Element balance studies, analysis

Analysis of Oil Shale Materials for Element Balance Studies... 

Spark source (SSMS) and thermal emission (TEMS) mass spectrometry are used to determine ppb to ppm quantities of elements in energy sources such as coal, fuel oil, and gasoline. Toxic metals—cadmium, mercury, lead, and zinc— may be determined by SSMS with an estimated precision of 5%, and metals which ionize thermally may be determined by TEMS with an estimated precision of 1% using the isotope dilution technique. An environmental study of the trace element balance from a coal-fired steam plant was done by SSMS using isotope dilution to determine the toxic metals and a general scan technique for 15 other elements using chemically determined iron as an internal standard. In addition, isotope dilution procedures for the analysis of lead in gasoline and uranium in coal and fly ash by TEMS are presented. 

The focus of this research and other mass balance studies has been on trace elements (1,2,3). However, in future studies on speciation it will be necessary to know the concentrations of the elements present in amounts above 1%. Therefore, analyses of the oil shale and spent shale samples were performed for these elements. Atomic absorption and colorimetry were used for many of these analyses. Some major element results also were obtained by the broad-range instrumental analysis surveys. The comparison of the results obtained by the different techniques shows large discrepancies. 

The material balance is consistent with the results obtained by OSA (S2+S4 in g/100 g). For oil A, the coke zone is very narrow and the coke content is very low (Table III). On the contrary, for all the other oils, the coke content reaches higher values such as 4.3 g/ 100 g (oil B), 2.3 g/ioo g (oil C), 2.5 g/ioo g (oil D), 2.4/100 g (oil E). These organic residues have been studied by infrared spectroscopy and elemental analysis to compare their compositions. The areas of the bands characteristic of C-H bands (3000-2720 cm-1), C=C bands (1820-1500 cm j have been measured. Examples of results are given in Fig. 4 and 5 for oils A and B. An increase of the temperature in the porous medium induces a decrease in the atomic H/C ratio, which is always lower than 1.1, whatever the oil (Table III). Similar values have been obtained in pyrolysis studies (4) Simultaneously to the H/C ratio decrease, the bands characteristics of CH and CH- groups progressively disappear. The absorbance of the aromatic C-n bands also decreases. This reflects the transformation by pyrolysis of the heavy residue into an aromatic product which becomes more and more condensed. Depending on the oxygen consumption at the combustion front, the atomic 0/C ratio may be comprised between 0.1 and 0.3 ... 

As with selenium analysis, HGAAS also finds a place in Te determination. Basnayake et al. amended cultures of P. fluorescens K27 with 0.1 mM tellurite and, after 92-h growth, determined that approximately 34% of added Te was present as either precipitated, elemental Te in/or on centrifuged cells the balance of added Te remained in solution.190 In this same study, GC/MS was used for determination of DMTe in the same facultative anaerobe amended with tellurate.190 Earlier, GC/MS was used to analyze the headspace of a tellurium-resistant fungus amended with tellurite.215 This last is one of the few reports of the detection of dimethyl ditelluride in microbial headspace (see below). 

Cluster analysis Is used to determine the particle types that occur in an aerosol. These types are used to classify the particles in samples collected from various locations and sampling periods. The results of the sample classifications, together with meteorological data and bulk analytical data from methods such as instrunental neutron activation analysis (INAA). are used to study emission patterns and to screen samples for further study. The classification results are used in factor analysis to characterize spatial and temporal structure and to aid in source attribution. The classification results are also used in mass balance comparisons between ASEM and bulk chemical analyses. Such comparisons allow the combined use of the detailed characterizations of the individual-particle analyses and the trace-element capability of bulk analytical methods. 

The bulk of the samples for this study came from TVA s Allen Steam Plant at Memphis, Tenn. The sampling points (Figure 4) included inlet air, coal, bottom ash, precipitator inlet, and outlet at the 268-ft stack level. During the 2-week sampling period the unit was operated under steady state conditions at 240 MW (12) with a uniform coal supply so that a mass balance might be established for a number of elements. All the coal from southern Illinois was washed and crushed so that 90% was less than 4 mesh. Nominal coal analysis indicated the following composition 9.5% moisture, 34% volatiles, 43% fixed carbon, 13% ash, and 3.4% sulfur. 

In their studies of metals in Chesapeake Bay, however, Bieri et al. (1982) claim that more than 60 % of both the Pb and Mn input is retained in the bed sediments. In their recent studies of heavy metals in Delaware Bay (USA), Church, Tramontano and Murray (1984 and later personal communication) calculated retention of 92 % of the Mn, 37% of the Cu and 32 % of the Cd input to that estuary. However, losses from the estuary in that analysis were based on calculations of the probable flux out of the mouth of the Bay using a layered flow model. When sediment concentrations and accumulation rates were used, only small amounts of Mn and Cd appeared to be retained in the system (Church, personal communication). At this point we are not aware of any convincing evidence that clearly contradicts the findings regarding the behavior of Pb, Cu,Mn or Cd in Narragansett Bay. Unfortunately, the number of mass balances for these elements is so small that this is not a particularly reassuring claim. 

In conclusion we emphasize that the final chemical composition of the surface films covering Li electrodes in solutions is the result of a delicate balance between several competing reduction processes of solvent, salt anion, and contaminants. In this section we emphasize the role of salt reduction processes. However, each solution has to be studied separately since the above balance is determined by factors such as salt concentration, the nature of the solvent, contamination level, etc., all of which differ from system to system. Table 4 presents element analysis by XPS of surface films formed on freshly prepared Li electrodes in several solutions. It demonstrates how the impact of salt reduction on the Li surface chemistry depends on the solution composition and the storage time. (The atomic percentage of fluorine on the surface is a good measure for the impact of the salt.)... 

In this study we have employed the simultaneous collection of atmospheric particles and gases followed by multielement analysis as an approach for the determination of source-receptor relationships. A number of particulate tracer elements have previously been linked to sources (e.g., V to identify oil-fired power plant emissions, Na for marine aerosols, and Pb for motor vehicle contribution). Receptor methods commonly used to assess the interregional impact of such emissions include chemical mass balances (CMBs) and factor analysis (FA), the latter often including wind trajectories. With CMBs, source-strengths are determined (1) from the relative concentrations of marker elements measured at emission sources. When enough sample analyses are available, correlation calculations from FA and knowledge of source-emission compositions may identify groups of species from a common source type and identify potential marker elements. The source composition patterns are not necessary as the elemental concentrations in each sample are normalized to the mean value of the element. Recently a hybrid receptor model was proposed by Lewis and Stevens (2) in which the dispersion, deposition, and conversion characteristics of sulfur species in power-plant emissions... 

A rigorous performance analysis is the key to a meaningful feasibility study. Performance analysis is essential in estimating system the costs. The design of industrial units, or more accurately, the prediction of industrial plant performance was the primary objective of the cunent work. Both the operating and investment costs, key elements in feasibility studies, were determined on the basis of mass and energy balances. 

Mass balance = RY + elemental analysis and/or reactivity studies... 

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