properties of the first- and second-order moments of polarized hydrogen lines, forming in the presence of stationary electric and magnetic fields, are reviewed. The analytical results presented here apply directly to the case of optically-thin emission lines in the LTE regime. Some applications of such results to electric- and magnetic-field diagnostics in (solar) plasmas are then briefly considered.On leave from the Dipartimento di Astronomia e Scienza dello Spazio, Università di Firenze, Largo E. Fermi 5, I-50125 Firenze, Italy     

Photoproduction of hydrogen peroxide in aqueous solution from model compounds for chromophoric dissolved organic matter (CDOM)

To explore whether quinone moieties are important in chromophoric dissolved organic matter (CDOM) photochemistry in natural waters, hydrogen peroxide (H₂O₂) production and associated optical property changes were measured in aqueous solutions irradiated with a Xenon lamp for CDOM model compounds (dihydroquinone, benzoquinone, anthraquinone, napthoquinone, ubiquinone, humic acid HA, fulvic acid FA). All compounds produced H₂O₂ with concentrations ranging from 15 to 500 μM. Production rates were higher for HA vs. FA (1.32 vs. 0.176 mM h⁻¹); values ranged from 6.99 to 0.137 mM h⁻¹ for quinones. Apparent quantum yields (Θ_app; measure of photochemical production efficiency) were higher for HA vs. FA (0.113 vs. 0.016) and ranged from 0.0018 to 0.083 for quinones. Dihydroquinone, the reduced form of benzoquinone, had a higher production rate and efficiency than its oxidized form. Post-irradiation, quinone compounds had absorption spectra similar to HA and FA and 3D-excitation–emission matrix fluorescence spectra (EEMs) with fluorescent peaks in regions associated with CDOM.     

Simulation of hydraulic fracture propagation near a natural fracture using virtual multidimensional internal bonds

A virtual multidimensional internal bond (VMIB) model developed to simulate the propagation of hydraulic fractures using the finite‐element method is formulated within the framework of the virtual internal bond theory (VIB) that considers a solid as randomized material particles in the micro scale, and derives the macro constitutive relation from the cohesive law between the material particles with an implicit fracture criterion. Hydraulic pressure is applied using a new scheme that enables simulation of hydraulically driven cracks. When the model is applied to study hydraulic fracture propagation in the presence of a natural fracture, the results show the method to be very effective. It shows that although the in situ stress ratio is the dominant factor governing the propagation direction, a natural fault can also strongly influence the hydraulic fracture behavior. This influence is conditioned by the shear stiffness of the fault and the distance to the original hydraulic fracture. The model results show that when the fault is strong in shear, its impact on hydraulic fracture trajectory is weak and the hydraulic fracture will likely penetrate the fault. For a weak fault, however, the fracture tends to be arrested at the natural fault. The distance between the fault and the hydraulic fracture is also important; the fault influence increases with decreasing distance. The VMIB does not require selection of a fracture criterion and remeshing when the fracture propagates. Therefore, it is advantageous for modeling fracture initiation and propagation in naturally fractured rock. Copyright © 2010 John Wiley & Sons, Ltd.     

Hydrachemical Characteristics at the Seismic Stations in Songyuan District,Jilin Province

The hydrochemical types and origins of underground water in Songyuan and vicinity, Liaoning Province were discussed based on the hydrochemical composition, δD and δ¹⁸O. The water samples from eight wells were collected 4 times during 2014 to 2015. The main ion concentrations of water were analyzed with an Ion Chromatography. Isotopic compositions of hydrogen and oxygen were analyzed with the Liquid Water Isotope Analyzer. The mineralization (TDS) of the water ranged from 125.4 mg/L to 19 350.9 mg/L. Values of δD and δ¹⁸O ranged from -71.7‰ to -98.1‰ and from -9.0‰ to -12.5‰, respectively. The isotopic data indicated that the water originated from meteorological precipitation. The chemical compositions of Taolaizhao phreatic water were influenced by the human activity while the other water samples collected from artesian well were less affected by the human activity. Water in Changling, Dongdashi, Taohaotai, Qianan and Ningjiang were characterized by HCO₃-Na with low TDS values. Such chemical types of water with fluctuations of Na⁺, SO42- and δ¹⁸O drift were resulted from dissolving silicate minerals and adding surfactant during oil exploitation. Fresh water in Fuyu well was Cl-Na type, which was influenced by acid injection during oil exploitation. Water in Qianguo well was characterized by Cl-Na type with TDS up to 19 350.9 mg/L, the obvious fluctuations of hydrogen and oxygen isotopes and increasing ion concentrations in the Qianguo well may be caused by the earthquakes that occurred in the sampling duration. The results will provide the background of hydrochemistry, and will be of benefit to monitoring earthquake and certificating seismic-chemical anomalies in the future.     

呼伦湖流域氢氧稳定同位素特征及其对水体蒸发的指示作用

以呼伦湖流域为例研究该区域氢氧稳定同位素在不同水体中的分布特征,并探讨氢氧稳定同位素对在该区域水文过程的指示作用.流域湖水、入湖河水、周边地下水水样的氢氧稳定同位素分析结果表明,夏季8月份湖水中的重氢氧稳定同位素比7月份的更加富集.而河水中氢氧稳定同位素在同一时间内的河流沿程上存在明显的差异,下游水体中的氢氧稳定同位素要比上游更加富集.研究区的河水和湖水的δ~(18)O-δD关系特征显示,河水和湖水的δ~(18)O-δD的关系点全部位于当地降水线的右下方,说明流域河水和湖水水体受到明显的蒸发作用.而井水的δ~(18)O-δD的关系点大都靠近当地大气降水线,说明这一区域的地下水主要是大气降水渗入地下形成.利用氢氧稳定同位素分馏过程中的氢氧稳定同位素的比率与剩余水体的关系,并在考虑湿度因子的动力分馏模拟下,计算出河水的剩余水体比例在0.85~0.96之间,而湖水的剩余水体比例在0.71~0.77之间.最后,利用氢氧稳定同位素质量平衡法对呼伦湖多年平均蒸发量进行了估算,估算的湖泊蒸发量结果与实测值相近,相对误差为5.4%,说明方法可靠.氢氧稳定同位素对于研究区域水文过程有着重要的作用,在今后呼伦湖流域水文研究中有着更加广泛的应用空间.