Analysis of Liquid Effluents

In terms of waste definition, there are three basic approaches (as it pertains to petroleum, petroleum products, and nonpetroleum chemicals) to defining petroleum or a petroleum product as hazardous (1) a qualitative description of the waste by origin, type, and constituents (2) classification by characteristics based on testing procedures and (3) classification as a result of the concentration of specific chemical substances (Chapter 1). 

A wide variety of liquid products are produced from petroleum, that varying from high-volatile naphtha to low-volatile lubricating oil (Guthrie, 1967 Speight, 1999). The liquid products are often characterized by a variety of techniques including measurement of physical properties and fractionation into group types (Chapter 7). 

The impact of the release of liquid products on the environment can, in part, be predicted from knowledge of the properties of the released liquid. Each part of an ocular liquid product from petroleum has its own set of unique analytical characteristics (Speight, 1999, 2002). Since these are well documented, there is no need for repetition here. The decision is to include the properties of the lowest-boiling liquid product (naphtha) and a high-boiling liquid product (fuel oil). For the properties of each product (as determined by analysis) a reasonable estimate can be made of other liquid products, but the relationship may not be linear and is subject to the type of crude oil and the distillation range of the product. 

Nevertheless, reference is made to the various test methods dedicated to these products which can be applied to the products boiling in the intermediate range. In the light of the various tests available for composition, such tests will be deemed necessary depending on the environmental situation and the requirements of the legislation as well as at the discretion of the analyst. 

Environmental Analysis and Technology for the Refining Industry, by James G. Speight Copyright 2005 John Wiley Sons, Inc. 

---

A second source of plutonium, dispersed more locally, is liquid effluent from fuel reprocessing facilities. One such is the fuel reprocessing plant at Windscale, Cumbria in the United Kingdom where liquid waste is released to the Irish Sea(6). Chemical analysis of this effluent shows that about one percent or less of the plutonium is in an oxidized form before it contacts the marine water(7). Approximately 95 percent of the plutonium rapidly adsorbs to particulate matter after discharge and deposits on the seabed while 5 percent is removed from the area as a soluble component ). Because this source provided concentrations that were readily detected, pioneering field research into plutonium oxidation states in the marine environment was conducted at this location. 

S. Direct Analysis of Liquid Chromatographic Effluents. J. Chromatogr. 1976, 722, 389-396. 

Precise hydrogen content of the liquid product, used in calculation of hydrogen consumption, was determined by NMR through the courtesy of Phillips Petroleum Company. Analysis of the effluent gas did not include hydrocarbons heavier than ethane. 

Other applications of high performance liquid chromatography to the analysis of trade effluents are listed in Table 4.5. 

UV-Vis analysis of the effluent liquid showed no significant change in conversion level of reactant and intermediates during experiment I, II and III. 

High-molecular-mass PAHs (302 amu or greater) are not normally detected by GC-MS owing to their low volatility. These groups of PAH isomers are present at very low levels yet they have been shown to be much more potent carcinogens. MS detection of liquid effluents allows for the detection of very high molecular mass PAHs such as coronene that are not sufficiently volatile for GC separation. The interface between the HPLC or CE column and the mass spectrometer represents a challenge for the analysis of neutral and nonpolar molecules. Also, the use of water as a mobile phase in reversed-phase LC is problematic due to its low volatility. Heated pneumatic... 

Ail the parameters on which various consents (or permissions to dispose of, waste streams) are based must be reliably measured and recorded. This is easier to achieve with gaseous emissions (Chapter 10) and liquid effluents than with heterogeneous solid wastes. Systematic analysis of solid wastes will cover as a minimum the information in Table 17.15. 

More interesting was the elemental analysis of the residue. Whereas a 2 1 AcOH [DMEpy]l should have contained 33% iodine, the elemental analysis indicated the residue contained only 0.7% iodine. This clearly indicated that we no longer had an iodide salt, but more likely had an acetate salt, most likely a 2 1 mixture of AcOH [DMEpy] [OAc]. (The formation of a 2 1 salt would be typical of our experience with ionic liquids. In practice they normally tenaciously retain ca. 2 mol AcOH/mol of ionic liquid, a phenomena we noted in om earlier reports. (3) Closer comparison of the salt obtained and low levels of Mel detected in the effluent indicated that the amount of [DMEpy] [OAc] generated closely matched the total Mel (ca. 90-95% yield of Mel based on [DMEpy][OAc].) Further, the elemental analysis was unable to detect any Rh in the effluent, so we could conclude that there was no aspiration occurring. This clearly indicated that our ionic liquid loss was due to metathesis of the ionic liquid from the iodide to the acetate salt, likely due to reaction (23) which likely sublimed overhead. In principle, the miniscule amount of Mel and ionic liquid could be returned to the reactor to maintain the process. 

Ware AR, Odell KJ, Martin JP. 1998. Analysis of radioactive metal ions in environmental and liquid effluent samples. J Radioanal Nucl Chem 228(l-2) 5-13. 

Direct liquid injection (DLI) has been used even less. Hirter et al. [579] have reported the early analysis of a synthetic antioxidant mixture (Irganox 1010/1076/1098) by means of iRPLC-DLI-QMS with Cl. In early studies, the HPLC effluent was vaporised by laser radiation [593] both El and solvent-mediated Cl spectra were obtained in the on-line mode from analytically difficult molecules. However, the instrumentation was complex the sensitivity was not as good as that obtained by GC-MS and thermal decomposition was observed with other compounds. This direct introduction approach with enrichment was used for the analysis of phthalates. 

Mass spectrometry is traditionally a gas phase technique for the analysis of relatively volatile samples. Effluents from gas chromatographs are already in a suitable form and other readily vaporized samples could be fairly easily accommodated. However the coupling of mass spectrometry to liquid streams, e.g. HPLC and capillary electrophoresis, posed a new problem and several different methods are now in use. These include the spray methods mentioned below and bombarding with atoms (fast atom bombardment, FAB) or ions (secondary-ion mass spectrometry, SIMS). The part of the instrument in which ionization of the neutral molecules occurs is called the ion source. The commonest method of... 

The liquid effluent, which consists of water from the evaporator/crystallizer used to produce the solid filter cake produced by the brine-recovery operation, should not pose a significant hazard to human health or to the environment. While the evaporator/crystallizer system has not been tested yet, the composition of the water and solid filter cake can be readily determined from an analysis of the SCWO liquid effluent. As shown in Table 5-10, the liquid effluent is essentially free of organics. The source of the chromium and nickel that were found in some of the effluents is generally believed to be corrosion products from the SCWO reactor components. These elevated levels of metals indicate that the solid filter cake will need to be treated (e.g., by stabilization) prior to disposal in a hazardous waste landfill. 7... 

---