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A supercritical fluid extraction procedure and a chromatographic separation/detection method were developed for the detection of Earth-based microorganisms. After microbes in a sand or a soil sample were hydrolyzed in a diluted NH(4)OH/acetone solution, several redox compounds from bacteria could be effectively extracted with trimethylamine-modified supercritical CO(2) at 35 degrees C and 300 atm. These signature redox-active compounds were separated by a reversed-phase HPLC column in an ion-pair mode and then monitored with a diode array detector and an electrochemical detector. The analytical results demonstrated the feasibility of using the reported techniques to detect the chemical signature of life in barren desert sand samples., (©2002 Elsevier Science (USA).)

Uranium dioxide can be dissolved in supercritical CO2 with a CO2-philic TBP-HNO3 complexant to form a highly soluble UO2(NO3)(2).2TBP complex; this new method of dissolving UO2 that requires no water or organic solvent may have important applications for reprocessing of spent nuclear fuels and for treatment of nuclear wastes.

Under ultrasonication, the ginkgo terpene trilactones, ginkgolides and bilobalide, in ginkgo extracts can be selectively dissolved in 10% aqueous NaH(2)PO(4) solution at a temperature of 50-60 degrees C and separated from the solution by extraction with a mixture of ethyl acetate/tetrahydrofuran in a capped vial. After derivatization, these terpene trilactones can be quantified using GC-FID. This method has a detection limit of 10 ng, and the RSD was 6% (n=5). Twelve commercial GBE products in powder, liquid, tablet and capsule forms were analyzed. The total time required for analyzing these samples from sample preparation to final data processing was less than 6 h, and the total organic solvent consumption was less than 40 ml. This procedure proves to be a simple, fast, safe, and effective method for all types of Ginkgo biloba extracts (GBE) including the "complex" or "advanced" formulas.

Due to increasingly stringent environmental regulations, supercritical fluid extraction (SFE) has gained wide acceptance in recent years as an alternative to conventional solvent extraction for separation of organic compounds in many analytical and industrial processes. In the past decade, SFE has been applied successfully to the extraction of a variety of organic compounds from herbs and other plants. This review article presents the practical aspects of SFE applications in sample preparation, selection of modifiers, collection methods, on-line coupling techniques, means for avoiding mechanical problems, and approaches to optimization of SFE conditions. SFE can also be used to clean up pesticides from herb medicines. SFE processes can be modeled to acquire useful information for better understanding of the extraction, mechanisms and optimization of the extraction procedures. With increasing public interest in natural products, SFE may become a standard extraction technique for studying herbal, food and agricultural samples.

A supercritical fluid extraction (SFE) method was developed for the extraction of polycyclic aromatic hydrocarbons (PAHs) from fresh and fallen pine needles. Toluene-modified CO2 was used as the extracting fluid, and the extracted PAHs were analyzed by GC-MS. Using a two-stage extraction procedure, a static extraction at 180 degrees C and a dynamic extraction at 60 degrees C, and an in-cell silica gel plug plus a post-oven silica gel column, the extraction and fractionation of PAHs can be accomplished in one step. Over a seven month period, a significant variation was observed for PAHs in urban samples, while PAHs in mountain samples were at much lower levels (by a factor of approximately 8) and showed little seasonal change. Although dry fallen needles and fresh needles contained similar amounts of PAHs, in the fallen needles the lower molecular weight PAHs were partially lost while the higher molecular weight PAHs were slightly enriched. Pollution in urban areas was found to be highly localized, and buildings and trees are believed to be important factors in the restriction of atmospheric PAHs.

A novel method for voltammetric measurement in supercritical CO2 is described. In this method a water-in-supercritical CO2 microemulsion is utilized to raise the conductivity of the fluid phase. Well-defined voltammograms for the redox reactions of ferrocene and tetramethyl-p-phenylenediamine were obtained in supercritical CO2 in the presence of the microemulsion. The electrolysis product is stabilized in the water core of the microemulsion. This implies a wide range of electrochemical synthesis involving ionic or radical species in supercritical CO2 may be possible utilizing the microemulsion. The electrochemical results obtained from the water-in-supercritical CO2 microemulsion system are different from that obtained from a supercritical CO2-ethanol mixture system.

A new approach to the measurement of solubilities in supercritical CO2 is reported, utilizing laser-induced fluorescence. This selective technique was found to be capable of rapid multipoint solubility measurements with high sensitivity (10(-9) M). The sensitivity enables measurements to be performed with small amounts of analytes and at low pressure, 80-130 atm, typically below the range of other methods. Four uranyl complexes were investigated using this method, UO2(TTA)2.H20, UO2(TTA)2.TBP, UO2(TTA)2.TOPO, and UO2(NO3)2.2TBP (where TTA = thenoyltrifluoroacetone, TBP = tributyl phosphate, and TOPO = trioctyl phosphine oxide). Comparison with solubility data previously obtained with UV-visible spectroscopy shows good agreement between the techniques. We have shown that the Chrastil solubility equation is equally valid at lower ScF densities, and consequently, solubility values determined at high pressures can be extrapolated to the low-pressure regions and vice versa for solid materials.

A method for separation and detection of divalent transition metal beta-diketonates by adduct formation/supercritical fluid chromatography (SFC) with an open-tubular capillary column and a FID detector is described. The crystal structures of copper (Cu)-hexafluoro-acetylacetone (HFA) and Cu bis(2,2,6,6-tetramethyl-3,5-heptanedionato) (THD) complexes have been determined by X-ray crystallography. The SFC behavior of Cu beta-diketonates shows a strong correlation with the structure of the complexes. The hydrated cu beta-diketonate complexes usually exhibit strong intermolecular interactions or decomposition in SFC. Formation of adducts with a neutral donor, such as tributyl phosphine oxide (TBPO), can greatly improve the SFC behavior and detection sensitivity of Cu(II) and Mn(II) beta-diketonates. The stoichiometry and thermal stability of the adducts Cu(II) and Mn(II) beta-diketonates with TBPO in supercritical CO(2) have also been investigated. The implications of utilizing adduct formation for supercritical fluid extraction (SFE) of divalent transition metals and for on-line coupled SFE/SFC analysis of divalent transition metals are discussed.

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.

Time-resolved laser-induced fluorescence has been shown to be effective for on-line measurement of uranyl chelates in supercritical carbon dioxide. Quenching and other factors affecting the method's accuracy were identified and quantified to allow for accurate measurements under variable supercritical fluid conditions. The method was applied to the kinetic analysis of uranium extraction from acidic solutions with tributyl phosphate modified supercritical carbon dioxide.

Dechlorination of a nonachloro biphenyl congener with zero-valent iron in water under high temperature and pressure was investigated over time. Temperature has the main influence on the speed of dechlorination. Determination of polychlorinated biphenyls (PCBs) according to the grade of chlorination was performed by gas chromatography with mass selective detection in single ion monitoring mode. Dechlorination results in a variety of lower chlorinated biphenyls. The level of chlorination decreases with time. The amount of PCB molecules decreases to one-third within 90 min at 250 degrees C and 100 atm. However, no increase of biphenyl could be detected over time. A first-order kinetic model fitted the data obtained.

Off-line supercritical fluid extraction (SFE) followed by gamma-radiolysis as an alternative treatment technique for PCB-contaminated soil was investigated in this study using BZ #54 (2, 2',6,6'-tetrachlorobiphenyl) as the model compound. The preliminary results indicate that removal of BZ #54 from spiked sand and soil using SFE at 150 degrees C and 20 MPa is 98% and 93%, respectively. The reduction efficiency of 864 mg/l BZ #54 in isooctane by gamma-radiolysis is 99.8% at an absorbed dose of 500 kGy.

A procedure is reported for synthesizing a novel, water-soluble bifunctional chelating agent derived from calix[4]arene. This chelate features tetracarboxylic acid groups at the lower rim as an actinium-225 ionophore, and an isothiocyanate functional group at the upper rim for labeling of the N-terminus of monoclonal antibodies through thiourea linkage.

Strontium (Sr(2+)) can be selectively extracted from aqueous solutions into supercritical fluid CO(2) at 60 °C and 100 atm with dicyclohexano-18-crown-6 (DC18C6) using CF(3)(CF(2))(6)CO(2) (-) (PFOA(-)) or CF(3)(CF(2))(6)CF(2)SO(3) (-) (PFOSA(-)) as a counter anion; at a mole ratio of Sr(2+) : DC18C6 : PFOA(-) = 1:10:50, the extraction of Sr (5.6 × 10(-5) M) from water at pH 3 is near quantitative whereas Ca(2+) and Mg(2+) at equal concentration are only extracted to a level of 7 and 1%, respectively; PFOSA(-) is an effective counter anion for selective extraction of Sr(2+) from 1.3 M HNO(3) with DC18C6 in supercritical CO(2).

Copper ferrocyanide can be immobilized on Chelex-20, a technical grade chelating resin, for selective removal of cesium from neutral to acidic solutions. The immobilized copper ferrocyanide is much easier to handle than the copper ferrocyanide powder in extraction and separation of cesium from aqueous solutions. In the presence of a reducing agent such as hydrazine, the immobilized copper ferrocyanide resin is able to remove 98% of the cesium from a simulated acid waste solution in one cycle of batch experiments. The resin shows promising properties for remediation of acidic nuclear wastes and for concentration of (137)Cs from environmental samples for quantitative analysis.

The response of a monoaza-15-crown-5 with an optically active aminobenzoxazinone moiety to divalent cations was investigated. The crown ether was found to undergo a strong emission shift to the blue when complexed with specific divalent metals that have ionic diameters between 1.9-2.4 A. Consequently the photoactive macrocycle is responsive to Mg(2+), Ca(2+), Ba(2+), Sr(2+), Cd(2+), and particularly responsive to Hg(2+)and Pb(2+). Macrocycle emission spectra are shown to be a function of cation concentration. Alkaline metal cations and smaller transition metals ions such as Ni(2+), Co(2+)and Zn(2+)do not cause significant changes in the macrocycle emission spectra. Emission, absorption, and complex stability constants are determined. Mechanisms of cation selectivity and spectral emission shifts are discussed. Challenges involving immobilization of the macrocycle while preserving its spectral response to cations are explored.

The design and construction of a microscale, fiber-optics-based system for the measurement of solubilities in supercritical CO(2) by UV-visible spectroscopy is described. This system consists of three high-pressure fiber-optic cells, with path lengths ranging from 38 μm to 1 cm, constructed from standard (1)/(16)-in. stainless steel fittings and silica fibers. It is capable of withstanding pressures in excess of 300 atm, and spectra over the entire UV-visible range (200-900 nm) can be obtained. Use of three cells with different path lengths enables compounds of high or low solubility to be measured over a concentration range of several orders of magnitude. The solubility of a uranium complex, UO(2)(tta)(2)·TBP, in supercritical CO(2) at 40 °C and over the pressure range 100-325 atm was determined, and it was found to be possible to attain solubilities in excess of 10(-)(2) M for metal species in unmodified supercritical CO(2). Also, the small volume of this system allows solubilities to be measured with relatively small amounts of compounds.

Reversed phase high-performance liquid chromatography (RP-HPLC) is demonstrated for hydrophobic analytes such as aromatic hydrocarbons on a chemically bonded stationary phase and a mobile phase consisting of only water. Reversed phase liquid chromatography separations using a water-only mobile phase has been termed WRP-LC for water-only reversed phase LC. Reasonable capacity factors are achieved through the use of a non-porous silica substrate resulting in a chromatographic phase volume ratio much lower than usually found in RP-HPLC. Two types of bonded WRP-LC columns have been developed and applied. A brush phase was synthesized from an organochlorosilane. The other phase, synthesized from an organodichlorosilane, is termed a branch phase and results in a polymeric structure of greater thickness than the brush phase. A baseline separation of a mixture containing benzaldehyde, benzene, toluene, and ethyl benzene in less than 5 min is demonstrated using a water mobile phase with 12 000 plates generated for the unretained benzaldehyde peak. The theoretically predicted minimum reduced plate height is also shown to be approached for the unretained analyte using the brush phase. As an application, subcritical water extraction (SWE) at 200 degrees C is combined with WRP-LC. This combination allows for the extraction of organic compounds from solid matrices immediately followed by liquid chromatographic separation of those extracted compounds all using a solvent of 100% water. We demonstrate SWE/WRP-LC by spiking benzene, ethyl benzene, and naphthalene onto sand then extracting the analytes with SWE followed by chromatographic separation on a WRP column. A sand sample contaminated with gasoline was also analyzed using SWE/WRP-LC. This extraction process also provides kinetic information about the rate of analyte extraction from the sand matrix. Under the conditions employed, analytes were extracted at different rates, providing additional selectivity in addition to the WRP-LC separation.

The solubility of 49 metal-containing compounds and 15 "free" ligands in supercritical fluid carbon dioxide is reviewed. Solubilities were found to range over eight orders of magnitude, with the highest value of solubility being 56 g l(-1). Metals complexed with fluorine substituted ligands were found to be the most soluble, and metals complexed with phenyl-substituted ligands the least soluble. A general trend for increasing solubility with increasing oxidation state is observed and this is correlated with the increased number of coordinating ligands protecting the metal center from interaction with the supercritical fluid and also due to the increased number of solvation interactions with the increased number of ligand groups.

The use of four dithiocarbamates and three fluorinated beta-diketones as potential chelating agents for three transition metal ions (Cd(2+), Pb(2+), and Hg(2+)) extracted from spiked sand and filter paper samples by supercritical fluid extraction (SFE) was investigated. The extractions were performed at 45 degrees C and 250 atm for spiked sand samples and at 60 degrees C and 200 atm for filter paper samples using supercritical carbon dioxide modified with 5% methanol. At 250 atm and using carbon dioxide modified with 5% methanol, the recoveries of Cd(2+), Pb(2+), and Hg(2+) ions from spiked sand samples were 95% with lithium bis(trifluoroethyl)dithiocarbamate (LiFDDC) as the chelating agent; they ranged from 83-97% with diethylammonium diethyldithiocarbamate and from 87-97% with sodium di-ethyldithiocarbamate as chelating agents, and from 68-96% with trifluoracetylacetone, hexafluoroacetylacetone, and thenoylfluoroacetone as chelating agents. Ammonium pyrrolidinedithiocarbamate was not effective in the chelation SFE of Cd(2+), Pb(2+), and Hg(2+) ions from either spiked sand or spiked filter paper samples under the extraction conditions used. Supercritical carbon dioxide alone gave consistently lower analyte recoveries than supercritical carbon dioxide modified with 5% methanol. The results suggest that the solubility of the metal chelate in the supercritical fluid plays a more important role than the solubility of the chelating agent in the supercritical fluid, as long as sufficient chelating agent is present in the fluid phase. Fluorination of the chelating agent, as in the case of LiFDDC, increases the solubility of the metal chelate, and subsequently enhances the extraction efficiency for the metal ions.

The solubilities of Cu, Hg, and Zn complexes with seven different dithiocarbamate ligands in supercritical fluid CO(2) at 60 °C and two pressures (100 and 230 atm) are reported. In each metal chelate system, the solubility of the metal-dithiocarbamate complex shows a strong correlation with the solubility parameters of the ligands, calculated using a group contribution method. Dithiocarbamate ligands with smaller solubility parameter values form metal complexes with higher solubilities in supercritical CO(2). The solubility parameter value may provide a general guideline for selecting effective ligands for metal extraction in supercritical CO(2).

Mercuric ions (Hg(2+)) can be extracted from solid samples (cellulose matrix) using methanol modified supercritical CO(2) containing the fluorinated chelating agent lithium bis(trifluoroethyl)dithiocarbamate (LiFDDC). Methylmercuric chloride (CH(3)HgCl) and dimethylmercury [(CH(3))(2)Hg] can be extracted by supercritical CO(2) without chelating agent and modifier. The solubility of Hg(FDDC)(2) in supercritical CO(2) has been determined to be 5 x 10(-3)M at 5O degrees C and 150 atm, which is about 3 orders of magnitude greater than that of the non-fluorinated analogue Hg(DDC)(2). Use of methanol (5%)-modified CO(2) further enhances the solubility of Hg(FDDC)(2) by a factor of 2.4. A small amount of water added to the sample matrix tends to facilitate the extraction of Hg(FDDC)(2) and CH(3)HgCl. Potential applications of this in situ chelation-supercritical fluid extraction method for the preconcentration of mercury species and treatment of mercury contaminated wastes are discussed.

Thorium and the lanthanides are extracted by alpha-(sym-dibenzo-16-crown-5-oxy)acetic acid and its analogues in different pH ranges. At pH 4.5, Th is quantitatively extracted by the crown ether carboxylic acids into chloroform whereas the extraction of the lanthanides is negligible. Separation of Th from the lanthanides can be achieved by solvent extraction under this condition. The extraction does not require specific counteranions and is reversible with respect to pH. Trace amounts of Th in water can be quantitatively recovered using this extraction system for neutron activation analysis. The nature of the extracted Th complex and the mechanism of extraction are discussed.

Simultaneous separation and quantitation of arsenic(III) and antimony(III) can be achieved by extraction with lithium bis(trifluoroethyl)dithiocarbamate followed by supercritical fluid chromatographic (SFC) analysis. Arsenic(V) and antimony(V) are extracted after reduction with potassium iodide and sodium thiosulfate. Detection limits of 7 pg As and 11 pg Sb are achieved using this extraction method and SFC. Application to natural water and biological sample analysis is discussed.

The selectivities during solvent extraction of lanthanoids with macrocycles can be modified with complexonates in the aqueous phase. In the case of solvent extraction of lanthanoids with 18-crown-6 and trichloroacetic acid (TCA), addition of EDTA to the aqueous phase enhances the selectivities of lanthanoids by 3-7 times compared to those without the complexonate. This is due to the fact that the stability of lanthanoid-EDTA complexes increases in the opposite direction to the crown-TCA complexes across the lanthanoid series. The selectivities observed in this system are among the largest reported for the light lanthanoids. The effect of the complexonate on lanthanoid extraction can be explained by a simple model presented in this paper.

Lipophilic crown ether carboxylic acids such as 2-(sym-dibenzo-16-crown-5-oxy)stearic acid with a cavity size comparable to the ionic radius of rare-earth elements are selective chelation agents for preconcentration and separation of lanthanides from natural waters for NAA. Interfering matrix elements such as sodium and bromine can be simultaneously eliminated during the extraction. The lanthanides can be back-extracted into a dilute acid solution for NAA, thus providing a large preconcentration factor. This two-step extraction method appears suitable for the determination of lanthanides in natural waters and in biological samples.

Arsenic and antimony in digested biological samples can be extracted with pyrrolidinecarbodithioate at pH 1 into chloroform and stripped with nitric acid for neutron-activation analysis (NAA). The extraction method eliminates interferences from matrix species, including Br and Na, making the accurate determination of low levels of As and Sb in biological materials feasible. The detection limits under the experimental conditions used are 0.005 and 0.006 mug/g for arsenic and antimony, respectively. A comparison of the results obtained for As and Sb in NBS biological standards by this method and by non-destructive instrumental neutron-activation analysis (INAA) is also given.