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J. Biochem. Biophys. Methods 43 (2000) 273–293 www.elsevier.

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Separation of metal chelates and organometallic compounds by SFC and SFE / GC
C.M. Wai*, Shaofen Wang
Department of Chemistry, University of Idaho, Moscow, ID 83844 -2343, USA

Abstract Supercritical fluid chromatography (SFC) combines the high diffusion coefficients of gas chromatography (GC) and the solubility properties of liquid chromatography (LC). SFC generally requires lower temperatures for chromatographic separations and thus is more suitable for analyzing thermally labile compounds including a number of metal chelates and organometallic compounds. SFC also allows interfacing between supercritical fluid extraction (SFE) and chromatographic analysis of metal-containing compounds. A large number of metal chelates and organometallic compounds can be separated by SFC. This article summarizes SFC separation of various chelates of transition metals, heavy metals, lanthanides and actinides as well as organometallic compounds of lead, mercury, and tin reported in the recent literature. This article also discusses SFC detection systems and the determination of solubility of organometallic compounds by SFC. © 2000 Elsevier Science B.V. All rights reserved.
Keywords: Supercritical fluid chromatography; Metal chelates; Organometallic compounds; Solubility

Abbreviations : acac, acetylacetone; AFS, atomic fluorescence spectrometry; CO 2 , carbon dioxide; CCl 2 F 2 , dichlorodifluoromethane; Cu(DDC) 2 , copper diethyldithiocarbamate; Cu(FDDC) 2 , copper bis(trifluoroethyl)dithiocarbamate; Cr(Phacac) 3 , tri(1-phenyl-1,3-butanedione)chromium(III); DMA, dimethylarsinic acid; Et 2 NHDDC, diethylammonium diethyldithiocarbamate; F 2 B(Phacac), difluoro(1-phenyl-1,3butanedione)boron(III); FID, flame ionization detection; FOD, 2,2-dimethyl 6,6,7,7,8,8,8-heptafluoro-3,5,octanedione; FPD, flame photometric detection; FT-IR, Fourier-transform infrared spectroscopy; GC, gas chromatography; GC-AED, gas chromatography with atomic emission detection; GC-ECD, gas chromatography with electron capture detection; GC-FPD, gas chromatography with flame photometric detection; H 2 DIB, 2,6-diacetylpyridine bis(benzoylhydrazone); HFA, hexafluoroacetylacetone; ICP-AES, inductively coupled plasma-atomic emission spectrometry; ICP-MS, inductively coupled plasma-mass spectrometric detection; LC, liquid chromatography; LiFDDC, lithium bis(trifluoroethyl)dithiocarbamate; MIP, microwaveinduced plasma; MMA, monomethylarsonic acid; NAA, neutron activation analysis; NaDDC, sodium diethyldithiocarbamate; Phacac, 1-phenyl-1,3-butanedione; SFC, supercritical fluid chromatography; SFE, supercritical fluid extraction; TBP, tributyl phosphate; TBPO, tributylphosphine oxide; TFA, trifluoroacetylacetone; THD, dipivaloylmethane; TOPO, trioctylphosphine oxide; TTA, thenoyltrifluoroacetone; TTA? Py, thenoyltrifluoroacetonepyridine *Corresponding author. Tel.: 1 1-208-885-6552; fax: 1 1-208-885-6173. E-mail address: (C.M. Wai) 0165-022X / 00 / $ – see front matter © 2000 Elsevier Science B.V. All rights reserved. PII: S0165-022X( 00 )00061-0


C.M. Wai, S. Wang / J. Biochem. Biophys. Methods 43 (2000) 273 – 293

1. Introduction Supercritical fluid extraction (SFE) of metal species and organometallic compounds has been the subject of many reports in recent years. Carbon dioxide (CO 2 ) is a gas of choice in SFE because of its moderate critical constants (T c 5 318C, Pc 5 73 atm, rc 5 0.47 g / ml), inertness, and availability in pure form. Major advantages of extracting metal species using supercritical CO 2 include minimization of waste solvent generation and direct removal of analytes from solid samples. One approach of SFE of metals is by converting charged metal ions into neutral metal chelates using organic chelating agents dissolved in supercritical CO 2 [1–4]. Important considerations for the selection of suitable ligands for this in situ chelation–SFE of metal ions include good solubility and stability of the complexing agents and their metal complexes in supercritical CO 2 . Organometallic compounds usually are extractable by supercritical CO 2 . Derivatization is sometimes needed to enhance the solubility of certain organometallic compounds in supercritical CO 2 . Quantification of the extracted metal chelates and organometallic compounds can be achieved by supercritical fluid chromatography (SFC). SFC combines the high diffusion coefficients of gas chromatography (GC) with the solubility properties of liquid chromatography (LC). Compared with GC, SFC generally requires lower temperatures for chromatographic separations and thus is more suitable for analyzing thermally labile compounds. Furthermore, using CO 2 as the mobile phase in SFC will enormously reduce the waste organic solvent generation. Although most of the SFC reports to date have dealt with organic compounds, the first report regarding the application of SFC in 1962 was with organometallic compounds [5]. Using GC for separation of metal chelates, difficulties often arise due to their low vapor pressures. To increase volatility of metal chelates by raising temperatures often causes decomposition of the analytes during GC separation. In LC, problems arise from limited resolution, degradation, and irreversible adsorption of the analytes to the stationary phase. SFC, which combines the solubility property of LC and the diffusivity of GC, can often overcome the detection and separation problems associated with GC or LC analysis of metal-containing compounds. Since solubility is an important factor in SFC separation, we shall start our discussion with the solubilities of metal chelates and organometallic compounds in supercritical CO 2 .

2. Solubility of metal chelates and organometallic compounds in supercritical CO 2 The solubilities of metal complexes in supercritical CO 2 reported in the literature vary significantly depending on the chemical nature of the complexes. In 1991, Wai et al. [6] first reported the solubilities of a number of metal dithiocarbamates in supercritical CO 2 determined by UV-VIS spectroscopy using a high-pressure view-cell with quartz windows. A significant finding in this study is the observation that fluorinated metal dithiocarbamates exhibit unusually high solubilities relative to their non-fluorinated analogues, typically by 2 to 3 orders of magnitude. For example, the solubility of copper

6) 3 10 2 6 (5. Carrott and Wai [12] measured the solubilities of UO 2 (NO 3 ) 2 ? 2TBP (uranyl nitrate tributyl phosphate) and UO 2 (TTA) 2 ? TBP in supercritical CO 2 . Biophys. a number of fluorinated chelating agents were tested for SFE of metals and for SFC of metal complexes [1–4. This solubility behavior was utilized by Lin et al. Metal chelates formed by fluorinated b-diketones and macrocyclic compounds were also found to have significantly higher solubilities in supercritical CO 2 relative to their non-fluorinated analogues [2. However. S. Biochem. Table 1 shows the solubilities of some metal dithiocarbamate chelates in supercritical CO 2 [1.5) 3 10 2 5 24 Pressure (atm) 100 100 100 100 100 100 150 150 150 150 150 150 SF phase CO 2 CO 2 CO 2 CO 2 CO 2 CO 2 CO 2 CO 2 CO 2 CO 2 CO 2 1 5% MeOH CO 2 1 5% MeOH . Wai. the solubility of copper bis(trifluoroethyl)dithiocarbamate Cu(FDDC) 2 . the solubility of the complex in supercritical CO 2 is about two orders of magnitude lower than its TBP coordinated complex UO 2 (TTA) 2 ? TBP. In recent years.6] Metal chelate Cu(FDDC) 2 Cu(DDC) 2 Ni(FDDC) 2 NI(DDC) 2 Co(FDDC) 3 Co(DDC) 3 Bi(FDDC) 3 Bi(DDC) 3 Hg(FDDC) 2 Hg(DDC) 2 Hg(FDDC) 2 Hg(DDC) 2 Solubility (mol / l) (9.060. [14. the solubility of the metal complex in supercritical CO 2 can be significantly increased. An interesting observation is that if a water molecule is coordinated with uranyl–TTA complex as in the case of UO 2 (TTA) 2 ? H 2 O. where TTA is thenoyltrifluoroacetone.M.2) 3 10 2 6 (7.0) 3 10 2 7 (8.060.260. Apparently.7–10].260. Wang / J.6) 3 10 2 6 (1. After this report.6) 3 10 2 4 (2. coordinated water molecules due to its polar nature can reduce the solubility of metal chelates in supercritical CO 2 .4) 3 10 2 2 (3.261.0) 3 10 2 4 (8.361.0) 3 10 2 4 (9.060.4) 3 10 2 6 (7. These uranyl complexes show very high solubilities in supercritical CO 2 . These high-pressure fiber-optic cells are simple and economic to build.1 3 10 2 4 M at the same temperature and pressure [6].060. high-pressure fiber-optic cells were developed for spectroscopic measurements in supercritical CO 2 [12.3) 3 10 (1.561. If the coordinated water molecule is replaced by a suitable organic ligand. Fiber-optic cells of different pathlengths can be assembled together allowing solubility measurements to be carried out over a wide concentration range.13]. a fluorinated analogue of Cu(DDC) 2 .11].15] for Table 1 Solubility of fluorinated (FDDC) and non-fluorinated diethyldithiocarbamates (DDC) in supercritical CO 2 at 508C [1.160.1 3 10 2 6 mol / l (M). The CO 2 -philic behavior of fluorinated metal chelates observed in this study is very important for the subsequent development of SFE techniques for metals.C. Using this technique.460.160. a fluorinated b-diketone commonly used for solvent extraction of lanthanides and actinides. was reported to be of the order of 9.6].4) 3 10 2 3 (8. Methods 43 (2000) 273 – 293 275 diethyldithiocarbamate Cu(DDC) 2 in CO 2 at 508C and 100 atm was found to be around 1.

1). oven temperature: 808C. (4) Eu(FOD) 3 ? 2TBPO. These authors used SFC retention data combined with a small number of experimentally determined solubility measurements to model the solubility of ferrocene in supercritical CO 2 . It was also shown that the same equation-of-state. 5 atm / min increase.M.18]. Peaks: A (1) chloroform. (6) La(FOD) 3 ? 2TBPO.008 0. Biophys.276 C. Biochem. could be used to predict quantitatively both supercritical fluid solubility and Table 2 Solubility of lanthanide b-diketonates in supercritical CO 2 at 408C [16] Metal complex UO 2 (TTA) 2 ? X X 5 TBP X 5 TOPO X 5 TBPO X5H2O UO 2 (NO 3 ) 2 ? 2TBP Solubility (mol / l) 200 atm 0. (5) Pr(FOD) 3 ? 2TOPO. B (1) chloroform.0003 0.0002 0. (5) Pr(FOD) 3 ? 2TBPO. Wang / J.003 0.4 SF phase CO 2 CO 2 CO 2 CO 2 CO 2 CO 2 . (2) TOPO. Methods 43 (2000) 273 – 293 Fig. (6) La(FOD) 3 ? 2TOPO.0015 0. SFC chromatograms of lanthanide FOD adducts with (A) TBPO and (B) TOPO.00017 0. S. (4) Eu(FOD) 3 ? 2TOPO. FID: 3908C (Ref. [14]). SFC conditions: initial 80 atm.0001 0. The solubility of ferrocene was studied extensively by Clifford and Bartle’s group at the University of Leeds [17. SFC separation of a number of lanthanide b-diketone complexes by means of adduct formation with organophosphorus reagents (Fig. (2) TBPO. Wai. (3) Er(FOD) 3 ? 2TBPO. Some relevant solubilities of lanthanide b-diketonates in supercritical CO 2 are shown in Table 2 [16].01 0. with the same parameters. 1. (3) Er(FOD) 3 ? 2TOPO.2 250 atm 0. Organometallic compounds usually are soluble in supercritical CO 2 .

07 9. Wai et al. as shown in Table 3 [21]. [20] demonstrated that the retention behavior of a range of ferrocene derivatives in SFC could be predicted based on a knowledge of simple parameters such as the solubility parameter of the solute.62 8. Biochem. Wang / J. correlating with the general observation for organic compounds where aromatic substituted systems showed the lowest solubilities. [22] have studied the solubilities of 10 copper(II) and five chromium(III) b-diketonates in supercritical fluid CO 2 . [22] observed that the fluorinated b-diketonates showed higher solubilities. The Peng–Robinson equation-ofstate and van der Waals’ mixing rules were employed in their modeling.M. This illustrates that for a given metal system. Similar trends were observed for the solubilities of the Cr(III) b-diketone complexes in supercritical CO 2 (Fig. molar volume of the solute and the physical characteristics of the chromatographic column. The prediction was further tested by studying a range of ferrocene derivatives with very different functionalities.8 9. The predicted solubilities fitted well with the Table 3 Solubility parameters of ferrocene derivatives in supercritical CO 2 [21] Compounds Ferrocene Ethyl ferrocene t-Butyl ferrocene n-Butyl ferrocene di-t-Butyl ferrocene tri-t-Butly ferrocene tetra-t-Butyl ferrocene N. The observed trends indicate that the solubility is strongly dictated by the character of the hydrocarbon or fluorocarbon shell surrounding the central metal atom. [6]. with the hexafluoroacetylacetone complexes having the highest values. The authors also measured the solubility of a number of metalcontaining complexes for thermodynamic modeling and prediction of solubility in supercritical CO 2 at varying operational conditions. 2). Lagalante et al. ranging from the parent compound ferrocene to N. Experimental results also indicated the inverse relationship between solubility and retention data in SFC if the same column was used [17–19].75 Molar volume (cm 3 / mol) 122.7 172. The lowest solubility was observed for the benzyl-substituted b-diketone complexes.6 447.39 9.33 8. Biophys. [24] recently developed a dynamic measurement technique to determine solubilities of chelating agents and metal chelates in supercritical CO 2 . the nature of the ligand side-chain influences the solubility of the metal complex in accordance with the ‘regular solution’ theory [23].3 204 204.N-Dimethylaminomethyl ferrocene Solubility parameter (mol / l) 10. Solubilities of cupric acetylacetonate and copper diethyldithiocarbamate were measured in supercritical CO 2 .9 196 . Methods 43 (2000) 273 – 293 277 the temperature dependence of retention in SFC.81 9. S. Lagalante et al. The solubility of copper diethyldithiocarbamate in supercritical CO 2 was found to agree with the results reported earlier by Laintz et al. Akgerman et al.N -dimethylaminomethyl ferrocene.C.5 285.73 8. Wai.3 366. A direct correlation was observed between the metal complex solubility and the Hildebrand solubility parameter of the free ligand.

The overall analytical results agreed well with those determined by solvent extraction followed by neutron activation analysis (NAA) and inductively coupled plasma-atomic emission spectrometry (ICP-AES). 3. Biochem. SFC separation of metal chelates-transition metals and heavy metals Arsenic and antimony are two toxic elements which show different toxicological and physiological behavior depending on their oxidation states and chemical forms. [22]).25]. The organic arsenic compounds. Plot of Ln( y 2 ) solubility of various copper(II) and chromium(III) b-diketonates in supercritical CO 2 at a density of 0. Ni. Sb and Bi with excellent resolutions using a 5-m SB-Methyl-100 100-mm i. Methods 43 (2000) 273 – 293 Fig. column (Fig. Wang / J. A number of inorganic and organic species of arsenic can also be determined using solvent extraction or SFE followed by the SFC method [8. Hg. Fe. For instance. As. Co. inorganic arsenite (As(III)) is more toxic than arsenate (As(V)) and organic arsenic compounds show less toxicity than the inorganic species. Wai. CH 3 AsO(OH) 2 (monomethylarsonic acid. S. Monitoring arsenic species in natural waters or waste streams is important for environmental studies. Laintz and Wai [8] in 1992 demonstrated that arsenic and antimony-bis(trifluoroethyl)dithiocarbamate complexes could be separated by SFC from a mixture containing Zn. 3). 2.874 g ml 2 1 versus Fendors’ solubility parameter of the free ligand (Ref.278 C. MMA) and (CH 3 ) 2 AsO(OH) (dimethylarsinic . Biophys.d. experimentally measured data for Cu(II) acetylacetonate and Cu(II) diethyldithiocarbamate.M.

Co(FDDC) 3 . Fe(FDDC) 2 . Wai. Pentavalent concentrations were then . [8]). in aqueous solutions were converted to CH 3 AsI 2 and (CH 3 ) 2 AsI. d. simultaneous separation and quantification of As(III) and Sb(III) in natural water and urine samples were demonstrated by the same authors using SFE with LiFDDC as an extractant followed by SFC analysis of the extracted FDDC complexes [9]. The resulting FDDC chelates. Sb(FDDC) 3 . Biophys. CH 3 As(FDDC) 2 and (CH 3 ) 2 As(FDDC). and sulfuric acid [8]. 3. f. S. Peaks: a. respectively. Zn(FDDC) 2 . Bi(FDDC) 3 .C. acid. Chromatogram produced using a Lee Scientific 5 m 3 100 mm I. sodium thiosulfate. 90%. i. The iodides were extracted with FDDC into chloroform as CH 3 As(FDDC) 2 and (CH 3 ) 2 As(FDDC). using a mixture of potassium iodide.M. Na(FDDC). b. In a subsequent report. Biochem. As(FDDC) 3 . As(FDDC) 3 . c. SFC conditions: 80-nl sample injected at 1008C oven temperature with a hold time of 6. A second aliquot of sample was reduced using sodium thiosulfate and potassium iodide for the determination of total As and Sb. Wang / J. were separated by SFC and the recovery was generally . SB-methyl-100 Superbond capillary column.5 min at 100 atm followed by a 4. Methods 43 (2000) 273 – 293 279 Fig. (Ref.0 atm / min ramp to 200 atm. g. Ni(FDDC) 2 . Hg(FDDC) 2 .D. h. DMA). e.

Co(III). Metal diisobutyldithiocarbamate complexes including Zn(II). Cd(II). Twenty-three out of these 43 metal acetylacetonates studied were eluted without apparent decomposition. Column adsorption and decomposition of some of the acetylacetonates also occurred during the SFC analysis. and Zn(II) ions from filter paper. In these studies.3-butanedione)boron(III)). Co(II). In the first SFC experiments with b-diketonates. Fe(III) and As(III) were also separated by capillary SFC using a 10 m 3 50 mm i. It was observed that increasing the concentration of the modifier would reduce the retention times of the analytes. The chromatographic separation was better . The best results for the SFC analysis of metal b-diketonates using methanol modified CO 2 were obtained with columns packed with polar stationary phases [30]. showed a shorter retention time than its non-fluorinated analogue Cr(acac) 3 .M. Ni(II). Wang / J. Biochem. Pb(II). and the most favorable isomeric resolution was obtained with a phenyl stationary phase. The recoveries of Cu(II). CCl 2 F 2 was also used in a subsequent investigation of 43 different metal acetylacetonates [29]. Cd(II). Co(acac) 3 and F 2 B(Phacac) (difluoro(1phenyl-1. Neat CO 2 or methanol modified CO 2 was used as the mobile phase. Co(II). and Cr(Phacac) 3 (1-phenyl-1. Cr(acac) 3 . SB-Phenyl-50 column at 1208C by Manninen et al. This analytical method produces satisfactory recovery results for arsenic and antimony speciation studies.3-butanedione) on a phenyl packed column at 998C and an inlet pressure of 3800 psi [30]. Utilizing a packed column. Metal b-diketonates are the most commonly studied metal chelate system using GC.d. Cu(II). Separation of 23 metal acetylacetone complexes including Ru(II). Cr(acac) 3 . Good resolutions were obtained in the separation of Cr(HFA) 3 (hexafluoroacetylacetone). and silica gel ranged from 70% to 100%. Biophys. [27].280 C. Laintz et al. Analyses were carried out using a Lee Scientific Series 600 SFC equipped with flame ionization detection (FID). SFC was also able to separate a mixture of b-diketonates including Fe(acac) 3 (acetylacetone). This probably is due to the fact that methanol increases the solubility of the b-diketonates in CO 2 and reduces their activity in the stationary phases. sand. Co(III). S. The extraction of Cu(II).31]. Wai. and Zn(II) ion from solid samples was carried out with LiFDDC in 5% methanol modified CO 2 at 200 atm and 408C followed by GC-AED. methanol was used as a modifier to reduce the retention times of the metal chelates and a UV detector was employed for quantification. Concentrations ranging from 1 to 150 ppb for natural water and 1 to 10 ppm for urine samples for both As and Sb trivalent and pentavalent species can be determined using this method. Methods 43 (2000) 273 – 293 determined by subtraction. Cd(II). Supercritical CO 2 was used as the mobile phase in several SFC studies on bdiketonate complexes [30. A number of transition metals were investigated in SFE-gas chromatography with atomic emission detection (GC-AED) [26]. Cr(HFA) 3 . LC and SFC. 14 different metal chelates of TTA were studied. [32] separated the geometric isomers of Cr(III) and Rh(III) chelates of trifluoroacetylacetone (TFA) and TTA using packed column SFC. a fluorinated acetylacetonate. with a phenyl column at 1008C and inlet pressure of 4750 psi [30]. Ir(III). Rh(III). as evidenced by broad peaks with considerable tailing. using dichlorodifluoromethane (CCl 2 F 2 ) as the mobile phase with a column packed with 2% Kel-F wax on Chromosorb W [28]. Pd(II) and Pt(II) using supercritical CCl 2 F 2 as the mobile phase and with columns made of Epon 1001 resin on Chromosorb W at 1158C and 800 psi was carried out by Karayannis and Corwin [29].

Biochem. Macrocyclic calixarene compounds can be made quite soluble in supercritical fluid CO 2 by fluorination. A number of metal ions are known to form lipophilic complexes with the deprotonated forms of the simplest phenolic calixarene.M. the ferric ions were extracted into supercritical CO 2 as a heptadecafluorodecane derivatized calix[4]arene hydroxamate Fe(III) complex. Zorbax Rx C18. This stationary phase was also chosen for a chromatographic study of the chelating agent H 2 DIB. Reports on the utilization of macrocyclic compounds as chelating agents in SFE and SFC are limited. They are described as ‘molecular baskets’ since they have high ionophoric selectivity and form inclusion complexes with many metal ions. The stability of metal complexes and high solubility in methanol modified supercritical CO 2 allowed a uranyl determination in SFC in less than 2 min. and the copper complex CuDIB.2-dimethyl 6. compared to the 10 ml used in reversed phased-liquid chromatography.6-Diacetylpyridine bis(benzoylhydrazone) (H 2 DIB) was used as a chelating agent for uranium. A lesser amount of solvent.7. The results indicate that packedcolumn SFC can provide quantitative. The hydrated lanthanide-FOD (2. 10% chloroform modified supercritical fluid CO 2 showed a better separation for the calixarenes C1 and C2 compared with that using methanol as the modifier. Calixarenes are macrocyclic complexing agents that possess a lipophilic moiety (upper rim) and a metal coordinating moiety (low rim). and a flow rate of 3 ml / min. Wang / J. peak efficiency. Spherisorb ODS2. [34] reported SFC and SFE of metals with the hexameric and tetrameric p -tert-butylcalixarenes.15] studied the separation of lanthanide b-diketone complexes using CO 2 as the mobile phase in SFC. reliable and fast uranium and copper determination. Inertsil ODS2. They demonstrated the extraction of Fe(III) using supercritical fluid CO 2 containing a new fluorinated calix[4]arene tetrahydroxamic acid.8-heptafluoro-3.7. SFC separation of lanthanide and actinide complexes A new approach of determination of uranium by packed-column SFC was reported by Martin-Daguet et al. The determination of chromium complexes was done by both FID and inductively-coupled plasma with mass spectrometric detection (ICP-MS). Biophys. Wai et al. Capcell-Pack C18.C.8.6. 2. [33] for the determination and separation of chromium b-ketonate complexes and a thermally labile organochromium dimer. SFC studies were carried out with p -tert-butylcalix[4]arene ( C1 ) and p -tert-butylcalix[6]arene ( C2 ) using a mobile phase of methanol / chloroform-modified CO 2 at 3700 psi and 558C. Capcell-Pack C18 provided the best results in terms of retention time. In this case.5-octanedione) complexes exhibit strong intermolecular interactions and decomposition in SFC. Formation of adducts of the lanthanide b-diketones . and symmetry for the study of chromatographic behavior of uranyl complex UO 2 DIB. is required for each analysis in SFC. Glennon et al. [14. 4. Methods 43 (2000) 273 – 293 281 for chelates with TFA than for the corresponding chelates with TTA. SFC has also been investigated by Caruso et al. Wai. | 500 ml. [35]. methanol consumption. SFC properties on different stationary phases such as Nova-Pack C18.8. S. Asahipac C18 and PRP-1 and the influence of the methanol content in the CO 2 mobile phase were investigated.

TTA. Pr(FOD) 3 . Typically. The SFC separation was done with an Inertsil 2. Ln(FOD) 3 ? 2TBP [15]. Wang / J. and a CO 2 flow rate of 0. Ln(FOD) 3 ? 2TBPO . in terms of industrial and agricultural applications. FOD and THD displayed high solubilities in supercritical CO 2 and have better chromatographic behavior compared to the corresponding chelates of TFA. mixed with a chelating agent. The organotin compounds are identified by comparison with the chromatograms obtained from a standard containing nine organotin compounds. In situ chelation-SFE and GC-AED for the determination and speciation of 13 organotin compounds in soils and sediments were also developed and evaluated by the same authors [38]. TTA. Recoveries ranging from 70% to 90% were obtained for most of ionic organotin compounds when sodium diethyldithiocarbamate (NaDDC) ligand was used. [37]. Analysis of the soil extracts was done by GC-AED. 3 250 mm 5 mm phenyl packed column. The chromatographic performance of lanthanide chelates of acac. FOD. Biophys. They are widely distributed in the environment.d. and TTA? Py. THD (dipivaloylmethane). when ionic compounds are bound to organic ligands or by ion-pair formation. and Pr(THD) 3 complexes showed excellent resolution at 1508C and 120 kg / cm 2 . However. and tin SFE of ionic compounds such as organotins (R m SnX 4 2 m . their solubility in supercritical CO 2 is significantly increased. Six tetraalkyltin compounds spiked to the topsoil samples were extracted by SFE with recoveries in the range of 90% to 110%. mercury.282 C. thus enabling the extraction of these compounds from environmental samples. [36]. m 5 1–3) from aqueous samples cannot be accomplished with neat CO 2 due to the charge neutralization requirement and weak solute–solvent interaction. TFA. Furthermore. Soil or sediment samples. Eu(TTA) 3 showed characteristic thermal decomposition in the mobile phase as a function of temperature. S. The ionic organotin compounds were derivatized to their corresponding pentylated derivatives before GCAED analysis. and are under intense scrutiny owing to their significant environmental impacts. and TTA? Py (thenoyltrifluoroacetonepyridine) adducts was investigated by Laintz et al. The stability sequence of lanthanide–FOD organophosphorus adducts was shown to follow the order Ln(FOD) 3 ? 2TOPO . retention behavior was demonstrated to be a temperature dependent function of volatility and solubility [36].M. Organotin compounds are becoming one of the most versatile groups of organometallic chemicals. SFC separation of organometallic compounds of lead.1 i. Lanthanide complexes of acac. The extracted analytes were treated with .03 ml / min. were extracted with 5% methanol modified CO 2 at 608C and 450 atm. SFC separation of Pr(acac) 3 . Biochem. diethylammonium diethyldithiocarbamate (Et 2 NHDDC). Six tetraalkyltin and seven ionic organotin compounds from spiked topsoil samples were extracted by 5% methanol modified supercritical CO 2 by Liu et al. Methods 43 (2000) 273 – 293 with a neutral donor such as tributylphosphine oxide (TBPO) or trioctylphosphine oxide (TOPO) could greatly improve their SFC behavior. Adduct formation was shown to improve the extraction efficiencies of lanthanides from different matrices by supercritical CO 2 containing a fluorinated b-diketone and an organophosphorus reagent [2]. Wai.3 ml / min and ethanol modifier flow rate of 0. 5.

[46] showed the application of supercritical CO 2 modified with 5% of MeOH to extract individual organomercury compounds including CH 3 HgCl. Liu et al. static extraction time. on line SFE-GC and SFE / SFC were also studied by the same authors [41]. An approach for simultaneous determination of butyl-. and cyclohexyltin compounds in aqueous environmental samples was subsequently investigated by the same authors [40]. followed by capillary GC-AED determination. Knochel et al. Methods 43 (2000) 273 – 293 283 pentylmagnesium bromide to convert the ionic organotin compounds into their neutral derivatives. hydrogen flow rate. [47] demonstrated that interfacing SFC with atomic fluorescence spectrometry (AFS) is suitable for the determination of organomercury compounds. In situ derivatization before SFE using neat CO 2 or modified CO 2 . Detection variables including temperature. The analytes recovered were analyzed by GC-FPD. SFE was conducted in mild thermal conditions at 408C and 350 atm. Ionic organotins were ethylated by sodium tetraethylborate first. The analytical procedures for methyl mercury determination were based on GC-ECD [45]. Organotin compounds in a marine paint and food matrices were determined and separated by SFC using formic acid modified CO 2 and polymer encapsulated silicabased stationary phases with FID [42]. temperature. HgS) in soil and sediment samples.M. whereas monoorganomercurials and inorganic mercury compounds have to be converted into compounds with lower polarity in order to be soluble in supercritical CO 2 . The favorable chromatographic properties of the ionic tin compounds are probably due to the formation of formate salts which show reduced tailing and decomposition.C. and air flow rate were optimized by a combination of factorial experimental design. (C 6 H 5 ) 2 Hg and inorganic mercury compounds (HgCl 2 . The recoveries of organotins from spiked seawater ranged from 82 to 104% at the higher spiked level and from 79 to 115% at the lower level. A recent review summarized the SFE conditions for methyl mercury extraction from aquatic sediments. amount of HCl and contact time between HCl and the sample prior to extraction. Wang / J. This can be done by complexation of monoorganomercurials with NaDDC. diphenyltin. These results indicate that SFE followed by GC-AED analysis is a promising technique for the determination of trace organotin compounds in environmental soil and sediment samples. Dibutyltin. and less irreversible adsorption in a separation system saturated with formic acid. A single flame photometric detector (FPD) has been optimized for capillary SFC of trialkyltin chlorides by Bayona et al. Biochem. which later were analyzed by GC-AED. phenyl-. followed by trace enrichment of the derivatized organotins on a C18 disk and extracted with supercritical CO 2 . With a hexyl derivatization by hexylmagnesium bromide to the organotin compounds on the sediment. Wai. and so on. Blake et al. Factor designs have been used for the simultaneous determination of various analytical SFC parameters such as CO 2 flow rate and density. S. The retention time of the individual compounds was found to depend only upon the structure of the cation. HgO. Biophys. Diorganomercurials can be analyzed without any prior treatment. Optimization of SFE of methylmercury in marine samples followed by GC analysis with electron capture detection (GC-ECD) was also developed [44]. pressure. [43] recently reported that organotin compounds could also be determined by capillary SFC with ICP-MS detection. and triphenyltin chlorides were successfully analyzed using a linear programming in SFC [39]. [39]. Even for thermal labile . C 6 H 5 HgCl.

In addition to metalloporphyrins. from spiked sediment samples were reported. Methanol modified CO 2 was required to elute the substituted ferrocenes from the columns in | 30 min. and dicyclopentadienyl TiCl 2 was successfully separated on a 1-m by 1 / 8-inch o. VO. 4a is given in Fig. and diethyl-lead. 5 [21]. at 50–808C and 2400–5000 psi [30].d. [5] separated nickel–etioporphyrin complexes using a column packed with 33% polyethyleneglycol (Carbowax 20 M) on Chromosorb W. 6. and 80%. Wai and co-workers [20] demonstrated the separation of a range of ferrocene derivatives using capillary SFC and discussed the prediction of SFC retention behavior of ferrocene derivatives using the Hildebrand Equation [23]. respectively. The major problems with separation of porphyrin-type complexes seem to be their irreversible adsorption on the chromatographic column. A synthetic mixture of ferrocene. Four nickel and vanadyl porphyrin complexes were investigated as a function of temperature (50 to 1008C) and pressure (3000 to 4000 psi) by Taylor et al. cyclopentadienyl complex and its derivatives were studied by Jentoft et al. S. The chromatography illustrates that a wide range of ferrocene derivatives can be baseline . Sn and VO etioporphyrin II complexes [49]. Co. Cu. Pd.M. A procedure for the SFE of ionic alkyl-lead species from solid samples was reported by Johansson et al. These nickel and vanadyl porphyrin complexes were successfully separated using 20% methanol modified CO 2 as the mobile phase on a C18 packed column and with UV detection. Klesper et al. This may be associated with the incomplete coordination of the metals with the porphyrin ring and their subsequent ionic interactions with the chromatographic column. Mg. with CCl 2 F 2 (1128C). and quantified by GC-MS. The separation of a mixture of the seven ferrocene derivatives shown in Fig. Ni.284 C. The same mobile phase was later used to separate Cu. Biochem. The results suggest that the C18 stationary phase is more selective for the separation of porphyrinic derivatives compared with silica or phenyl stationary phases. for trimethyl-lead. at a maximum pressure of 2000 psi. using CO 2 as the mobile phase [52]. triethyllead. Wai. TiO. phenyl. Biophys.19-diacetylferrocene was separated by CO 2 / methanol (98 / 2) mobile phase on four different SFC columns of ODS. acetylferrocene and 1. These etioporphyrin II metal chelates were studied at 1458C and 1000–1700 psi and separation of Ag. SFC separation of other organometallic compounds In the early work on high pressure gas chromatography above critical temperatures. Mn. which decompose in GC conditions. Ni. Etioporphyrin II complexes of other transition metals were analyzed by Karayannis et al. Mg. Pt. [51]. Wang / J. cyclopentadienyl Mn(CO) 3 . can still be analyzed using this SFC-AFS system. Recoveries of 96%. such as alkoxyethylmercurials. [48]. and Zn etioporphyrin II complexes was carried out with a column of 10% Epon 1001 resin on Chromosorb W [50]. [50] in subsequent studies. and silica. The ionic alkyl-leads were extracted as diethyldithiocarbamate complexes into hexane. PRP-1. propylated using a Grignard reagent. Methanol was found to be a better modifier compared with water and acetone in this separation. 106%. stainless steel column packed with a commercially available Carbowax 400. and CHClF 2 (968C) as the mobile phases. [52]. In another report. a mixture of ferrocene. Methods 43 (2000) 273 – 293 compounds.

. ethyl ferrocene (2). (b) Structures of ferrocene. phenyl ferrocene (5). 4. Wang / J. Wai. Biochem. (a) Structures of ferrocene derivatives shown in Fig. 5: ferrocene (1).M. Methods 43 (2000) 273 – 293 285 Fig. 6: acetyl ferrocene (1). S. n -butyl ferrocene (4). t -butyl ferrocene (3). acetyl ruthenocene (2). Biophys. acetyl osmocene (3).C. benzoyl ferrocene (6). dibenzoyl ferrocene (7). ruthenocene and osmocene derivatives shown in Fig.

Biophys. S. and osmocene. a different central atom in a dicyclopentadienyl system (Fig. Wang / J. Phenyl ferrocene. n -butyl ferrocene (4).5 atm / min from 80 to 400 atm. dibenzoyl ferrocene (7). ruthenocene. benzoyl ferrocene and dibenzoyl ferrocene were all strongly retained on the column at low pressures but were eluted when the pressure reached 400 atm. ethyl ferrocene (2). 4b). Insert: pressure ramp used. 5. Methods 43 (2000) 273 – 293 Fig. The separation of cyclopentadienyl complexes involving row 2 metals from row 3 metals in the Periodic Table is more challenging since for these groups the transition metals are very similar in terms of size and physical properties. t -butyl ferrocene (3). 6) suggest that SFC can provide baseline resolution for these three compounds [21]. SFC separations of ferrocene.286 C. Conditions: T 5 1008C. t -butyl ferrocene and n -butyl ferrocene are all eluted within 10 min at low pressures (80–120 atm). Solvent: methylene chloride. benzoyl ferrocene (6). SFC determination of solubility of organometallic compounds A number of studies concerning the behavior of organometallic compounds in . Typical chromatogram demonstrating baseline separation of a range of ferrocene derivatives of varying physical properties: ferrocene (1). resolved using pressure-programmed capillary SFC. Biochem. The results (Fig.M. The compounds of ferrocene. ethyl ferrocene. 7. were conducted at 1008C using a pressure ramp of 2. phenyl ferrocene (5). Wai. A pressure program was thus used which caused all seven compounds to elute with baseline resolution being achieved under 12 min.

acetyl osmocene (3). The solubility of Ru catalyst was measured quantitatively by passing Ru catalyst / supercritical CO 2 through a fine filter at 508C and 120 atm [53]. Wai et al. Biochem. p. acetyl ruthenocene (2). Wang / J. Conditions: T 5 1008C. [18] used SFC retention data coupled with a small number of experimentally determined solubility data to determine the solubility of ferrocene in supercritical CO 2 under various conditions. Solvent: methylene chloride.18. Ferrocene and its derivatives have been extensively studied with regard to supercritical CO 2 solubility [17. [21] studied the behavior of ferrocene and its derivatives and separated ferrocene derivatives using capillary SFC.M.5 atm / min ramp from 80 to 400 atm. The catalytically active compound RuCl 2 [P(CH 3 ) 3 ] 4 was shown to be soluble in supercritical CO 2 . since it has been shown that the retention behavior of solutes is directly related to the solubility in the supercritical fluid [17. S. These studies indicate that a wide range of organometallic systems show high solubility in supercritical CO 2 . as evidenced by SFC investigations. It was shown that the SFC retention could be predicted from knowledge of simple parameters such as the . The high solubility of ferrocene can be interpreted as being due to the nature of bonding.20. Methods 43 (2000) 273 – 293 287 Fig. supercritical CO 2 have been carried out in terms of solubility. and catalysis [53–55]. 6. using a 2.C. Chromatogram demonstrating baseline separation of acetyl ferrocene (1). The capacity factors of the ferrocene derivatives were found to vary significantly with the chromatographic temperature and pressure.18].21]. Ferrocene is a system in which the metal’s 3d. and s orbitals are filled so that no free coordination sites are available for interaction with the solvating CO 2 . SFC provides a means for investigating the behavior of ferrocene and its derivatives. Wai. Cowey et al. reactivity. resulting in a system having properties resembling those of an aromatic compound. Biophys.

dsp is the solubility parameter of the stationary phase (cal 1 / 2 cm 2 3 / 2 ). The limitations of UV detection for SFC are related to sensitivity considerations. Eq. Vi is the pure solute molar volume (cm 3 ). the quicker it will elute from the column. As the supercritical fluid temperature increases at constant pressure. 2 2 (RT / Vi ) Ln(k 9 / r) 5 2 (d sp 2 d sf ) 2 2(dsp 2 dsf )di 1/2 23 / 2 (1) where di is the solubility parameter of the solute (cal cm ). which leads to a decrease in the solvating power of the supercritical fluid and leads to an increase in the analyte’s retention. Thus. and the physical characteristics of the chromatographic column. Wang / J. dsf is the solubility parameter of the supercritical fluid phase (cal 1 / 2 cm 2 3 / 2 ). and have the potential for high selectivity. For isobaric and isocratic SFC. at relatively low temperatures and low analyte vapor pressures. r is the ratio of the volume of the stationary phase to the volume of SF in the column.M. The following equation was derived by Brauer et al. and T is temperature (K). Biochem. This general relationship has been used to determine solubility [19. R is the ideal gas constant (cal mol 2 1 K 2 1 ). as the supercritical fluid temperature is increased. [30] described the separation of metal–acetylacetone complexes and porphyrinic derivatives by SFC with UV detection. (1) predicts a linear relationship between di and (RT / Vi ) Ln(k 9 / r). the density of the fluid decreases. Wai et al.51]. the volatility of the analyte also increases until the analyte vapor pressure becomes more important than supercritical fluid density.31. However. ranging from the parent compound ferrocene to N.288 C. the density of the supercritical fluid is the dominant factor.56]. the ratio of the solute between the two phases. [20] utilized SFC equipped with a FID with a 5-cm methyl silicone open tubular capillary column for determination of ferrocene. At this point. k 9 is the capacity factor. In general the more soluble a compound is in supercritical fluid CO 2 . Wenclawiak [31] and Ashraf-Khorassani et al. Detection system for SFC of metal-containing compounds Currently. A discussion of these assumptions was given by Bartle et al.57]. hence allowing a quantitative means of predicting retention behavior of solutes in SFC. resulting in a decrease in analyte retention time. Biophys. Methods 43 (2000) 273 – 293 solubility parameter of the solute. For instance. This phenomenon has been observed for the retention of lanthanide b-diketone complexes and polyaromatic compounds analyzed by packed column SFC [36. The theory was further verified by a range of ferrocene derivatives with very different functionalities.20. There are some assumptions that must be made for a specific equation to work. 8. whereas FID is constrained to fluids yielding no significant ionization during detection (such as CO 2 ). the solubility of the analyte in the supercritical fluid starts to increase. which are universal. S. most commonly used detectors for SFC and GC are UV absorption and FID [8. [19]. . Wai. molar volume of the solute.N -dimethylaminomethyl ferrocene [20]. sensitive. [20] to show the relationship between di and (RT / Vi ) Ln(k 9 / r).

Several element-selective optical detectors.d. [69] used photodiode array UV and ICP serial detectors coupled with packed micro-column SFC for determination of metal–acac complexes.63]. and ICP [62.M. more interference will appear by FID than by ICP-MS. expense. element-selective detectors seem attractive for the detection of metal-containing compounds in SFC.66] succeeded in coupling the ICP-MS with SFC for the separation and determination of organometallic compounds. Both ICP-AES [67] and microwave induced plasma-atomic emission spectrometer (MIP-AES) [58] have been successfully used as element selective detectors in the SFC separation of ferrocene compounds.d. and differences were attributed to fluctuations in the temperature of the transfer line used in the SFC-ICP-MS interface. This new approach suggests the potential for simultaneous determination of mixtures of organometallic pollutants of environmental interest such as As. [64] interfaced the ICP-MS with SFC to separate the tetraalkyltin compounds with detection levels in the sub-picogram range. The SFC-ICP-MS system was also evaluated by comparing the results from an SFC-FID for the determination of tri. radiofrequency plasma detector [61].C. A single FPD attached to a capillary SFC system was used by Bayona et al. ICP-MS detection limits are superior to the FID results by one order of magnitude.53-mm i. Baseline resolution for the organotin compounds is accomplished in both FID and ICP-MS detection by using a longer column. Biophys. The use of a high-resolution MS can further enhance the capacity to resolve components of the same nominal molecular weight. Better resolution was obtained with FID. The major advantages of FID are low cost and ease of operation. and packed capillary columns of 0. to aid identification. sensitivity (in some cases).68] that greatly limits on-line detection. A number of authors [64. Pb. as in the case of nonspectrometric detectors such as FID. whereas the ICP-MS detector is more sensitive and selective. The off-line approach for FT-IR detection is particularly attractive because of the enhanced detection limits and the practical elimination of the solvent modifier [56. Biochem. For the same organotin compounds. ICP-MS provides excellent selectivity [64–66].and tetraorganotin compounds [66]. Jinno et al.94 nm. For the analysis of a real sample. The use of a micro-column in SFC allows the total effluent to be introduced into the plasma. Among several element-selective techniques. These detectors were employed in conjunction with packed microbore columns of 1-mm i. For example. The performance was evaluated by monitoring the Fe emission line at 259. and to eliminate background complication. and the absence of commercial instrumentation. Sn and Hg at ultra-trace levels. Wang / J. Shen et al.68]. have been studied extensively for SFC. [39] for analyzing trialkyltin chlorides. FT-IR has the ability to interpret quickly and unambiguously the presence or absence of specific organic functional groups in a sample molecule. Significant progress has been reported using Fourier transform infrared spectroscopy (FT-IR) as a detection method [56. Wai. The linear range was over three orders of magnitude (1–1000 pg). These metal– . The major disadvantages of off-line FT-IR detection include mechanical complexity. The advantage of FT-IR is that one can obtain molecular structure information from the compounds eluting from the column and not just retention times or area counts. such as the microwave-induced plasma detector (MIP) [58–60]. Methods 43 (2000) 273 – 293 289 In addition to UV and FID detection. S.

Supercritical fluid extraction of organic and inorganic mercury from solid materials. Wang / J.290 C. The development of more selective stationary phases for both packed and capillary column SFC is desirable. Biochem. and Zn(II). Wai CM. Yonker CR. Supercritical fluid extraction of lanthanides with fluorinated b-diketones and tributyl phosphate. . Brauer RD. The extraction and separation of metal chelates and organometallic compounds by SFE / SFC depend largely on the proper selection of chelating agents. The UV detector can provide UV spectra of acac complexes separated by SFC. Mn(III). [2] Lin Y. while ICP detector can supply elemental information for complex identification.and gas-phase detectors and particularly with FID.M. Anal Chem 1994.22:2875–8. Future developments With increasing demands for speciation information of elements of biological and environmental concern. Extraction of metal ions from liquid and solid materials by supercritical carbon dioxide. One attraction of SFC with CO 2 as the mobile phase is its compatibility with both liquid. Co(III). References [1] Wai CM. The compatibility of SFC with GC-type detectors and its usefulness for analyzing metal-containing compounds not amenable to GC or LC indicate that the future of SFC is bright. With modifiers.66:1971–5. Co(II). SFC analysis of more polar compounds is feasible.40:1325–30. Wai. Beckert WF. Wai CM. 9. It is expected that SFC applications will expand into the areas new to chromatographic methods or in which shortcomings of either GC or LC are well established. Supercritical fluid extraction of trace metals from solid and liquid materials for analytical applications. Phosphorus and silicon-containing ligands also form highly soluble metal complexes in supercritical CO 2 . Wang S. Talanta 1993. Smith RD. Fluorinated ligands are effective for in situ chelation-SFE of metal ions and SFC of metal-containing compounds. Adduct formation is another technique for improving SFE and SFC efficiency of metal chelates. Methods 43 (2000) 273 – 293 acac complexes included Al(III). [3] Wai CM. Selective extraction and separation of metals using macrocyclic compounds in supercritical CO 2 is another area of interest for future development of SFE / SFC technology. Biophys. Ni(II). Lin Y. Replacing coordinated water in a metal chelate with an organic ligand has also been shown to increase its solubility in supercritical CO 2 and improving SFC separation. Mn(II). S. [4] Laintz KE. Cu(II). Anal Chem 1992. Cr(III). Anal Sci 1995.11:165–7. The range of application and sensitivity of detectors will probably be the major factor in determining the future growth of SFC. The preparation of columns that are stable to the solvating influences of polar supercritical fluids at elevated temperatures remains challenging. SFC offers the possibility of performing chromatographic analysis of metal chelates and organometallic compounds at lower temperatures and in less time than obtained with traditional GC. SFC should play a role in preparation and analysis of metalcontaining compounds in complicated matrices.

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