Options volatility

Major new options in SOLMINEQ.88 include a boiling option, volatile fractionation between oil, gas and water, an adsorption and ion exchange option and a dissolution/precipitation option. Interactive programs have been written which facilitate input, running and examination of the output. 

Optional volatile organic compound (VOC) recovery system... 

Conventionally, PAG, GAC, or extruded activated carbon serves as adsorbents for contaminants from treated waters directly (Fig. 11, solid lines) or indirectly (dotted lines in the Fig. 11). In the latter option, volatiles from water are first transferred to the gas phase by air stripping [45]. The contaminated air is subsequently passed throu the carbon bed, which enables the effective removal of the stripped compounds. The removal of contaminants Irom waters with the use of carbon adsorption systems is particularly effective for final purification of water discharges from other remedial technologies. 

The fourth option, shown in Fig. 4.4FEED-IMPURITY separation is expensive. To use a purge, the FEED and IMPURITY must be adjacent to each other in order of volatility (again, assuming distillation as the means of separation). Care should be taken to ensure that the resulting increase in concentration of IMPURITY in the reactor does not have an adverse effect on reactor performance. 

Fundamentally, introduction of a gaseous sample is the easiest option for ICP/MS because all of the sample can be passed efficiently along the inlet tube and into the center of the flame. Unfortunately, gases are mainly confined to low-molecular-mass compounds, and many of the samples that need to be examined cannot be vaporized easily. Nevertheless, there are some key analyses that are carried out in this fashion the major one i.s the generation of volatile hydrides. Other methods for volatiles are discussed below. An important method of analysis uses lasers to vaporize nonvolatile samples such as bone or ceramics. With a laser, ablated (vaporized) sample material is swept into the plasma flame before it can condense out again. Similarly, electrically heated filaments or ovens are also used to volatilize solids, the vapor of which is then swept by argon makeup gas into the plasma torch. However, for convenience, the methods of introducing solid samples are discussed fully in Part C (Chapter 17). 

A major advantage of this hydride approach lies in the separation of the remaining elements of the analyte solution from the element to be determined. Because the volatile hydrides are swept out of the analyte solution, the latter can be simply diverted to waste and not sent through the plasma flame Itself. Consequently potential interference from. sample-preparation constituents and by-products is reduced to very low levels. For example, a major interference for arsenic analysis arises from ions ArCE having m/z 75,77, which have the same integral m/z value as that of As+ ions themselves. Thus, any chlorides in the analyte solution (for example, from sea water) could produce serious interference in the accurate analysis of arsenic. The option of diverting the used analyte solution away from the plasma flame facilitates accurate, sensitive analysis of isotope concentrations. Inlet systems for generation of volatile hydrides can operate continuously or batchwise. 

Deeper contamination may be remedied with bioventing, where air is injected through some wells, and extracted through others to both strip volatiles and provide oxygen to indigenous organisms. Fertilizer nutrients may also be added. This is usually only a viable option with lighter refined products. 

For VOCs, control options are multiple. Source reduction or removal includes product substitution or reformulation. Particleboard or pressed w ood has been developed and used extensively in building materials for cabinet bases and subflooring and in furniture manufacturing for frames. If the product is not properly manufactured and cured prior to use as a building material, VOCs can outgas into the interior of the residence or building. Other sources of VOCs may be paints, cleaning solutions, fabrics, binders, and adhesives. Proper use of household products will lower volatile emissions. 

The on-eolumn interfaee is the one whieh is most often used in LC-GC of aqueous samples beeause it ean be applied to a wider range of eompounds.The loop-type interfaee is limited for determining volatile eompounds that are volatilized together with the solvent and not retained in the retention gap. Several attempts at solving this problem have been made. One option is to add a eo-solvent whieh enters the retention gap before the analytes and thus forms a eo-solvent film in front of the eluate. 

Obviously, the use of a nonvolatile ionic liquid simplifies the distillative workup of volatile products, especially in comparison with the use of low-boiling solvents, where it may save the distillation of the solvent during product isolation. Moreover, common problems related to the formation of azeotropic mixtures of the volatile solvents and the product/by-products formed are avoided by use of a nonvolatile ionic liquid. In the Rh-catalyzed hydroformylation of 3-pentenoic acid methyl ester it was even found that the addition of ionic liquid was able to stabilize the homogeneous catalyst during the thermal stress of product distillation (Figure 5.2-1) [21]. This option may be especially attractive technically, due to the fact that the stabilizing effects could already be observed even with quite small amounts of added ionic liquid. 

Reliable analytical methods are available for determination of many volatile nitrosamines at concentrations of 0.1 to 10 ppb in a variety of environmental and biological samples. Most methods employ distillation, extraction, an optional cleanup step, concentration, and final separation by gas chromatography (GC). Use of the highly specific Thermal Energy Analyzer (TEA) as a GC detector affords simplification of sample handling and cleanup without sacrifice of selectivity or sensitivity. Mass spectrometry (MS) is usually employed to confirm the identity of nitrosamines. Utilization of the mass spectrometer s capability to provide quantitative data affords additional confirmatory evidence and quantitative confirmation should be a required criterion of environmental sample analysis. Artifactual formation of nitrosamines continues to be a problem, especially at low levels (0.1 to 1 ppb), and precautions must be taken, such as addition of sulfamic acid or other nitrosation inhibitors. The efficacy of measures for prevention of artifactual nitrosamine formation should be evaluated in each type of sample examined. 

Major emphasis in studies of N-nitroso compounds in foods has been placed upon volatile nitrosamines, in part because these compounds are relatively easy to isolate from complex matrices by virtue of their volatility. Procedures utilizing atmospheric pressure or vacuum distillation have been used by most investigators, with variations of the method of Fine e al. (2) being among the most popular. This procedure employs vacuum distillation of a mineral oil suspension of the sample with optional addition of water to improve nitrosamine recovery from low moisture content samples (6) The usual approach to prevention of nitrosamine formation during analysis involves adding sulfamic acid or ascorbate to destroy residual nitrite at an early stage of sample preparation. 

Intelligent engineering can drastically improve process selectivity (see Sharma, 1988, 1990) as illustrated in Chapter 4 of this book. A combination of reaction with an appropriate separation operation is the first option if the reaction is limited by chemical equilibrium. In such combinations one product is removed from the reaction zone continuously, allowing for a higher conversion of raw materials. Extractive reactions involve the addition of a second liquid phase, in which the product is better soluble than the reactants, to the reaction zone. Thus, the product is withdrawn from the reactive phase shifting the reaction mixture to product(s). The same principle can be realized if an additive is introduced into the reaction zone that causes precipitation of the desired product. A combination of reaction with distillation in a single column allows the removal of volatile products from the reaction zone that is then realized in the (fractional) distillation zone. Finally, reaction can be combined with filtration. A typical example of the latter system is the application of catalytic membranes. In all these cases, withdrawal of the product shifts the equilibrium mixture to the product. 

Cl and El are both limited to materials that can be transferred to the ion source of a mass spectrometer without significant degradation prior to ionisation. This is accomplished either directly in the high vacuum of the mass spectrometer, or with heating of the material in the high vacuum. Sample introduction into the Cl source thus may take place by a direct insertion probe (including those of the desorption chemical ionisation type) for solid samples a GC interface for reasonably volatile samples in solution a reference inlet for calibration materials or a particle-beam interface for more polar organic molecules. This is not unlike the options for El operation. 

HSPF. The Hydrologic Simulation Program (FORTRAN) ( 1, 42) is based on the Stanford Watershed Model. Version 7 of HSPF incorporates the process models of SERATRA in its aquatic section, with several (user-selectable) options for sediment transport computations. HSPF includes the generation of transformation products, each of which is in turn subject to volatilization, phototransformation, biolysis, etc. 

---