On-line coupled systems

Although SFE and SFC share several common features, including the use of a superaitical fluid as the solvent and similar instrumentation, their goals are quite distinct. While SFE is used mainly for the sample preparation step (extraction), SFC is employed to isolate (chr-omatography) individual compounds present in complex samples (11 -15). Both techniques can be used in two different approaches off-line, in which the analytes and the solvent are either vented after analysis (SFC) or collected (SFE), or on-line coupled with a second technique, thus providing a multidimensional approach. Off-line methods are slow and susceptible to solute losses and contamination the on-line coupled system makes possible a deaease in the detection limits, with an improvement in quantification, while the use of valves for automation results in faster and more reproducible analyses (16). The off-line... 

For these techniques, a dissolved sample is usually employed in the analysis to form a liquid spray which is delivered to an atomiser e.g. a flame or electrically generated plasma). Concerning optical spectrometry, techniques based on photon absorption, photon emission and fluorescence will be described (Section 1.2), while for mass spectrometry (MS) particular attention will be paid to the use of an inductively coupled plasma (TCP) as the atomisation/ionisation source (Section 1.3). The use of on-line coupled systems to the above liquid analysis techniques such as flow injection manifolds and chromatographic systems will be dealt with in Section 1.4 because they have become commonplace in most laboratories, opening up new opportunities for sample handling and pretreatment and also to obtain element-specific molecular information. 

It is worth mentioning that the reasons for moving towards more complicated but also more comprehensive on-line coupled systems can also be different, as can be the actual means of the on-line coupling. For instance, the access to NWP fields at each time step is clearly an advantage providing that the dynamic core is unique for... 

Recently it has been shown that rotating coiled columns (RCC) can be successfully applied to the dynamic (flow-through) fractionation of HM in soils and sediments [1]. Since the flow rate of the extracting reagents in the RCC equipment is very similar to the sampling rate that is used in the pneumatic nebulization in inductively coupled plasma atomic emission spectrometer (ICP-AES), on-line coupling of these devices without any additional system seems to be possible. 

A similar on-line LLF system, equipped with an on-line derivatization system, has also been reported. Brinkman and co-workers, for example, have presented a complete automated on-line system that allows both the LLF and alkylation of organic acids (38). More recently, this same group have reported the coupling of... 

J. Beens and R. Tijssen, An on-line coupled HPLC-HRGC system for the quantitative chai acterization of oil fractions in the middle distillate range , J. Microcolumn Sep. 7 345-354(1995). 

The System is built by using three independent modules (SPE, SEE and GC) in Such a way that it can be assembled to perform experiments in the on-line coupled mode (SPE-SEE, SEE-GC, SPE-GC and SPE-SEE-GC) or as independent units (GC, SPE, and SEE). This means that if we want to use the system for standard GC, there will be no problems, with the same applying for both SPE and SEE. 

In coupled LC-GC, specific components or classes of components of complex mixtures are pre-fractionated by LC and are then transferred on-line to a GC system for analytical separation. Because of the ease of collecting and handling liquids, off-line LC-GC techniques are very popular, but they do present several disadvantages, e.g. the numerous steps involved, long analysis times, possibility of contamination, etc. The on-line coupled LC-GC techniques avoid all of these disadvantages, thus allowing us to solve difficult analytical problems in a fully automated way. 

Figure 11.3 Typical configuration for the on-line coupling of an achiral and chiral cliro-matograpliic system by means of a switching valve. The non-enantio-resolved solute is isolated on the achiral phase and then stereochemically separated on the chiral phase. Reprinted from G. Subramanian, A Practical Approach to Chiral Separation by Liquid Chromatography, 1994, pp. 357-396, with permission from Wiley-VCH.

Analogous to two-dimensional LC, the on-line coupling of LC and CE has been carried out both in the heart-cut and the comprehensive mode. In a heart-cut LC-CE study, a protein G immunoaffinity LC column was used to selectively preconcentrate insulin from serum (171). A 1 p.1 elution plug comprising the insulin was switched on-line to the CE system where a part was injected into the capillary for final separation. With CE, efficient separations can be obtained in a... 

A more sophisticated method, giving a much more detailed characterization, involves the on-line coupling of EC and GC (LC-GC). Analysis schemes for middle distillates (kerosine, diesel and jet fuels) combining EC and GC have been reported by various authors (25-31). However, only Davies et al. (25) andMunari et al. (27) have reported on the required automatic transfer of all of the individual separated fractions from the EC unit the GC system. Davies used the loop-type interface and Munari the on-column interface. Only Beens and Tijssen report a full quantitative characterzation by means of LC-GC (31). 

Figure 14.17 Schematic diagram of the on-line coupled LC-GC system VI, valve foi switcliing the LC column outlet to the GC injector V2, valve for switching the LC column to back-flush mode V3, LC injection valve RI, refractive index monitor detector UV, ulti avio-let monitor detector FID, flame-ionization detector.

Heumann kg, Gallus SM, Radlinger G, and Vogl J (1998) Accurate determination of element species by on-line coupling of chromatographic systems with ICP-MS using isotope dilution technique. Spectrochim Acta 53B z73-287. 

Cortes, H. J., Campbell, R. M., Himes, R. P., and Pfeiffer, C. D., On-line coupled liquid chromatography and capillary supercritical fluid chromatography large-volume injection system for capillary SFC, ]. Microcol. Sep., 4, 239, 1992. 

On-line coupled sample preparation/separation/iden-tification systems (e.g. SFE-GC, PFE/automated evaporation/HPLC). 

A recent extension of the scope of SPE-GC and SPE-GC-MS concerns the use of AED detection with its multielement detection capability and unusually high selectivity. Hankemeier [67] has described on-line SPE-GC-AED with an on-column interface to transfer 100 iL of desorbing solvent to the GC. The fully on-line set-up is characterised by detection limits of 5-20 ngL because of quantitative transfer of the analytes from the SPE to the GC module. On-line coupling of SPE with GC is more delicate than SPE-LC, because of the inherent incompatibility between the aqueous part of the SPE step and the dry part of the GC system. 

For the analysis of nonvolatile compounds, on-line coupled microcolumn SEC-PyGC has been described [979]. Alternatively, on-line p,SEC coupled to a conventional-size LC system can be used for separation and quantitative determination of compounds, in which volatility may not allow analysis via capillary GC [976]. An automated SEC-gradient HPLC flow system for polymer analysis has been developed [980]. The high sample loading capacity available in SEC makes it an attractive technique for intermediate sample cleanup [981] prior to a more sensitive RPLC technique. Hence, this intermediate step is especially interesting for experimental purposes whenever polymer matrix interference cannot be separated from the peak of interest. Coupling of SEC to RPLC is expected to benefit from the miniaturised approach in the first dimension (no broadening). Development of the first separation step in SEC-HPLC is usually quite short, unless problems are encountered with sample/column compatibility. 

Integration of sample preparation and chromatography by on-line coupling aims at reduction of analysis time. It is apparent from Section 7.1 that these hyphenated techniques are not yet contributing heavily to the overall efficiency of polymer/additive analysis in industry. On-line SFE-SFC requires considerable method development, and MAE-HPLC is off-line. Enhancement of sensitivity for trace analysis requires appropriate sample preparation and preconcentration schemes, as well as improved detection systems. 

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