燃煤过程中微量元素砷和硒形态转化的热力学平衡模拟

砷和硒是煤中的易挥发有毒微量元素。由于砷和硒在燃煤烟气中的浓度极低以及实验条件的限制 ,目前化学热力学平衡分析已成为预报烟气中砷和硒等有毒元素形态分布的主要理论分析方法。本文综述了热力学平衡分析方法应用于砷和硒在燃煤过程中形态转化和平衡分布等方面的研究进展。首先用于热力学平衡分析的是只含有砷或硒一种微量元素和煤中主量元素及氯元素的简单体系 ,并假设烟气中只有理想气体组成的气相和纯凝聚相的理想模型。然而是否考虑砷和硒与其他微量、主量或次量元素的相互作用 ,砷和硒所有可能存在的反应 ,以及在熔融相砷和硒与熔融物的结合会严重地影响模型的预报结果 ,因此 ,目前热力学平衡体系已发展成为含有包括砷和硒在内的多个微量元素和煤中所有主量、次量元素 ,以及包括熔融相在内的非理想多相复杂体系     

Air pollution assessment based on elemental concentration of leaves tissue and foliage dust along an urbanization gradient in Vienna

Foliage dust contains heavy metal that may have harmful effects on human health. The elemental contents of tree leaves and foliage dust are especially useful to assess air environmental pollution. We studied the elemental concentrations in foliage dust and leaves of Acer pseudoplatanus along an urbanization gradient in Vienna, Austria. Samples were collected from urban, suburban and rural areas. We analysed 19 elements in both kind of samples: aluminium, barium, calcium, copper, iron, potassium, magnesium, sodium, phosphor, sulphur, strontium and zinc. We found that the elemental concentrations of foliage dust were significantly higher in the urban area than in the rural area for aluminium, barium, iron, lead, phosphor and selenium. Elemental concentrations of leaves were significantly higher in urban than in rural area for manganese and strontium. Urbanization changed significantly the elemental concentrations of foliage dust and leaves and the applied method can be useful for monitoring the environmental load.     

Study on transformation and enrichment behavior of selenium in particulate matter in combustion flame

An ethylene/air inverse diffusion flame (IDF) burner was employed to generate a stable flame, and selenium was introduced into the combustion flame in vapor phase under different air-fuel ratio (A/F) with SO2 additive. At different height above burner (HAB) along the flame edge, selenium of different speciation (gaseous selenium and particulate selenium) was sampled via the U.S. EPA method 29, and the samples were determined by hydride generation atomic fluorescence spectrometry (HG-AFS), in order to study the mechanism of transformation and enrichment behavior of selenium during the combustion process. The results showed that selenium presented in vapor phase, crossing the flame into air, which means gaseous phase is the main form of selenium during combustion process. Both gaseous selenium and particulate selenium increased with elevated temperature from 820K to 1650K, suggesting that higher temperature is beneficial to the release of selenium. Low concentration of sulfur dioxide would increase the concentration of particulate selenium and gaseous selenium, and accelerate the release of selenium.

Implications: The enrichment behavior of selenium and its transformation in combustion flame were studied. The results showed that gaseous selenium is found in higher quantity in compared to particulate selenium during combustion. Higher temperature and air–fuel ratio will cause an increase in the formation of selenium. While the presence of sulfur dioxide in a range of 0–200 ppm will promote the release of selenium, higher sulfur dioxide level in a range of 200–350 ppm will have a reverse effect.     

Metallothionein levels in Algerian mice (Mus spretus) exposed to elemental pollution: an ecophysiological approach

The potential use of metallothioneins (MTs) as biomarkers of trace metal contamination was evaluated for the first time in the Algerian mouse (Mus spretus). Mice were collected seasonally in an abandoned mining area (Aljustrel) and in a reference area, both located in southern Portugal. MT levels were quantified in liver and kidney by differential pulse polarography and hepatic elemental concentrations (Mn, Fe, Cu, Zn, Se) were determined by particle-induced X-ray emission. Hepatic iron and selenium concentrations were elevated in mice from Aljustrel mine when compared to reference animals. MTs levels were averagely higher in mice from Aljustrel than those originated from the reference area. A season-dependent significant effect was found on the hepatic and renal MT concentrations, characterized by higher levels in winter and lower in autumn. In contaminated mice positive relationship between liver elemental contents (Cu in autumn and Fe in winter) and MTs were found. The seasonal variation of MT suggests that probably physiological and environmental factors could influence hepatic and renal MT induction. Results seem to imply that some environmental disturbance occur in the vicinity of the Aljustrel mine. Therefore, for the management purposes MT levels should be followed in liver of M. spretus, especially in winter. Furthermore, other physiological factors that could influence MT expression and turnover in Algerian mouse should also be monitored.     

Absorption of selenium by Lactuca sativa as affected by carboxymethylcellulose

Several organic compounds of high molecular weight present in soil interact with selenium and may act as active binding agents affecting its availability in soil, and, consequently, selenium uptake by plants. This study is aimed at investigating the effects of polysaccharides on selenium speciation in soil and on selenium absorption by Lactuca sativa L. plants. Three-week-old seedlings were transplanted into pots filled with soil, and sodium selenite at rates of 1.5 and 5mgSekg(-1) of soil, or sodium selenate at a rate of 1.5mgSekg(-1) of soil were applied. Carboxymethylcellulose (CMC) was added to the soil at rates of 0, 3 and 30mgkg(-1) of soil. After 48 and 110d from transplanting plants were harvested, separated into root and shoot, and fresh and dry matter weights were recorded. Total selenium was determined in both soil and plant samples. A sequential extraction was used to investigate the different Se oxidation states and assess the availability of Se in soil after the final harvesting. Both selenite and selenate were absorbed by roots, but plants amended with Se(VI+) showed higher selenium concentration than plants amended with Se(IV+). Selenite appears to be less mobile than selenate both in soil and plants. The addition of carboxymethylcellulose to soil decreased the amount of selenium absorbed by plants. CMC interacted with Se, making it less mobile as evidenced by the increase in the insoluble fractions. The insoluble Se forms in soil may represent environmental Se sinks potentially available for plants if the substrate is re-used for subsequent growth cycles and selenium species are mobilized as a result of biological and chemical processes.     

The recovery of selenious acid aerosols on glass fiber filters

Previous workers have shown that selenium is only partially trapped on a filter during air sampling. In some cases, these losses have been attributed to volatilization of selenium dioxide. Our results demonstrate that selenium dioxide, in the presence of moist air, is completely recovered (apparently as selenious acid aerosols) and that the previous shortfalls must be due to other selenium species as yet unidentified. Selenious acid aerosols in our study were formed by volatilizing selenium dioxide (approximately 3 mg) into a stream of moist ambient air (relative humidity, greater than 50%), and trapped on glass fiber filters using a high-volume air sampler. Selenium(IV) was ultrasonically extracted from the filter with water and analyzed by atomic absorption spectrometry. Selenious acid aerosols were trapped on the filters with high efficiency (105 +/- 5 percent) using a 50 minute sampling period. With an extended sampling period (24 hours) the recovery was 103 +/- 6 percent.     

The Recovery of Selenious Acid Aerosols on Glass Fiber Filters

Previous workers have shown that selenium is only partially trapped on a filter during air sampling. In some cases, these losses have been attributed to volatilization of selenium dioxide. Our results demonstrate that selenium dioxide, In the presence of moist air, is completely recovered (apparently as selenious acid aerosols) and that the previous shortfalls must be due to other selenium species as yet unidentified. Selenious acid aerosols In our study were formed by volatilizing selenium dioxide (≈3 mg) Into a stream of moist ambient air (relative humidity, >50%), and trapped on glass fiber filters using a high-volume air sampler. Selenium(IV) was ultrasonlcally extracted from the filter with water and analyzed by atomic absorption spectrometry. Selenious acid aerosols were trapped on the filters with high efficiency (105 ± 5 percent) using a 50 minute sampling period. With an extended sampling period (24 hours) the recovery was 103 ± 6 percent.     

Contamination of different portions of raw and boiled specimens of Norway lobster by mercury and selenium

The aim of this study was to evaluate mercury and selenium distribution in different portions (exoskeleton, white meat and brown meat) of Norway lobster (Nephrops norvegicus). Some samples were also analysed as whole specimens. The same portions were also examined after boiling, in order to observe if this cooking practice could affect mercury and selenium concentrations. The highest mercury concentrations were detected in white meat, exceeding in all cases the maximum levels established by European legislation. The brown meat reported the highest selenium concentrations. In all boiled samples, mercury levels showed a statistically significant increase compared to raw portions. On the contrary, selenium concentrations detected in boiled samples of white meat, brown meat and whole specimen showed a statistically significant decrease compared to the corresponding raw samples. These results indicate that boiling modifies mercury and selenium concentrations. The high mercury levels detected represent a possible risk for consumers, and the publication and diffusion of specific advisories concerning seafood consumption is recommended.     

Reproduction of mallards following overwinter exposure to selenium

Forty pairs of mallards (Anas platyrhynchos) were fed 15 ppm selenium as selenomethionine for about 21 weeks during winter. Twenty pairs served as controls. At the end of 21 weeks, which coincided with the onset of the reproductive season, selenium treatment was ended. Four birds died while on selenium treatment. Treated females lost weight, and their egg-laying was delayed. Hatching success of some of the first eggs laid by selenium-treated females was lower than that of controls, and a few of these early eggs contained deformed embryos, but, after a period of about two weeks off the selenium-treated diet, reproductive success returned to a level comparable with that of controls. The return to normal reproductive success was the result of a corresponding decrease in selenium concentrations in eggs once selenium treatment ended.     

Forms and distribution of selenium at different depths and among particle size fractions of three Taiwan soils

The bioavailability of selenium in soils for plants depends more on its forms than on its total concentration. The purpose of the present study was to examine the solid-phase forms of selenium at different depths of three soil series representing major farming soil groups in Taiwan as well as the amounts of selenium in sand, silt and clay fractions of the soils. The study was conducted by means of sequential extraction to obtain the amounts of selenium and the distribution of various solid-phase forms of selenium at different depths of Pinchen (121 degrees 11(')E, 24 degrees 55(')N), Toulun-Sheto (120 degrees 55(')E, 24 degrees 50(')N), and Chunliao (120 degrees 25(')E, 23 degrees 57(')N) soil series. The amounts of metal oxide-bound form of selenium in the three soil series were the largest, with those of Pinchen and Toulun-Sheto soil series exceeding 50% of the total amounts of selenium and that of Chunliao soil series maintained at 30-40%. In the Pinchen and Toulun-Sheto soil series, the amounts of selenium in clay fractions were the largest, with a significant difference between the clays with and without metal oxides and organic matter removed. The amounts of selenium remained high in silt and/or sand fractions of the Chunliao soil series with metal oxides and organic matter removed. Metal oxide and organic matter contents of the three soil series mainly affect the amounts of various solid-phase forms of selenium and their distribution in different depths and particle size fractions of the soils. This observation of selenium associated with soil constituents was in good agreement with the results of the adsorption of selenite and selenate by the three soil series.     

Mercury and selenium in wild and experimental seals

This paper describes the tissue distribution of inorganic mercury, organic mercury and selenium in Dutch and British seals as well as in seals which were dosed with methylmercury under experimental conditions.In the experimental animals, a time-related increase of both mercury and selenium was found in liver and kidney after the administration of methylmercury, while in the other tissues examined, e.g. brain, thyroid, blood, only the concentrations of mercury increased.In the wild seals, it was also demonstrated that the selenium concentrations showed a positive correlation with the concentrations of mercury.Atomic ratios of mercury and selenium were close to one in the wild seals as was also found in previous studies. However, atomic ratios above one were found in seals fed additional methylmercury.In vitro studies with liver homogenates of seals did not provide evidence for the presence of a biochemical demethylation mechanism nor for any effect of selenium on the demethylation process.     

Effects of a selenium-enriched diet on antioxidant response in adult crayfish (Procambarus clarkii)

Many diets employed in aquaculture are enriched with selenium to improve the diet quality and its conservation. The aim of the study was to investigate the effects of a diet enriched in selenium (1.21 mg kg(-1)) on the antioxidant response of Procambarus clarkii (Girard, 1852). Crayfish fed a diet with lower selenium content (0.30 mg kg(-1)) were the control. Selenium accumulation, enzymatic activities, and total glutathione were evaluated in hepatopancreas of adults of both sexes fed with both diets for 50 days at two experimental times (T(30), T(50) days). Treated females exhibited the highest selenium bioaccumulation during both experimental times, while treated males displayed the highest selenium concentration after 30 days, compared to control crayfish. A sex-related difference was found for the response of the analyzed enzymes in the selenium diet-treated specimens. In fact, superoxide dismutase, glutathione peroxidase and glyoxalase I activities in males were more sensitive compared with females, showing depleted activities in both experimental times. Catalase activity was induced in females (T(50)), while glutathione S-transferase activity was the highest in treated females and the lowest in treated males, compared with own controls. Only glutathione reductase activity and glutathione content showed the same trend in both sexes, which were both lowered in treated specimens, when compared with control crayfish. This result might be due to the effect of selenium toxicity on this freshwater species. Males and females of P. clarkii showed a different susceptibility to the prooxidant effects in a Se-enriched diet.     

Studies of selenium in environmental samples and synthetic mixtures by spectrophotometry

A rapid, highly sensitive and selective spectrophotometric method for the determination of traces of selenium(IV) is described. The method is based on oxidation of p-nitroaniline by selenium(IV) followed by coupling reaction with N-(1-naphthalene-1-yl)ethane-1,2-diamine dihydrochloride (NEDA) in neutral medium to give red colored derivative with lambda(max) 515 nm and is stable for more than 10 days at 35 degrees C. Beer's law is obeyed for selenium(IV) in the concentration range of 0.02-3.2 microg ml(-1) at the wavelength of maximum absorption. The optimum reaction conditions and other analytical parameters were investigated to enhance the sensitivity of the present method. The detailed study of various interferences made the method more selective. The proposed method was successfully applied to the analysis of selenium in polluted water, natural water samples, plant material, soil samples, and synthetic mixtures. The results obtained were agreed with the reported methods at the 95% confidence level. The performance of proposed method was evaluated in terms of Student's t-test and Variance ratio f-test which indicates the significance of proposed method over reported method.     

Protein bound selenium in some marine organisms

Total selenium levels and the fraction of element associated with protein have been determined in several marine organisms by gas-liquid chromatography. A large fraction of selenium in all organisms was associated with protein.     

Comparison of the effects of seleno-L-methionine, seleno-DL-methionine, and selenized yeast on reproduction of mallards

The toxicities of seleno-L-methionine, seleno-DL-methionine, and selenized yeast were compared. Ten pairs of mallards were fed a control diet and 15 pairs were fed diets containing 10 ppm selenium as seleno-DL-methionine, seleno-L-methionine, or selenized yeast. Hatching of fertile eggs was significantly lower for females fed 10 ppm selenium as seleno-DL-methionine (7.6%) and seleno-L-methionine (6.4%) than for controls (41.3%). Survival of ducklings was lower when their parents had been fed 10 ppm selenium as seleno-L-methionine (20.0%) than for controls (98.4%). The number of 6-day-old ducklings produced per female was significantly lower for mallards fed 10 ppm selenium as seleno-DL-methionine (0.47) or selenized yeast (2.67) than for controls (6.10), and was significantly lower for mallards fed seleno-L-methionine (0.13) than for mallards fed selenized yeast. The eighth eggs of females fed the DL or L forms of selenomethionine contained means of 9.2 and 8.9 ppm selenium, wet weight; these means were higher than the mean (6.6 ppm) for females fed selenized yeast. Among embryos that died at 7 days of age or older, the percentage of embryos that were deformed was 1.3% for controls, 24.6% for seleno-DL-methionine, 28.2% for seleno-L-methionine, and 11.0% for selenized yeast. The results suggested that seleno-DL-methionine and seleno-L-methionine were of similar toxicity and were both more toxic than selenium from selenized yeast.     

The effect of consumption of pork enriched by organic selenium on selenium status and lipid profile in blood serum of consumers

Abstract

The aim of the research was to evaluate the effect of consumption of selenium-enriched pork on selected health indicators of probands. The intake of feed mixture with increased organic selenium at the dose of 0.3?mg.kg^?1 probably increases selenium concentration in MSM (musculus semimembranosus). In the pork enriched with organic selenium, the concentration was higher by 1.045?±?0.10?mg.kg^?1 compared with the control group 0.701?±?0.05?mg.kg^?1 at significance P?<?0.001. Sixteen participants in the experiment were represented by 8 men at the average age of 41.5?±?11.9?years and 8 women at the average age of 41.4?±?7.9?years. All the probands consumed meat enriched with selenium three times a week during one month. By consumption of the enriched pork, there was an increase of the selenium concentration in blood serum of probands traced with selenium increase from 73.19?±?15.68?μg.L^?1 to 73.73?±?15.13?μg.L^?1 (P?>?0.05). From the results we can see that consumption of enriched pork with selenium was significantly manifested in lowering of total cholesterol levels, which was associated with LDL cholesterol lowering (P?<?0.05). Differences among the HDL cholesterol and triglycerides samples were not significant.     

Recovery studies of selenium using dry ashing procedure with ashing aid.

A previously reported dry ashing procedure for the decomposition of marine samples prior to arsenic determination is demonstrated to be equally applicable to the analysis of selenium. Quantitative recovery of selenium as inorganic or organic compounds in a variety of plants and animal tissues is demonstrated using 75Se tracer and X-ray fluorescence techniques. The dry ashing procedure is simpler than the official AOAC method, which uses a mixture of H2SO4, HNO3 and HC10(4).     

Total arsenic and selenium analysis in Marcellus shale,high-salinity water,and hydrofracture flowback wastewater

Trace levels of arsenic and selenium can be toxic to living organisms yet their quantitation in high ionic strength or high salinity aqueous media is difficult due to the matrix interferences which can either suppress or enhance the analyte signal. A modified thiol cotton fiber (TCF) method employing lower flow rates and centrifugation has been used to remove the analyte from complex aqueous media and minimize the matrix interferences. This method has been tested using a USGS (SGR-1b) certified reference shale. It has been used to analyze Marcellus shale samples following microwave digestion as well as spiked samples of high salinity water (HSW) and flow back wastewater (WRF6) obtained from an actual gas well drilling operation. Quantitation of arsenic and selenium is carried out by graphite furnace atomic spectroscopy (GFAAS). Extraction of arsenic and selenium from Marcellus shale exposed to HSW and WRF6 for varying lengths of time is also reported.     

Total arsenic and selenium analysis in Marcellus shale, high-salinity water, and hydrofracture flowback wastewater

Trace levels of arsenic and selenium can be toxic to living organisms yet their quantitation in high ionic strength or high salinity aqueous media is difficult due to the matrix interferences which can either suppress or enhance the analyte signal. A modified thiol cotton fiber (TCF) method employing lower flow rates and centrifugation has been used to remove the analyte from complex aqueous media and minimize the matrix interferences. This method has been tested using a USGS (SGR-1b) certified reference shale. It has been used to analyze Marcellus shale samples following microwave digestion as well as spiked samples of high salinity water (HSW) and flow back wastewater (WRF6) obtained from an actual gas well drilling operation. Quantitation of arsenic and selenium is carried out by graphite furnace atomic spectroscopy (GFAAS). Extraction of arsenic and selenium from Marcellus shale exposed to HSW and WRF6 for varying lengths of time is also reported.     

Phyto-products may be essential for sustainability and implementation of phytoremediation

Interest in selenium pollution and remediation technology has escalated during the past two decades. Although not known to be essential for plants, selenium is essential but could be toxic for humans and animals, depending on its concentration. A major selenium controversy in the 1980's emerged in California when the general public and scientific community became aware of selenium's potential as an environmental contaminant. After extensive research on several strategies to reduce loads of mobile Se for entering the agricultural ecosystem a plant-based technology, defined as 'phytoremediation' received increasing recognition, as a low-cost environmentally friendly approach for managing soluble Se in the soil and water environment. Successful long-term field remediation of Se by plants is, however, dependent upon acceptance and widespread use by growers, who are also concerned about potential commercial value from using the plant-based technology. Obtaining products with economic value from plants used in the cleanup of soil would certainly be an additional benefit to phytoremediation, which could help sustain its long-term use.