HRMS

Corporate environmentalism is an evolving concept for environmental protection. In this case, business takes a pro-active stance independent of regulatory authorities. This can be in recognition of social responsibilities, but is more successful when compelled by competition in the market place. Thus, a hrm can conscientiously target environmentally aware consumers (through marketing environmentally friendly products or processes) or can be better placed for hnancial support from ethical investment funding bodies. 

HRMS Human Reliability Management System Kirwan, 1992... 

Having agreed to bid, if a hrm does not submit a bid without good reason consideration should be given to removing it from the bid list for a short period, because when a hrm does not bid, it reduces the competitive element, possibly increasing the cost of the job. It also denies another hrm the opportunity of biding. 

The number of bidders invited to bid should be determined by the size of the works. Good contractors should be encouraged to bid and not be disillusioned by too many bidders. For most contracts, a bid list of six hrms should be sufficient to keep the biding competitive and allow for the odd hrm that does not return its bid. 

The addition may be correct, but a bidder may have underestimated a particular item. With an itemized bid it is possible to spot an error of this kind. For example, referring to Table 8.1 and looking at item 3, bidder 2 has less than half in his bid for item 3 than any other bidder. On the other hand, item 2 appears to have made up for it. Where an apparent mistake has occurred, the hrm concerned should be contacted, and should be asked to look closely at a certain item, which appears low. For example, bidder 1 has a much lower amount for item 7 than any other, and if he had bided similarly to the other... 

Bids received can vary by up to 100 per cent over a range of hrms. The higher bids may be from hrms who do not want the job but wish to keep contact with the client. Where there is a difference of more than 10 per cent between the lowest and second-lowest bidder, this can cause problems. For example, the Electrical Contractors Association offer a guarantee of completing through their members, at no extra cost, in the event that a member is unable to do so, but only if the difference between the contractors appointed and the next bid is not more than 10 per cent. In some instances, this could be enough to seriously consider not accepting the lowest bid. 

However, despite their practical and societal value, vaccines remain only a small component of the global pharmaceutical market ( 5 billion out of 350 billion sales in 2000). The vaccine market is dominated by just four large manufacturers GlaxoSmithKline, Aventis Pasteur, Wyeth, and Merck Co. There is, however, a strong resurgence of interest in vaccines, with a growing cluster of small vaccine companies and biotech hrms, led by Chiron. 

State-of-the-art ToF-MS employs reflection lenses and delayed extraction [176] to improve resolution by minimising small differences in ion energies, and in these cases up to 12000 mass resolution (FWHM, m/z 600) is available. This is sufficient for most modern applications. Solid probe ToF-MS (or direct inlet high-resolution mass spectrometry, DI-HRMS) is a breakthrough. DIP-ToFMS is a thermal separation technique. Advantages of DIP-ToFMS are ... 

FTICR-MS is capable of powerful mixture analysis, due to its high mass range and ultrahigh mass resolving power. However, in many cases it is still desirable to couple a chromatographic interface to the mass spectrometer for sample purification, preconcentration, and mixture separation. In the example given above, DTMS under HRMS conditions provides the elementary composition. Apart from DTMS, PyGC-MS can be performed to preseparate the mixture of molecules and to obtain the MS spectrum of a purified unknown. Direct comparison with the pure reference compound remains the best approach to obtain final proof. 

Direct solid-state polymer/additive mass analysis has involved various ionisation modes El (Section 6.2.1), Cl (Section 6.2.2), DCI (Section 6.2.2.1), FAB (Section 6.2.4), FI (Section 6.2.5), FD (Section 6.2.6) and LD. Survey mass spectra obtained with soft ionisation methods (FI-MS, CI-MS) provide diagnostic overviews of chemical composition. The supplemental tandem (MS/MS) and atomic composition (AC-MS) techniques are used to make specific identifications of various organic ingredients. Direct analysis of polymer systems for more than a few thousand daltons has only just begun. Ionisation methods employed are FD, ESI and MALDI. Solid-probe ToF-MS (or DI-HRMS) is a breakthrough [188]. 

Biicherl et al. [431] have described direct SFE-cSFC-HRMS/FID coupling (Figure 7.18) with reduced effective flow of C02 into the mass spectrometer and significant loss of sample molecules (except for some low-MW compounds). 

Satisfactory performance of the SFE-SFC-HRMS instrumentation (resolution 1200) was only possible after optimisation (temperatures, restrictor and quartz tube positions, flow characteristics and sample transfer conditions). Mass spectra obtained for Irganox 1010/1076/1330 and Irgafos 168/P-EPQ by SFC-HRMS were identical with those obtained by use of DIP [431]. However, the sensitivity of the SFE-SFC-MS interface is low (at best 4 % of that obtained with sample introduction via DIP). An enormous amount of sample is lost in all parts of the coupling system (SFE, SFC and... 

Figure 7.18 Schematic diagram of an SFE-cSFC-HRMS/FID system. After Biicherl et al. [431]. From T. Biicherl et al., Journal of High Resolution Chromatography, 17, 765-769 (1994). Wiley-VCH, 1994. Reproduced by permission of Wiley-VCH...

As evident from Scheme 7.13, most modern ionisation techniques have been used for TLC-MS, and no single ionisation method is used exclusively with TLC-MS. Various ionisation methods may be applied that avoid the need to evaporate the sample into an El or Cl source these are based in particular on sputtering (FAB, SIMS) or laser desorption. Several sputtering methods of ionisation do not require the use of a liquid matrix, e.g. TLC-SIMS [797], Recent developments include the use of matrix-assisted laser desorption ionisation (MALDI) and surface-assisted laser desorption ionisation (SALDI). It is obvious that TLC-MS is complemented with TLC-MS11 [800] and TLC-HRMS techniques. Table 7.82 lists the general characteristics of TLC-MS. 

Figure 8.14 Layout of an ICP-HRMS instmment. After Jakubowski and Stuewer [386]. Reproduced by permission of the authors...

Application to solid polymer/additive formulations is restricted, for obvious reasons. SS-ETV-ICP-MS (cup-in-tube) has been used for the simultaneous determination of four elements (Co, Mn, P and Ti) with very different furnace characteristics in mg-size PET samples [413]. The results were compared to ICP-AES (after sample dissolution) and XRF. Table 8.66 shows the very good agreement between the various analytical approaches. The advantage of directly introducing the solid sample in an ETV device is also clearly shown by the fact that the detection limit is even better than that reported for ICP-HRMS. The technique also enables speciation of Sb in PET, and the determination of various sulfur species in aramide fibres. ETV offers some advantages over the well-established specific sulfur analysers very low sample consumption the possibility of using an aqueous standard for calibration and the flexibility to carry out the determination of other analytes. The method cannot be considered as very economic. 

Mass spectrometry combines exquisite sensitivity with a precision that often depends more on the uncertainties of sampling and sample preparation than on those of the method itself. Mass spectrometry is a supreme identification and recognition method in polymer/additive analysis through highly accurate masses and fragmentation patterns quantitation is its weakness. Direct mass spectrometry of complex polymeric matrices is feasible, yet not often pursued. Solid probe ToF-MS (DI-HRMS) is a breakthrough. Where used routinely, mass spectrometrists are usually still in charge. At the same time, however, costs need to be watched. 

The use of GC-MS in polymer/additive analysis is now well established. Various GC-based polymer/additive protocols have been developed, embracing HTGC-MS, GC-HRMS and fast GC-MS with a wide variety of front-end devices (SHS, DHS, TD, DSI, LD, Py, SPE, SPME, PTV, etc.). Ionisation modes employed are mainly El, Cl (for gases) and ICPI (for liquid and solid samples). Useful instrumental developments are noticed for TD-GC-MS. GC-SMB-MS is a fast analytical tool as opposed to fast chromatography only [104]. GC-ToFMS is now about to take off. GC-REMPI-MS represents a 3D analytical technique based on compound-selective parameters of retention time, resonance ionisation wavelength and molecular mass [105]. 

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