Supercritical fluid extraction and gas chromatography analysis of arsenic species from solid matrices

A method in combination with derivatization-supercritical fluid extraction(SFE) and gas chromatography(GC) for the speciation and quantitative determination of dimethylarsinate(DMA), monomethylarsonate(MMA) and inorganic arsenic in solid matrices was investigated. Thioglycolic acid methyl ester(TGM) and thioglycolic acid ethyl ester(TGE) were evaluated as derivatization reagents. The effects of pressure, temperature, flow rate of supercritical CO_2, extraction time, modifier and microemulsion on the efficiency of extraction were systematically investigated. The procedure was applied to the analysis of real soil and sediment samples. Results showed that TGE was more effective for arsenic speciation as a derivatization reagent. Modifying supercritical CO_2 with methanol can greatly improve the extraction efficiency. Further, the addition of microemulsion containing surfactant Triton X-100 can further enhance recoveries of arsenic species. The optimum extraction conditions were 100 ℃, 30 MPa, 10 min static and 25 min dynamic extraction with 5%(v/v) methanol, and surfactant modified supercritical CO_2. Detection limits in solid matrices were 0.15, 0.3 and 1.2 mg/kg for DMA, MMA and inorganic arsenic,respectively. The method was validated by the recovery data. The resulting method was fast, easy to perform and selective in the extraction and detection of various arsenic species in solid matrices.     

Simultaneous determination of dimethylarsinic acid and monomethylarsonic acid after derivatization with thioglycol methylate by gas chromatography/mass spectrometry

A gas chromatography/mass spectrometry (GC/MS) method has been developed to determine two methylated arsenic species in human urine samples. The yield of derivatization for dimethylarsinic acid (DMA) and monomethylarsonic acid (MMA) using thioglycol methylate (TGM) was measured. The detection limit for the derivatized DMA and MMA using the GC/MS method are 0.95 and 0.8 ng cm-3, respectively. This simple and rapid method has good precision and accuracy. Fragmentation routes of derivatized MMA and DMA are suggested on accurate mass measurements.     

Qualitative supercritical fluid extraction coupled to capillary gas chromatography

The usefulness and ease of utilizing supercritical fluid extraction (SFE) directly coupled to capillary gas chromatography (GC) as quantitative or qualitative analytical problem-solving tools will be demonstrated. As an alternative to conventional liquid solvent extractions, SFE presents itself as a means to achieve high extraction efficiencies of different compounds in complex solid matrices in very rapid tims frames. Moreover, SFE has an additional advantage of being able to achieve distinct extraction selectivities as a function of the solubilizing power of the supercritical fluid extracting phase. For on-line SFE/GC, the extraction effluent is directly transferred to the analytical chromatograph. On-line SFE/GC involves the decompression of pressurized extraction effluent directly into a heated, unmodified capillary split injection port of the GC. In this respect, SFE introduction into GC can be used as an alternative means of GC injection, comparable to such modes of injection as pyrolysis and thermal desorption. This paper will show applications of SFE/GC where mass spectrometric detection together with flame ionization detection was used for component identification from environmental, tobacco, and petroleum matrices.     

Optimization of the extraction for the determination of arsenic species in plant materials by high-performance liquid chromatography coupled with hydride generation atomic fluorescence spectrometry

A study has been conducted for the separation and the determination of arsenic species in plants using high-performance liquid chromatography–hydride generation atomic fluorescence spectrometry with emphasis on sample extraction procedures. Various extraction solvents have been applied to extract arsenic species from plants in order to investigate the uptake, transfer and accumulation processes of arsenic. The method was optimized with respect to the selection of extraction solvent, extraction time and the number of extraction steps. The analytical procedure has been validated by analyzing standard reference material GBW 82301 (peach leaves) and successfully used for the arsenic speciation in plants grown on contaminated soil near an arsenic mine. Inorganic arsenic, especially arsenate (As(V)) appears to be the major component in plants and organic arsenic species of monomethylarsenic acid and dimethylarsenic acid were detected at low concentrations.     

Determination of arsenic species in solid matrices utilizing supercritical fluid extraction coupled with gas chromatography after derivatization with thioglycolic acid n‐butyl ester

A method using derivatization and supercritical fluid extraction coupled with gas chromatography was developed for the analysis of dimethylarsinate, monomethylarsonate and inorganic arsenic simultaneously in solid matrices. Thioglycolic acid n‐butyl ester was used as a novel derivatizing reagent. A systematic discussion was made to investigate the effects of pressure, temperature, flow rate of the supercritical CO₂, extraction time, concentration of the modifier, and microemulsion on extraction efficiency. The application for real environmental samples was also studied. Results showed that thioglycolic acid n‐butyl ester was an effective derivatizing reagent that could be applied for arsenic speciation. Using methanol as modifier of the supercritical CO₂ can raise the extraction efficiency, which can be further enhanced by adding a microemulsion that contains Triton X‐405. The optimum extraction conditions were: 25 MPa, 90°C, static extraction for 10 min, dynamic extraction for 25 min with a flow rate of 2.0 mL/min of supercritical CO₂ modified by 5% v/v methanol and microemulsion. The detection limits of dimethylarsinate, monomethylarsonate, and inorganic arsenic in solid matrices were 0.12, 0.26, and 1.1 mg/kg, respectively. The optimized method was sensitive, convenient, and reliable for the extraction and analysis of different arsenic species in solid samples.     

Simultaneous determination of arsenic and antimony species in environmental samples using bis(trifluoroethyl)dithiocarbamate chelation and supercritical fluid chromatography.

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.     

北苍术超临界CO2萃取产物的成分

用气相色谱－质谱－计算机联用法分析了北苍术的超临界CO2萃取产物的成分,鉴定出苍术酮、β－桉叶油醇、苍术醇31化合物,占出峰总面积的88．1％,并与传统水蒸汽蒸馏法（SD）提取的挥发油成分进行了对比。结果证明,两种方法抽提的苍术主成分基本相同,但超临界CO2萃取产物比SD产物多出现了一些重质组分,萃取更完全而有效。     

Metal Ions Extraction with Glucose Derivatives as Chelating Reagents in Supercritical Carbon Dioxide

A series of glucose derivatives have been used as chelating reagents to extract metal ions in supercritical carbon dioxide. With perfluoro-1-octanesulfonic acid tetraethylammonium salt as additive, glucose derivatives were selective for Sr2 and Pb2 extraction in supercritical carbon dioxide.     

Speciation of arsenic in natural waters by HPLC-NAA

Neutron activation analysis (NAA) in combination with mainly high-performance liquid chromatography (HPLC) has been developed for the determination of low levels of five arsenic species, namely As(III), As(V), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), and arsenobetaine (AsB) in water samples. Organically bound arsenic (OBAs) and total arsenic have also been determined. In addition to anion-exchange HPLC, solid phase extraction and open-column cation-exchange chromatographic methods have also been used. The detection limits of the method have been found to be 0.005 ng·cm⁻³ for OBAs, 0.02 ng·cm⁻³ for AsB, DMA, MMA, As(III), and As(V) and 0.12 ng·cm⁻³ for total arsenic. This revised version was published online in July 2006 with corrections to the Cover Date.     

Selective determination of arsenic(III) and arsenic(V) with ammonium pyrrolidinedithiocarbamate, sodium diethyldithiocarbamate and dithizone by means of flameless atomic-absorption spectrophotometry with a carbon-tube atomizer

The extraction behaviour of arsenic(III) and arsenic(V) with ammonium pyrrolidinedithiocarbamate, sodium diethyldithiocarbamate and dithizone in organic solvents has been investigated by means of nameless atomic-absorption spectrophotometry with a carbon-tube atomizer. The selective extraction of arsenic(III) and differential determination of arsenic(III) and arsenic(V) have been developed. With ammonium pyrrolidinedithiocarbamate and methyl isobutyl ketone or nitrobenzene, when the aqueous phase/solvent volume ratio is 5 and the injection volume in the carbon tube is 20 μl, the sensitivities for 1% absorption are 0.4 and 0.5 part per milliard of arsenic, respectively. The relative standard deviations are ca. 3%. Interference by many metal ions can be prevented by masking with EDTA. The proposed methods are applied satisfactorily for determination of As(III) and As(V) in various types of water.     

Simultaneous determination of antimony,arsenic and copper by neutron activation analysis

A rapid procedure has been developed for the mutual separation of antimony and arsenic using tribenzylamine as the extracting agent. The extraction behaviours of Sb(III), Sb(V), As(III), As(V) and Au(III) have been studied as a function of the acidity of the aqueous phase. Various factors which affect the extraction of these complexes have been studied and optimized. The procedure was then applied to lead base alloy for the simultaneous determination of antimony, arsenic and copper. Chemical recoveries were quantitative and only about one hour is required for the chemical processing of duplicate samples.     

Fat content for nutritional labeling by supercritical fluid extraction and an on-line lipase catalyzed reaction

A method using sequential supercritical fluid extraction (SFE) and enzymatic transesterification has been developed for the rapid determination of total nutritional fat content in meat samples. SFE conditions of 12.16 MPa and 50°C were utilized to extract lipid species from the sample matrix. The enzymatic transesterification of the lipids by methanol was catalyzed by an immobilized lipase isolated from Candida antarctica. Conversion of the triglycerides to fatty acid methyl esters was monitored by supercritical fluid chromatography, while the fatty acid content of the extract was determined by capillary gas chromatography (GC). Total fat, saturated fat and monounsaturated fat contents were calculated from the GC data and compared to values from traditional extraction and lipid determination methods. Both off-line SFE and automated SFE followed by on-line GC analysis using two different instruments were utilized in this study. The enzymatic-based SFE method gave comparable results to the organic solvent extraction-based method followed by conventional BF₃-catalyzed esterification.     

Supercritical fluid extraction of vapor-deposited pyrene from carbonaceous coal stack ash

The efficiencies of extraction of vapor-deposited pyrene from a high-carbon coal stack ash by Soxhlet extraction with methanol, ultrasonic extraction with toluene, acid pretreatment and subsequent ultrasonic extraction with toluene, batch extraction with toluene, and supercritical fluid extraction (SFE) are compared. SFE using CO(2) or isobutane yielded extraction recoveries virtually identical with those obtained using ultrasonic or Soxhlet extraction processes. Collection of the SFE extract was performed by expansion into a solvent or onto the head of a gas chromatography (GC) column. No loss of extracted pyrene was observed upon collection of methanol-modified CO(2) SFE by expansion into methanol. Also, no loss of pure CO(2) SFE extract was observed upon collection on the head of a GC column. However, use of a methanol or toluene modifier for CO(2) SFE directly coupled to GC effected complete loss of extracted pyrene.     

HPLC-ICP-MS for a comparative study on the extraction approaches for arsenic speciation in terrestrial plant, Ceratophyllum demersum

For the determination of arsenic compounds in terrestrial plant samples, a crucial step is the efficient extraction of arsenic from the solid plant matrix. However, the use of methanol-water extraction often resulted in low extraction efficiencies of less than 50%. In this study, eight solid-liquid extraction procedures (mainly based on mechanical mixing and sonication) were evaluated for the recovery of arsenic species from a submerged freshwater plant, coontail (Ceratophyllum demersum), collected in Moira River, Ontario, Canada. Speciation of As in the extracts was carried out with both anion-, and cation-exchange HPLC with sector-field inductively coupled plasma mass spectrometric (SF-ICP-MS) detection. The results obtained depended critically on the extraction solvents used in different extraction procedures. Extraction with methanol-water led only to 9%–44% recoveries of As. A high extraction yield (approximately 82%) was obtained by water extraction. Alkaline hydrolysis also resulted in high extraction efficiencies (86%–98%), but severe oxidation of As(III) to As(V) was observed. A protease enzymatic extraction led to a recovery of 48%. Approximately 0.5% of the total As in the plant sample was lipid-soluble. It was found that the extraction of inorganic arsenic species was suppressed by the presence of methanol in the extraction solvents, while high content of methanol in the extraction solvents was effective for the extraction of organic arsenic species. Therefore, it is recommended to perform the extraction both with water alone and with methanol-water (9+1, v/v), in order to obtain the complete As species profile in terrestrial plants.     

Direct solventless supercritical fluid extraction of chlorbiphenyls from aqueous solutions at 0.1 × 10–12 g/g level and whole extract analysis by GC/ECD

A method of PCB determination in water based on direct supercritical fluid extraction (SFE) and off-line solventless SFE/GC coupling has been developed. High SFE recovery of the targeted compounds from water and high efficiency of their solventless transfer into GC were achieved. The method can be used for fast screening of water samples for PCBs at ultratrace levels.     

Direct solventless supercritical fluid extraction of chlorbiphenyls from aqueous solutions at 0.1 × 10–12 g/g level and whole extract analysis by GC/ECD

A method of PCB determination in water based on direct supercritical fluid extraction (SFE) and off-line solventless SFE/GC coupling has been developed. High SFE recovery of the targeted compounds from water and high efficiency of their solventless transfer into GC were achieved. The method can be used for fast screening of water samples for PCBs at ultratrace levels.     

Analytical supercritical fluid extraction of Chinese herbal medicines

Summary An analytical supercritical fluid extraction (SFE) technique, followed by GC/MS, was developed to separate and determine the volatile components in Chinese herbal medicine. Three kinds of herbs, frankincense, myrrh, andEvodia rutaecarpa were extracted and analyzed. The extraction was carried out using supercritical fluid CO₂ at 20 MPa and 50°C. The main factors affecting the efficiency and selectivity of the extraction are discussed. The results revealed the potential of supercritical fluid extraction as an analytical procedure for the study of medicinal plants.     

Arsenic extraction and speciation in carrots using accelerated solvent extraction, liquid chromatography and plasma mass spectrometry

Arsenic present in freeze-dried carrots was extracted using accelerated solvent extraction (ASE). Several parameters, including selection of the dispersing agent, extraction time, number of extraction cycles, particle size and extraction temperature, were evaluated to optimize the ASE method. Filtering and treatment with C-18 SPE cartridges were also evaluated as part of the sample preparation procedure before speciation analysis. The method was validated by spiking single arsenical and mixed arsenical standards on the dispersing agent and on portions of freeze-dried carrot prior to extraction. LC-ICP-MS was used to determine individual arsenic species in the carrot extracts. A weak anion-exchange column was used for the separation of As(III), As(v), monomethylarsonic acid (MMA), dimethylarsinic acid and arsenobetaine. Optimized sample preparation conditions were applied to the extraction of arsenic in nine freeze-dried carrot samples. Total arsenic concentration in the carrot samples ranged from less than 20 ng g(-1) to 18.7 microg g(-1), dry mass. Extraction efficiency, defined as the ratio of the sum of individual arsenic species concentrations to total arsenic, ranged from 80 to 102% for freeze-dried carrots with arsenic concentrations greater than the limit of quantitation. Inorganic As(III) and As(v) were the only species found in samples that contained less than 400 ng g(-1) total arsenic. MMA and an unidentified arsenic compound were present in some of the samples with higher total arsenic content.     

GC and MS Properties of β-Blockers as tert-Butyldimethylsilyl Derivatives and as Ethoxycarbonyl/Trimethylsilyl Derivatives

Fourteen β-blockers in pre-dried free base forms were simultaneously converted into tert-butyldimethylsilyl (TBDMS) derivatives in one-step. As a different approach, β-blockers were directly transformed into N-ethoxycarbonyl (EOC) derivatives in aqueous solution, followed by extraction and trimethylsilyl (TMS) derivatization. The retention index sets measured by DB-5 and DB-17 dual-column GC were characteristic for each β-blocker as TBDMS- and EOC/TMS derivatives. Their characteristic fragmentation patterns obtained by GC–MS facilitated easier peak identification of each β-blocker. The overall EOC/TMS method for assays of 14 β-blockers in aqueous solution was linear with acceptable precision and accuracy.     

Feasibility of on-line supercritical fluid extraction of steroids from aqueous-based matrices with analysis via gas chromatography-mass spectrometry

The solubility of testosterone, boldenone, androstenone, etiocholanolone, and epitestosterone are measured in pure supercritical CO2. Testosterone exhibited the highest solubility in supercritical CO2. The solubility of all steroids except epitestosterone increased by one order of magnitude with increasing pressure from 100 to 400 atm. Epitestosterone had the lowest solubility in supercritical CO2 and its solubility was not affected by pressure. The extraction efficiency of steroids from an aqueous saline environment exceeded 95%. Because of the partial solubility of water in supercritical CO2, the addition of a moisture trap after the aqueous vessel is necessary to prevent the plugging and deterioration of the gas chromatographic (GC) column. It is demonstrated that on-line supercritical fluid extraction-GC-mass spectrometry is feasible for the quantitative extraction and analysis of steroids from both saline and urine solutions. However, it is determined that the adsorbent vessel filled with Hydromatrix is not sufficient to trap all the moisture, and after 3 to 4 extractions, the GC column efficiency lowered.