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J. Biochem. Biophys. Methods 43 (2000) 273293 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 uid chromatography (SFC) combines the high diffusion coefcients 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 uid 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 uid chromatography; Metal chelates; Organometallic compounds; Solubility

Abbreviations : acac, acetylacetone; AFS, atomic uorescence spectrometry; CO 2 , carbon dioxide; CCl 2 F 2 , dichlorodiuoromethane; Cu(DDC) 2 , copper diethyldithiocarbamate; Cu(FDDC) 2 , copper bis(triuoroethyl)dithiocarbamate; Cr(Phacac) 3 , tri(1-phenyl-1,3-butanedione)chromium(III); DMA, dimethylarsinic acid; Et 2 NHDDC, diethylammonium diethyldithiocarbamate; F 2 B(Phacac), diuoro(1-phenyl-1,3butanedione)boron(III); FID, ame ionization detection; FOD, 2,2-dimethyl 6,6,7,7,8,8,8-heptauoro-3,5,octanedione; FPD, ame 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 ame photometric detection; H 2 DIB, 2,6-diacetylpyridine bis(benzoylhydrazone); HFA, hexauoroacetylacetone; ICP-AES, inductively coupled plasma-atomic emission spectrometry; ICP-MS, inductively coupled plasma-mass spectrometric detection; LC, liquid chromatography; LiFDDC, lithium bis(triuoroethyl)dithiocarbamate; MIP, microwaveinduced plasma; MMA, monomethylarsonic acid; NAA, neutron activation analysis; NaDDC, sodium diethyldithiocarbamate; Phacac, 1-phenyl-1,3-butanedione; SFC, supercritical uid chromatography; SFE, supercritical uid extraction; TBP, tributyl phosphate; TBPO, tributylphosphine oxide; TFA, triuoroacetylacetone; THD, dipivaloylmethane; TOPO, trioctylphosphine oxide; TTA, thenoyltriuoroacetone; TTA? Py, thenoyltriuoroacetonepyridine *Corresponding author. Tel.: 1 1-208-885-6552; fax: 1 1-208-885-6173. E-mail address: cwai@uidao.edu (C.M. Wai) 0165-022X / 00 / $ see front matter 2000 Elsevier Science B.V. All rights reserved. PII: S0165-022X( 00 )00061-0

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1. Introduction Supercritical uid 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 [14]. Important considerations for the selection of suitable ligands for this in situ chelationSFE 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 . Quantication of the extracted metal chelates and organometallic compounds can be achieved by supercritical uid chromatography (SFC). SFC combines the high diffusion coefcients 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 rst report regarding the application of SFC in 1962 was with organometallic compounds [5]. Using GC for separation of metal chelates, difculties 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 signicantly depending on the chemical nature of the complexes. In 1991, Wai et al. [6] rst 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 signicant nding in this study is the observation that uorinated metal dithiocarbamates exhibit unusually high solubilities relative to their non-uorinated analogues, typically by 2 to 3 orders of magnitude. For example, the solubility of copper

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diethyldithiocarbamate Cu(DDC) 2 in CO 2 at 508C and 100 atm was found to be around 1.1 3 10 2 6 mol / l (M). However, the solubility of copper bis(triuoroethyl)dithiocarbamate Cu(FDDC) 2 , a uorinated analogue of Cu(DDC) 2 , was reported to be of the order of 9.1 3 10 2 4 M at the same temperature and pressure [6]. The CO 2 -philic behavior of uorinated metal chelates observed in this study is very important for the subsequent development of SFE techniques for metals. After this report, a number of uorinated chelating agents were tested for SFE of metals and for SFC of metal complexes [14,710]. Metal chelates formed by uorinated b-diketones and macrocyclic compounds were also found to have signicantly higher solubilities in supercritical CO 2 relative to their non-uorinated analogues [2,11]. Table 1 shows the solubilities of some metal dithiocarbamate chelates in supercritical CO 2 [1,6]. In recent years, high-pressure ber-optic cells were developed for spectroscopic measurements in supercritical CO 2 [12,13]. These high-pressure ber-optic cells are simple and economic to build. Fiber-optic cells of different pathlengths can be assembled together allowing solubility measurements to be carried out over a wide concentration range. Using this technique, 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 , where TTA is thenoyltriuoroacetone, a uorinated b-diketone commonly used for solvent extraction of lanthanides and actinides. These uranyl complexes show very high solubilities in supercritical CO 2 . An interesting observation is that if a water molecule is coordinated with uranylTTA complex as in the case of UO 2 (TTA) 2 ? H 2 O, 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. Apparently, coordinated water molecules due to its polar nature can reduce the solubility of metal chelates in supercritical CO 2 . If the coordinated water molecule is replaced by a suitable organic ligand, the solubility of the metal complex in supercritical CO 2 can be signicantly increased. This solubility behavior was utilized by Lin et al. [14,15] for

Table 1 Solubility of uorinated (FDDC) and non-uorinated diethyldithiocarbamates (DDC) in supercritical CO 2 at 508C [1,6] 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) (9.160.3) 3 10 (1.160.2) 3 10 2 6 (7.261.0) 3 10 2 4 (8.561.0) 3 10 2 7 (8.060.6) 3 10 2 4 (2.460.4) 3 10 2 6 (7.361.0) 3 10 2 4 (9.060.6) 3 10 2 6 (5.060.4) 3 10 2 3 (8.260.6) 3 10 2 6 (1.260.4) 3 10 2 2 (3.060.5) 3 10 2 5
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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

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Fig. 1. SFC chromatograms of lanthanide FOD adducts with (A) TBPO and (B) TOPO. Peaks: A (1) chloroform, (2) TBPO, (3) Er(FOD) 3 ? 2TBPO, (4) Eu(FOD) 3 ? 2TBPO, (5) Pr(FOD) 3 ? 2TBPO, (6) La(FOD) 3 ? 2TBPO. B (1) chloroform, (2) TOPO, (3) Er(FOD) 3 ? 2TOPO, (4) Eu(FOD) 3 ? 2TOPO, (5) Pr(FOD) 3 ? 2TOPO, (6) La(FOD) 3 ? 2TOPO. SFC conditions: initial 80 atm, 5 atm / min increase, oven temperature: 808C, FID: 3908C (Ref. [14]).

SFC separation of a number of lanthanide b-diketone complexes by means of adduct formation with organophosphorus reagents (Fig. 1). Some relevant solubilities of lanthanide b-diketonates in supercritical CO 2 are shown in Table 2 [16]. Organometallic compounds usually are soluble in supercritical CO 2 . The solubility of ferrocene was studied extensively by Clifford and Bartles group at the University of Leeds [17,18]. 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, with the same parameters, could be used to predict quantitatively both supercritical uid 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 0.008 0.0015 0.0002 0.0001 0.2 250 atm 0.01 0.003 0.0003 0.00017 0.4 SF phase CO 2 CO 2 CO 2 CO 2 CO 2 CO 2

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the temperature dependence of retention in SFC. Experimental results also indicated the inverse relationship between solubility and retention data in SFC if the same column was used [1719]. Wai et al. [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, 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, ranging from the parent compound ferrocene to N,N -dimethylaminomethyl ferrocene, as shown in Table 3 [21]. Lagalante et al. [22] have studied the solubilities of 10 copper(II) and ve chromium(III) b-diketonates in supercritical uid CO 2 . A direct correlation was observed between the metal complex solubility and the Hildebrand solubility parameter of the free ligand. This illustrates that for a given metal system, the nature of the ligand side-chain inuences the solubility of the metal complex in accordance with the regular solution theory [23]. Lagalante et al. [22] observed that the uorinated b-diketonates showed higher solubilities, with the hexauoroacetylacetone complexes having the highest values. The lowest solubility was observed for the benzyl-substituted b-diketone complexes, correlating with the general observation for organic compounds where aromatic substituted systems showed the lowest solubilities. Similar trends were observed for the solubilities of the Cr(III) b-diketone complexes in supercritical CO 2 (Fig. 2). The observed trends indicate that the solubility is strongly dictated by the character of the hydrocarbon or uorocarbon shell surrounding the central metal atom. Akgerman et al. [24] recently developed a dynamic measurement technique to determine solubilities of chelating agents and metal chelates in supercritical CO 2 . Solubilities of cupric acetylacetonate and copper diethyldithiocarbamate were measured in supercritical CO 2 . 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. The PengRobinson equation-ofstate and van der Waals mixing rules were employed in their modeling. The solubility of copper diethyldithiocarbamate in supercritical CO 2 was found to agree with the results reported earlier by Laintz et al. [6]. The predicted solubilities tted 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,N-Dimethylaminomethyl ferrocene Solubility parameter (mol / l) 10.8 9.81 9.39 9.62 8.73 8.33 8.07 9.75 Molar volume (cm 3 / mol) 122.7 172.3 204 204.5 285.3 366.6 447.9 196

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Fig. 2. Plot of Ln( y 2 ) solubility of various copper(II) and chromium(III) b-diketonates in supercritical CO 2 at a density of 0.874 g ml 2 1 versus Fendors solubility parameter of the free ligand (Ref. [22]).

experimentally measured data for Cu(II) acetylacetonate and Cu(II) diethyldithiocarbamate.

3. 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. For instance, inorganic arsenite (As(III)) is more toxic than arsenate (As(V)) and organic arsenic compounds show less toxicity than the inorganic species. 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(triuoroethyl)dithiocarbamate complexes could be separated by SFC from a mixture containing Zn, Ni, Co, Fe, Hg, As, Sb and Bi with excellent resolutions using a 5-m SB-Methyl-100 100-mm i.d. column (Fig. 3). 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). A number of inorganic and organic species of arsenic can also be determined using solvent extraction or SFE followed by the SFC method [8,25]. The organic arsenic compounds, CH 3 AsO(OH) 2 (monomethylarsonic acid, MMA) and (CH 3 ) 2 AsO(OH) (dimethylarsinic

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Fig. 3. Chromatogram produced using a Lee Scientic 5 m 3 100 mm I.D. SB-methyl-100 Superbond capillary column. SFC conditions: 80-nl sample injected at 1008C oven temperature with a hold time of 6.5 min at 100 atm followed by a 4.0 atm / min ramp to 200 atm. Peaks: a, Na(FDDC); b, Zn(FDDC) 2 ; c, Ni(FDDC) 2 ; d, Co(FDDC) 3 ; e, Fe(FDDC) 2 ; f, Hg(FDDC) 2 ; g, As(FDDC) 3 ; h, Sb(FDDC) 3 ; i, Bi(FDDC) 3 . (Ref. [8]).

acid, DMA), in aqueous solutions were converted to CH 3 AsI 2 and (CH 3 ) 2 AsI, respectively, using a mixture of potassium iodide, sodium thiosulfate, and sulfuric acid [8]. The iodides were extracted with FDDC into chloroform as CH 3 As(FDDC) 2 and (CH 3 ) 2 As(FDDC). The resulting FDDC chelates, As(FDDC) 3 , CH 3 As(FDDC) 2 and (CH 3 ) 2 As(FDDC), were separated by SFC and the recovery was generally . 90%. In a subsequent report, simultaneous separation and quantication 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]. A second aliquot of sample was reduced using sodium thiosulfate and potassium iodide for the determination of total As and Sb. Pentavalent concentrations were then

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determined by subtraction. This analytical method produces satisfactory recovery results for arsenic and antimony speciation studies. 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. A number of transition metals were investigated in SFE-gas chromatography with atomic emission detection (GC-AED) [26]. The extraction of Cu(II), Co(II), Cd(II), and Zn(II) ion from solid samples was carried out with LiFDDC in 5% methanol modied CO 2 at 200 atm and 408C followed by GC-AED. The recoveries of Cu(II), Co(II), Cd(II), and Zn(II) ions from lter paper, sand, and silica gel ranged from 70% to 100%. Metal diisobutyldithiocarbamate complexes including Zn(II), Cd(II), Cu(II), Ni(II), Pb(II), Co(III), Fe(III) and As(III) were also separated by capillary SFC using a 10 m 3 50 mm i.d. SB-Phenyl-50 column at 1208C by Manninen et al. [27]. Analyses were carried out using a Lee Scientic Series 600 SFC equipped with ame ionization detection (FID). Metal b-diketonates are the most commonly studied metal chelate system using GC, LC and SFC. In the rst SFC experiments with b-diketonates, 14 different metal chelates of TTA were studied, using dichlorodiuoromethane (CCl 2 F 2 ) as the mobile phase with a column packed with 2% Kel-F wax on Chromosorb W [28]. CCl 2 F 2 was also used in a subsequent investigation of 43 different metal acetylacetonates [29]. Utilizing a packed column, SFC was also able to separate a mixture of b-diketonates including Fe(acac) 3 (acetylacetone), Cr(acac) 3 , Co(acac) 3 and F 2 B(Phacac) (diuoro(1phenyl-1,3-butanedione)boron(III)), with a phenyl column at 1008C and inlet pressure of 4750 psi [30]. Good resolutions were obtained in the separation of Cr(HFA) 3 (hexauoroacetylacetone), Cr(acac) 3 , and Cr(Phacac) 3 (1-phenyl-1,3-butanedione) on a phenyl packed column at 998C and an inlet pressure of 3800 psi [30]. Supercritical CO 2 was used as the mobile phase in several SFC studies on bdiketonate complexes [30,31]. In these studies, methanol was used as a modier to reduce the retention times of the metal chelates and a UV detector was employed for quantication. It was observed that increasing the concentration of the modier would reduce the retention times of the analytes. 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. Column adsorption and decomposition of some of the acetylacetonates also occurred during the SFC analysis, as evidenced by broad peaks with considerable tailing. Cr(HFA) 3 , a uorinated acetylacetonate, showed a shorter retention time than its non-uorinated analogue Cr(acac) 3 . The best results for the SFC analysis of metal b-diketonates using methanol modied CO 2 were obtained with columns packed with polar stationary phases [30]. Separation of 23 metal acetylacetone complexes including Ru(II), Co(III), Rh(III), Ir(III), 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]. Twenty-three out of these 43 metal acetylacetonates studied were eluted without apparent decomposition. Laintz et al. [32] separated the geometric isomers of Cr(III) and Rh(III) chelates of triuoroacetylacetone (TFA) and TTA using packed column SFC. Neat CO 2 or methanol modied CO 2 was used as the mobile phase, and the most favorable isomeric resolution was obtained with a phenyl stationary phase. The chromatographic separation was better

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for chelates with TFA than for the corresponding chelates with TTA. SFC has also been investigated by Caruso et al. [33] for the determination and separation of chromium b-ketonate complexes and a thermally labile organochromium dimer. The determination of chromium complexes was done by both FID and inductively-coupled plasma with mass spectrometric detection (ICP-MS). Reports on the utilization of macrocyclic compounds as chelating agents in SFE and SFC are limited. Calixarenes are macrocyclic complexing agents that possess a lipophilic moiety (upper rim) and a metal coordinating moiety (low rim). They are described as molecular baskets since they have high ionophoric selectivity and form inclusion complexes with many metal ions. A number of metal ions are known to form lipophilic complexes with the deprotonated forms of the simplest phenolic calixarene. Macrocyclic calixarene compounds can be made quite soluble in supercritical uid CO 2 by uorination. Glennon et al. [34] reported SFC and SFE of metals with the hexameric and tetrameric p -tert-butylcalixarenes. They demonstrated the extraction of Fe(III) using supercritical uid CO 2 containing a new uorinated calix[4]arene tetrahydroxamic acid. In this case, the ferric ions were extracted into supercritical CO 2 as a heptadecauorodecane derivatized calix[4]arene hydroxamate Fe(III) complex. 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-modied CO 2 at 3700 psi and 558C, and a ow rate of 3 ml / min; 10% chloroform modied supercritical uid CO 2 showed a better separation for the calixarenes C1 and C2 compared with that using methanol as the modier.

4. 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. [35]. 2,6-Diacetylpyridine bis(benzoylhydrazone) (H 2 DIB) was used as a chelating agent for uranium. SFC properties on different stationary phases such as Nova-Pack C18, Spherisorb ODS2, Zorbax Rx C18, Inertsil ODS2, Capcell-Pack C18, Asahipac C18 and PRP-1 and the inuence of the methanol content in the CO 2 mobile phase were investigated. Capcell-Pack C18 provided the best results in terms of retention time, methanol consumption, peak efciency, and symmetry for the study of chromatographic behavior of uranyl complex UO 2 DIB. This stationary phase was also chosen for a chromatographic study of the chelating agent H 2 DIB, and the copper complex CuDIB. The stability of metal complexes and high solubility in methanol modied supercritical CO 2 allowed a uranyl determination in SFC in less than 2 min. A lesser amount of solvent, | 500 ml, is required for each analysis in SFC, compared to the 10 ml used in reversed phased-liquid chromatography. The results indicate that packedcolumn SFC can provide quantitative, reliable and fast uranium and copper determination. Wai et al. [14,15] studied the separation of lanthanide b-diketone complexes using CO 2 as the mobile phase in SFC. The hydrated lanthanide-FOD (2,2-dimethyl 6,6,7,7,8,8,8-heptauoro-3,5-octanedione) complexes exhibit strong intermolecular interactions and decomposition in SFC. Formation of adducts of the lanthanide b-diketones

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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 efciencies of lanthanides from different matrices by supercritical CO 2 containing a uorinated b-diketone and an organophosphorus reagent [2]. The stability sequence of lanthanideFOD organophosphorus adducts was shown to follow the order Ln(FOD) 3 ? 2TOPO . Ln(FOD) 3 ? 2TBPO . Ln(FOD) 3 ? 2TBP [15]. The chromatographic performance of lanthanide chelates of acac, TFA, TTA, FOD, THD (dipivaloylmethane), and TTA? Py (thenoyltriuoroacetonepyridine) adducts was investigated by Laintz et al. [36]. SFC separation of Pr(acac) 3 , Pr(FOD) 3 , and Pr(THD) 3 complexes showed excellent resolution at 1508C and 120 kg / cm 2 , and a CO 2 ow rate of 0.3 ml / min and ethanol modier ow rate of 0.03 ml / min. The SFC separation was done with an Inertsil 2.1 i.d. 3 250 mm 5 mm phenyl packed column. Lanthanide complexes of acac, FOD and THD displayed high solubilities in supercritical CO 2 and have better chromatographic behavior compared to the corresponding chelates of TFA, TTA, and TTA? Py. Typically, Eu(TTA) 3 showed characteristic thermal decomposition in the mobile phase as a function of temperature. Furthermore, retention behavior was demonstrated to be a temperature dependent function of volatility and solubility [36].

5. SFC separation of organometallic compounds of lead, mercury, and tin SFE of ionic compounds such as organotins (R m SnX 4 2 m , m 5 13) from aqueous samples cannot be accomplished with neat CO 2 due to the charge neutralization requirement and weak solutesolvent interaction. However, when ionic compounds are bound to organic ligands or by ion-pair formation, their solubility in supercritical CO 2 is signicantly increased, thus enabling the extraction of these compounds from environmental samples. Organotin compounds are becoming one of the most versatile groups of organometallic chemicals, in terms of industrial and agricultural applications. They are widely distributed in the environment, and are under intense scrutiny owing to their signicant environmental impacts. Six tetraalkyltin and seven ionic organotin compounds from spiked topsoil samples were extracted by 5% methanol modied supercritical CO 2 by Liu et al. [37]. Analysis of the soil extracts was done by GC-AED. The ionic organotin compounds were derivatized to their corresponding pentylated derivatives before GCAED analysis. Six tetraalkyltin compounds spiked to the topsoil samples were extracted by SFE with recoveries in the range of 90% to 110%. Recoveries ranging from 70% to 90% were obtained for most of ionic organotin compounds when sodium diethyldithiocarbamate (NaDDC) ligand was used. The organotin compounds are identied 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]. Soil or sediment samples, mixed with a chelating agent, diethylammonium diethyldithiocarbamate (Et 2 NHDDC), were extracted with 5% methanol modied CO 2 at 608C and 450 atm. The extracted analytes were treated with

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

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compounds, such as alkoxyethylmercurials, which decompose in GC conditions, can still be analyzed using this SFC-AFS system. A procedure for the SFE of ionic alkyl-lead species from solid samples was reported by Johansson et al. [48]. Methanol was found to be a better modier compared with water and acetone in this separation. The ionic alkyl-leads were extracted as diethyldithiocarbamate complexes into hexane, propylated using a Grignard reagent, and quantied by GC-MS. Recoveries of 96%, 106%, and 80%, for trimethyl-lead, triethyllead, and diethyl-lead, respectively, from spiked sediment samples were reported.

6. SFC separation of other organometallic compounds In the early work on high pressure gas chromatography above critical temperatures, Klesper et al. [5] separated nickeletioporphyrin complexes using a column packed with 33% polyethyleneglycol (Carbowax 20 M) on Chromosorb W, at a maximum pressure of 2000 psi, with CCl 2 F 2 (1128C), and CHClF 2 (968C) as the mobile phases. The same mobile phase was later used to separate Cu, Mg, Ni, Sn and VO etioporphyrin II complexes [49]. Etioporphyrin II complexes of other transition metals were analyzed by Karayannis et al. [50] in subsequent studies. These etioporphyrin II metal chelates were studied at 1458C and 10001700 psi and separation of Ag, Co, Cu, Mg, Mn, Ni, Pd, Pt, TiO, VO, and Zn etioporphyrin II complexes was carried out with a column of 10% Epon 1001 resin on Chromosorb W [50]. 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. [51]. These nickel and vanadyl porphyrin complexes were successfully separated using 20% methanol modied CO 2 as the mobile phase on a C18 packed column and with UV detection. The results suggest that the C18 stationary phase is more selective for the separation of porphyrinic derivatives compared with silica or phenyl stationary phases. The major problems with separation of porphyrin-type complexes seem to be their irreversible adsorption on the chromatographic column. This may be associated with the incomplete coordination of the metals with the porphyrin ring and their subsequent ionic interactions with the chromatographic column. In addition to metalloporphyrins, cyclopentadienyl complex and its derivatives were studied by Jentoft et al. [52]. A synthetic mixture of ferrocene, cyclopentadienyl Mn(CO) 3 , and dicyclopentadienyl TiCl 2 was successfully separated on a 1-m by 1 / 8-inch o.d. stainless steel column packed with a commercially available Carbowax 400, using CO 2 as the mobile phase [52]. In another report, a mixture of ferrocene, acetylferrocene and 1,19-diacetylferrocene was separated by CO 2 / methanol (98 / 2) mobile phase on four different SFC columns of ODS, phenyl, PRP-1, and silica, at 50808C and 24005000 psi [30]. Methanol modied CO 2 was required to elute the substituted ferrocenes from the columns in | 30 min. 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]. The separation of a mixture of the seven ferrocene derivatives shown in Fig. 4a is given in Fig. 5 [21]. The chromatography illustrates that a wide range of ferrocene derivatives can be baseline

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Fig. 4. (a) Structures of ferrocene derivatives shown in Fig. 5: ferrocene (1), ethyl ferrocene (2), t -butyl ferrocene (3), n -butyl ferrocene (4), phenyl ferrocene (5), benzoyl ferrocene (6), dibenzoyl ferrocene (7). (b) Structures of ferrocene, ruthenocene and osmocene derivatives shown in Fig. 6: acetyl ferrocene (1), acetyl ruthenocene (2), acetyl osmocene (3).

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Fig. 5. Typical chromatogram demonstrating baseline separation of a range of ferrocene derivatives of varying physical properties: ferrocene (1), ethyl ferrocene (2), t -butyl ferrocene (3), n -butyl ferrocene (4), phenyl ferrocene (5), benzoyl ferrocene (6), dibenzoyl ferrocene (7). Solvent: methylene chloride. Conditions: T 5 1008C. Insert: pressure ramp used.

resolved using pressure-programmed capillary SFC. The compounds of ferrocene, ethyl ferrocene, t -butyl ferrocene and n -butyl ferrocene are all eluted within 10 min at low pressures (80120 atm). Phenyl ferrocene, benzoyl ferrocene and dibenzoyl ferrocene were all strongly retained on the column at low pressures but were eluted when the pressure reached 400 atm. A pressure program was thus used which caused all seven compounds to elute with baseline resolution being achieved under 12 min. 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. SFC separations of ferrocene, ruthenocene, and osmocene, a different central atom in a dicyclopentadienyl system (Fig. 4b), were conducted at 1008C using a pressure ramp of 2.5 atm / min from 80 to 400 atm. The results (Fig. 6) suggest that SFC can provide baseline resolution for these three compounds [21].

7. SFC determination of solubility of organometallic compounds A number of studies concerning the behavior of organometallic compounds in

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Fig. 6. Chromatogram demonstrating baseline separation of acetyl ferrocene (1), acetyl ruthenocene (2), acetyl osmocene (3). Solvent: methylene chloride. Conditions: T 5 1008C, using a 2.5 atm / min ramp from 80 to 400 atm.

supercritical CO 2 have been carried out in terms of solubility, reactivity, and catalysis [5355]. These studies indicate that a wide range of organometallic systems show high solubility in supercritical CO 2 , as evidenced by SFC investigations. The catalytically active compound RuCl 2 [P(CH 3 ) 3 ] 4 was shown to be soluble in supercritical CO 2 . The solubility of Ru catalyst was measured quantitatively by passing Ru catalyst / supercritical CO 2 through a ne lter at 508C and 120 atm [53]. Ferrocene and its derivatives have been extensively studied with regard to supercritical CO 2 solubility [17,18,20,21]. The high solubility of ferrocene can be interpreted as being due to the nature of bonding. Ferrocene is a system in which the metals 3d, p, and s orbitals are lled so that no free coordination sites are available for interaction with the solvating CO 2 , resulting in a system having properties resembling those of an aromatic compound. SFC provides a means for investigating the behavior of ferrocene and its derivatives, since it has been shown that the retention behavior of solutes is directly related to the solubility in the supercritical uid [17,18]. Cowey et al. [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. Wai et al. [21] studied the behavior of ferrocene and its derivatives and separated ferrocene derivatives using capillary SFC. The capacity factors of the ferrocene derivatives were found to vary signicantly with the chromatographic temperature and pressure. It was shown that the SFC retention could be predicted from knowledge of simple parameters such as the

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solubility parameter of the solute, molar volume of the solute, and the physical characteristics of the chromatographic column. In general the more soluble a compound is in supercritical uid CO 2 , the quicker it will elute from the column. This general relationship has been used to determine solubility [19,56]. There are some assumptions that must be made for a specic equation to work. A discussion of these assumptions was given by Bartle et al. [19]. As the supercritical uid temperature increases at constant pressure, the density of the uid decreases, which leads to a decrease in the solvating power of the supercritical uid and leads to an increase in the analytes retention. Thus, at relatively low temperatures and low analyte vapor pressures, the density of the supercritical uid is the dominant factor. However, as the supercritical uid temperature is increased, the volatility of the analyte also increases until the analyte vapor pressure becomes more important than supercritical uid density. At this point, the solubility of the analyte in the supercritical uid starts to increase, resulting in a decrease in analyte retention time. This phenomenon has been observed for the retention of lanthanide b-diketone complexes and polyaromatic compounds analyzed by packed column SFC [36,57]. The theory was further veried by a range of ferrocene derivatives with very different functionalities, ranging from the parent compound ferrocene to N,N -dimethylaminomethyl ferrocene [20]. The following equation was derived by Brauer et al. [20] to show the relationship between di and (RT / Vi ) Ln(k 9 / r),
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 ); dsf is the solubility parameter of the supercritical uid phase (cal 1 / 2 cm 2 3 / 2 ); dsp is the solubility parameter of the stationary phase (cal 1 / 2 cm 2 3 / 2 ); k 9 is the capacity factor, the ratio of the solute between the two phases; r is the ratio of the volume of the stationary phase to the volume of SF in the column; Vi is the pure solute molar volume (cm 3 ); R is the ideal gas constant (cal mol 2 1 K 2 1 ); and T is temperature (K). For isobaric and isocratic SFC, Eq. (1) predicts a linear relationship between di and (RT / Vi ) Ln(k 9 / r), hence allowing a quantitative means of predicting retention behavior of solutes in SFC.

8. Detection system for SFC of metal-containing compounds Currently, most commonly used detectors for SFC and GC are UV absorption and FID [8,20,31,51], which are universal, sensitive, and have the potential for high selectivity. For instance, Wenclawiak [31] and Ashraf-Khorassani et al. [30] described the separation of metalacetylacetone complexes and porphyrinic derivatives by SFC with UV detection. Wai et al. [20] utilized SFC equipped with a FID with a 5-cm methyl silicone open tubular capillary column for determination of ferrocene. The limitations of UV detection for SFC are related to sensitivity considerations, whereas FID is constrained to uids yielding no signicant ionization during detection (such as CO 2 ).

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In addition to UV and FID detection, element-selective detectors seem attractive for the detection of metal-containing compounds in SFC. Several element-selective optical detectors, such as the microwave-induced plasma detector (MIP) [5860], radiofrequency plasma detector [61], and ICP [62,63], have been studied extensively for SFC. A single FPD attached to a capillary SFC system was used by Bayona et al. [39] for analyzing trialkyltin chlorides. Among several element-selective techniques, ICP-MS provides excellent selectivity [6466]. The use of a high-resolution MS can further enhance the capacity to resolve components of the same nominal molecular weight, to aid identication, and to eliminate background complication. A number of authors [64,66] succeeded in coupling the ICP-MS with SFC for the separation and determination of organometallic compounds. For example, Shen et al. [64] interfaced the ICP-MS with SFC to separate the tetraalkyltin compounds with detection levels in the sub-picogram range. The linear range was over three orders of magnitude (11000 pg). This new approach suggests the potential for simultaneous determination of mixtures of organometallic pollutants of environmental interest such as As, Pb, Sn and Hg at ultra-trace levels. The SFC-ICP-MS system was also evaluated by comparing the results from an SFC-FID for the determination of tri- and tetraorganotin compounds [66]. Better resolution was obtained with FID, and differences were attributed to uctuations in the temperature of the transfer line used in the SFC-ICP-MS interface. Baseline resolution for the organotin compounds is accomplished in both FID and ICP-MS detection by using a longer column. For the same organotin compounds, ICP-MS detection limits are superior to the FID results by one order of magnitude. The major advantages of FID are low cost and ease of operation, whereas the ICP-MS detector is more sensitive and selective. For the analysis of a real sample, more interference will appear by FID than by ICP-MS. 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. These detectors were employed in conjunction with packed microbore columns of 1-mm i.d. and packed capillary columns of 0.53-mm i.d. The use of a micro-column in SFC allows the total efuent to be introduced into the plasma. The performance was evaluated by monitoring the Fe emission line at 259.94 nm. Signicant progress has been reported using Fourier transform infrared spectroscopy (FT-IR) as a detection method [56,68]. The off-line approach for FT-IR detection is particularly attractive because of the enhanced detection limits and the practical elimination of the solvent modier [56,68] that greatly limits on-line detection. 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, as in the case of nonspectrometric detectors such as FID. FT-IR has the ability to interpret quickly and unambiguously the presence or absence of specic organic functional groups in a sample molecule. The major disadvantages of off-line FT-IR detection include mechanical complexity, expense, sensitivity (in some cases), and the absence of commercial instrumentation. Jinno et al. [69] used photodiode array UV and ICP serial detectors coupled with packed micro-column SFC for determination of metalacac complexes. These metal

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acac complexes included Al(III), Co(II), Co(III), Cr(III), Cu(II), Mn(II), Mn(III), Ni(II), and Zn(II). The UV detector can provide UV spectra of acac complexes separated by SFC, while ICP detector can supply elemental information for complex identication.

9. Future developments With increasing demands for speciation information of elements of biological and environmental concern, SFC should play a role in preparation and analysis of metalcontaining compounds in complicated matrices. 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. With modiers, SFC analysis of more polar compounds is feasible. The range of application and sensitivity of detectors will probably be the major factor in determining the future growth of SFC. One attraction of SFC with CO 2 as the mobile phase is its compatibility with both liquid- and gas-phase detectors and particularly with FID. The development of more selective stationary phases for both packed and capillary column SFC is desirable. The preparation of columns that are stable to the solvating inuences of polar supercritical uids at elevated temperatures remains challenging. The extraction and separation of metal chelates and organometallic compounds by SFE / SFC depend largely on the proper selection of chelating agents. Fluorinated ligands are effective for in situ chelation-SFE of metal ions and SFC of metal-containing compounds. 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. Adduct formation is another technique for improving SFE and SFC efciency of metal chelates. Phosphorus and silicon-containing ligands also form highly soluble metal complexes in supercritical CO 2 . 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. 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. 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.

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