University of North Florida
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Stuart Chalk, Ph.D.
Department of Chemistry
University of North Florida
Phone: 1-904-620-1938
Fax: 1-904-620-3535
Email: schalk@unf.edu
Website: @unf

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Joseph A. Caruso

Abbrev:
Caruso, J.A.
Other Names:
Address:
Department Chemistry, University of Cincinnati, P.O. Box 210172, Cincinnati, OH 45221 USA
Phone:
+1-5135569306
Fax:
+1-5135569239

Citations 15

"Determination Of As(III), As(V), Monomethylarsonic Acid, Dimethylarsinic Acid And Arsenobetaine By HPLC-ICP-MS: Analysis Of Reference Materials, Fish Tissues And Urine"
Talanta 2002 Volume 58, Issue 5 Pages 899-907
Kazimierz Wrobel, Katarzyna Wrobel, Bryan Parker, Sasi S. Kannamkumarath and Joseph A. Caruso

Abstract: In this study, a rapid and sensitive high performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) determination of primary As species in fish tissues and urine is reported. The separation was achieved on an Altima C 18 column with a mobile phase containing citric acid and hexanesulfonic acid (pH 4.5). As(V), monomethylarsonic acid (MMA), As(III), dimethylarsinic acid (DMA) and arsenobetaine (AsB) were separated in less than 4 min with retention times of 83, 99, 130, 166 and 208 s, respectively. This separation of five species in less than 4 min should be attractive to those interested in As speciation. The quantification limits were 44, 56, 94, 64, 66 ng L-1 and the relative standard deviations (RSD) for day-to-day injections of As at 2 µg L-1 were 2.0, 3.1, 2.4, 3.8 and 4.0%. The procedure was tested using two reference materials (DORM-2 dogfish muscle tissue, NIST SRM 2670 Freeze-dried Urine, normal level) and then applied to real-world samples. The results obtained demonstrate the suitability of the procedure for screening and quantification at physiological levels of primary As species in biological samples. (C) 2002 Elsevier Science B.V. All rights reserved.
Speciation Speciation Extraction

"A Gradient Anion Exchange Chromatographic Method For The Speciation Of Arsenic In Lobster Tissue Extracts"
Talanta 2002 Volume 58, Issue 1 Pages 133-145
Judith A. Brisbin, Clayton B'Hymer and Joseph A. Caruso

Abstract: A gradient anion exchange chromatographic technique was developed for the separation of arsenobetaine (AsB), arsenocholine (AsC), arsenite (As(III)), arsenate (As(V)), monomethylarsonic acid (MMAA) and dimethylarsinic acid (DMAA) in one chromatographic run. This technique used low residue ammonium carbonate buffer and the inductively coupled plasma-mass spectrometry (ICP-MS) chromatograms showed little baseline drift. Gradient elution improved peak shape and peak separation. The separation was completed in approximately 27 min with low detection limits (0.017-0.029 µg As kg-1). Baseline resolution of all the arsenic species evaluated was achieved when the concentration of AsC was less than approximately 12.5 µg As kg-1. This technique was successfully applied to different extracts of a standard reference material, TORT-2, and lobster tissue. AsB was found to be the major arsenic species present. AsC, DMAA, MMAA and As(V) were also found, although MMAA was not detected in all of the TORT-2 extracts. Two unknown peaks found may be due to the presence of arsenosugars or other arsenic species. Discrepancy between extraction recoveries previously determined using flow injection-ICP-MS and the high-performance liquid chromatography-ICP-MS was observed in some cases. The differences may be due to the extraction technique and/or conditions at which the extractions were performed.

"Gas Chromatography/plasma Spectrometry--an Important Analytical Tool For Elemental Speciation Studies"
Spectrochim. Acta B 2004 Volume 59, Issue 6 Pages 755-792
Jorgelina C. A. Wuilloud, Rodolfo G. Wuilloud, Anne P. Vonderheide and Joseph A. Caruso

Abstract: In this review, a full discussion and update of the state-of-the-art of gas chromatography (GC) coupled to all known plasma spectrometers is presented. A brief introductive discussion of the advantages and disadvantages of GC-plasma interfaces, as well as types of plasmas and mass spectrometers, is given. The plasma-based techniques covered include inductively coupled plasma mass spectrometry (ICP-MS) microwave-induced plasma optical emission spectrometry (MIP-OES), and inductively coupled plasma optical emission spectrometry (ICP-OES). Also, different variants of plasma sources, such as low power plasmas and glow discharge (GD) sources, are described and compared with respect to their capabilities in elemental speciation. Recent advances and alternative mass analyzers (collision/reaction cell; time-of-flight; double-focusing sector field) are also mentioned. Different aspects of the GC-plasma coupling are discussed with particular attention to the applications of these hyphenated techniques to the analysis of elemental species. Additionally, classical and modern sample preparation methods, including extraction and/or pre-concentration and derivatization reactions, are presented and evaluated.

"Solid Phase Micro-extraction Of Anions Of Environmental Interest: Application Of Conducting Polymer Micro-fiber Electrodes For Injection System For HPLC And FIA"
Proc. Electrochem. Soc. 2001 Volume 18, Issue 1 Pages 239-244
H. B. Mark, Jr., O . Ceylan, T. Gbatu, A. Galal, J. F. Rubinson,

Abstract: As the limits imposed on heavy metal content in aqueous samples have become more stringent it has become necessary to devise more rapid and efficient pre-concentration methods which maintain speciation. We propose to develop an on-line pre-concentration method and device based on Coulombic attraction between the charged form of a conducting polymer and ionic analytes in solution. Upon electrochemical conversion of the polymer back to its neutral, hydrophobic form, the analytes would be released within seconds into carrier stream for analysis by ICP/MS, HPLC/ICP-MS or FIA. [Conference Paper; 5 Refs]
Metals, heavy Mass spectrometry Preconcentration

"Micro-column High-pressure Liquid Chromatography With A Glass-frit Nebulizer Interface For Plasma Emission Detection"
J. Chromatogr. Sci. 1985 Volume 23, Issue 4 Pages 144-150
Mona Ibrahim, Wipawan Nisamaneepong and Joseph Caruso

Abstract: Microcolumn high pressure liquid chromatography (micro-HPLC) is rapidly gaining recognition as a practical separation tool for organometallic compounds. The use of the inductively coupled plasma (ICP) as a detector for micro-HPLC is studied. Several miniaturized glass-frit nebulizers are investigated as interfaces between the output of the microbore column and the ICP torch. Their performance with aqueous and methanolic solutions is evaluated by direct nebulization and flow injection analysis. The most efficient of these nebulizers is used in the micro-HPLC/ICP study of some Cd, Pb, and Zn organometallic compounds. Detection limits of 1.92 ng of Pb for tetramethyllead and 5.01 ng of Pb for tetraethyllead are obtained and compared with regular HPLC/ICP of these same compounds. Approximately equivalent detection limits were obtained when using a microwave induced plasma as an alternate plasma source. Several miniaturized glass-frit nebulizers were investigated as interfaces between the outlet of the micro-bore column and the ICP torch. Their performance was evaluated by using aqueous and methanolic solution of Cd with direct nebulization and flow injection analysis. The most suitable nebulizer was used in micro-HPLC of some organometallic Cd, Pb and Zn compounds, on a reversed-phase column of C2 material. Detection limits of 1.92 ng of Pb for tetramethyl-lead and 5.01 ng of Pb for tetraethyl-lead were obtained. These were compared with results of regular HPLC - ICP analysis; similar results were obtained with use of a microwave-induced plasma.
Cadmium Lead Zinc HPLC Spectrophotometry Method comparison Nebulizer Optimization

"Investigation Of Matrix-induced Interferences In Mixed-gas Helium-argon Inductively Coupled Plasma Mass Spectrometry"
J. Am. Soc. Mass Spectrom. 1991 Volume 2, Issue 5 Pages 355-361
Brenda S. Sheppard, Wei-Lung Shen and Joseph A. Caruso*

Abstract: The effects of various matrix constituents, Cd, Co, Pb, and synthetic ocean water, on analyte ion signal were investigated in He-Ar plasma source mass spectrometry. Analyte ion signal suppressions and enhancements were observed in the presence of varying concomitants. The method used for optimizing analyte ion lens signal determined whether suppression or enhancement was encountered. Tuning on a nitric acid standard solution results in a suppressed signal, whereas tuning on the analyte in the presence of the matrix results in signal enhancement, relative to that obtained with no concomitant present. The heavier mass lead concomitant had the greatest effect on the ion signal. Additionally, lighter analyte elements were affected to a greater extent than heavier analytes in the presence of high concomitant concentrations.
Mass spectrometry Interferences

"Multielemental Speciation Analysis Of Fungi Porcini (Boletus Edulis) Mushroom By Size Exclusion Liquid Chromatography With Sequential On-line UV-ICP-MS Detection"
J. Agric. Food Chem. 2004 Volume 52, Issue 5 Pages 1315-1322
Rodolfo G. Wuilloud, Sasi S. Kannamkumarath and Joseph A. Caruso

Abstract: An analytical methodology to determine the molecular weight (MW) distribution patterns of several elements among different compounds present in commonly consumed edible mushrooms is presented in this work. A hyphenated technique based on size exclusion liquid chromatography (SEC) coupled on-line to UV and inductively coupled plasma mass spectrometry (ICP-MS) detection was used. The association of the elements to high and low MW fractions was confirmed with sequential detection by UV and ICP-MS. Separation of the fractions was performed by injecting a 100 µL sample volume to a Superdex 75 column. The effect of different mobile phases on the separation was evaluated. Additionally, three different extraction conditions including 0.05 mol L-1 NaOH, 0.05 mol L-1 HCl, and hot water at 60°C were applied to extract the elemental species from the mushroom samples. Significant differences were observed in the chromatograms depending on the extraction conditions utilized. Optimization of the experimental variables involved in the SEC-UV-ICP-MS coupling was carried out. The method was applied to investigate the fractionation patterns of Bi, Co, Cu, Fe, I, Mo, Ni, Se, and Zn in fungi porcini (Boletus edulis) mushroom. The results obtained in this work indicate an important association of most of the elements to high MW fractions. Keywords: Multielemental speciation; edible mushrooms; metalloproteins; SEC-UV-ICP-MS

"Minimization Of Non-spectroscopic Matrix Interferences For The Determination Of Trace Elements In Fusion Samples By Flow Injection Inductively Coupled Plasma Mass Spectrometry"
J. Anal. At. Spectrom. 1991 Volume 6, Issue 8 Pages 605-608
Jiansheng Wang, E. Hywel Evans and Joseph A. Caruso

Abstract: The efficiency of various ion lens tuning strategies, flow injection and the use of an internal standard were investigated for the determination of trace elements in real samples. Spiked recoveries showed that the use of an internal standard was preferable, if a 100% recovery was to be obtained. Good recoveries were also obtained by tuning the ion lenses for a max. 115In+ signal in a matrix blank solution containing 100 ng g-1 of In, while using continuous nebulization sample introduction. Tuning the ion lenses in the presence of the matrix yielded improved recoveries compared with tuning the lenses for a standard solution This work supplements Ibid., 1990, 5, 445.
Trace elements Mass spectrometry Sample preparation Interferences Internal standard Nebulizer

"Effect Of Ion-lens Tuning And Flow Injection On Non-spectroscopic Matrix Interferences In Inductively Coupled Plasma Mass Spectrometry"
J. Anal. At. Spectrom. 1990 Volume 5, Issue 6 Pages 445-449
Jiansheng Wang, Wei-Lung Shen, Brenda S. Sheppard, E. Hywel Evans, Joseph A. Caruso and Fred L. Fricke

Abstract: The effects on the 138Ba+ signal of Co, Pb and synthetic seawater in ICP-MS were studied as a model for general non-spectroscopic matrix interference, and to examine ways to minimize such interference. Each matrix suppressed the signal, with Pb having the largest effect. Suppression was compensated for, in part, by using In as internal standard, and by tuning the ion lenses for the analyte in presence of the matrix, rather than for an acidic standard solution. Flow injection and continuous sample introduction showed no significant difference. By continual reference of analyte signals with and without matrix, any bias due to nebulizer or cone blockage was effectively eliminated.
Barium Sea Mass spectrometry Interferences Internal standard

"Evaluation Of Three Low-volume Interfaces For Organic Solvent Introduction To The Inductively Coupled Plasma - Applications To Flow Injection"
J. Anal. At. Spectrom. 1989 Volume 4, Issue 4 Pages 341-345
Timothy J. Brotherton, Peter E. Pfannerstill, John T. Creed, Douglas T. Heitkemper, Joseph A. Caruso and Sotiris E. Pratsinis

Abstract: Three low-volume sample delivery systems (described and illustrated) were evaluated for continuous solution nebulization and for flow injection introduction into the ICP: (i) a cooled mini-spray chamber, (ii) a desolvation interface, and (iii) a partial-suction injector. Each system was operated under the same conditions (tabulated). The max. solution delivery rates for each interface were >2 mL min-1 for both methanol and acetonitrile. Calibration graphs were rectilinear over three to four orders of magnitude in each instance. Detection limits under continuous solution nebulization conditions were in the mid- to sub ng mL-1 range. Flow injection peak widths were narrower for (i), (ii) and (iii) than for systems involving spray chambers with larger volume.
Spectrophotometry Nebulizer Interface Detection limit Sensitivity Peak width

"Investigation Of Problems Associated With The Determination Of Iodine In Glacial Acetic Acid Samples Using Flow Injection Analysis-inductively Coupled Plasma-mass Spectrometry"
Anal. Commun. 1999 Volume 36, Issue 8 Pages 295-298
Kathryn L. Ackley, Jason A. Day, Karen L. Sutton and Joseph A. Caruso

Abstract: Determination of iodine in glacial acetic acid is a major concern of acetic acid manufacturers and consumers. The use of ICP-MS for iodine determinations in acetic acid is hindered by memory effects that produce an elevated background signal necessitating long rinse times between samples. In this work, different analysis methods are employed in an attempt to minimize memory and matrix effects allowing for the accurate determination of iodine in glacial acetic acid using ICP-MS. Ammonium hydroxide solutions (3.7 and 7.4 M) were better at reducing the elevated iodine signal present after the introduction of an acetic acid sample than water or 0.3 M nitric acid. Memory effects were decreased when the sample was introduced by flow injection rather than constant sample aspiration. Peak areas generated by flow injection decreased significantly with increasing ammonium hydroxide concentration in the carrier solution. Iodine determinations made with 1.7 M ammonium hydroxide as the carrier solution were higher than determinations made with 3.7 M ammonium hydroxide as the carrier solution for the same samples, however, the percentage difference between the two determinations varied widely from sample to sample. All samples were analyzed by the method of standard additions in an attempt to compensate for matrix effects. This work illustrates the importance of the carrier solution in the determination of iodine in glacial acetic acid samples.
Iodine Organic compound Optimization Carry over

"Electrochemical Control Of Solid Phase Micro-extraction Using Unique Conducting Polymer Coated Fibers"
Anal. Commun. 1999 Volume 36, Issue 5 Pages 203-205
Thompson P. Gbatu, Ozcan Ceylan, Karen L. Sutton, Judith F. Rubinson, Ahmed Galal, Joseph A. Caruso and Harry B. Mark Jr

Abstract: The use of a solid phase micro-extraction (SPME) method with poly(3-methylthiophene) coated platinum micro-fiber electrodes to extract arsenate ions from aqueous solutions without derivatization is described. The fibers were fabricated by cycling the working electrode between -0.20 and +1.7 V (vs. Ag/AgCl) in an acetonitrile solution containing 50 mM 3-methylthiophene monomer and 75 mM tetrabutylammonium tetrafluoroborate (TBATFB) electrolyte. All electrochemical procedures (extraction and expulsion) were conducted in a three-electrode system. After fabrication, the conducting polymer film was immersed in the sample solution and converted to its oxidized, positively charged form by applying a constant potential of +1.2 V with respect to Ag/AgCl reference electrode. Arsenate ions migrated into the film to maintain electroneutrality. Upon subsequent reversal of the potential to -0.60 V vs. Ag/AgCl, the polymer film was converted to its reduced, neutral form and the arsenate ions were expelled into a smaller volume (200 µL) Of de-ionized water for analysis using flow injection with inductively coupled plasma mass spectrometric (ICP-MS) detection.
Derivatization Optimization

"Hydride Generation Interface For Speciation Analysis Coupling Capillary Electrophoresis To Inductively Coupled Plasma Mass Spectrometry"
Anal. Chem. 2004 Volume 76, Issue 23 Pages 7137-7142
Douglas D. Richardson, Sasi S. Kannamkumarath, Rodolfo G. Wuilloud and Joseph A. Caruso

Abstract: A novel hydride generation (HG) interface for coupling capillary electrophoresis (CE) with inductively coupled plasma mass spectrometry (ICPMS) is presented in this work. The CE-HG-ICPMS interface was applied to the separation and quantitation of common arsenic species. Lack of a commercially available HG interface for CE-ICPMS led to a three concentric tube design allowing alleviation of back pressure commonly observed in CE-HG-ICPMS. Due to the high sensitivity and element-specific detection of ICPMS, quantitative analysis of As(III), As(V), monomethylarsonic acid, and dimethylarsinic acid was achieved. Optimization of CE separation conditions resulted in the use of 20 mmol L-1 sodium borate with 2% osmotic flow modifier (pH 9.0) and -20 kV applied potential for baseline resolution of each arsenic species in the shortest time. Hydride generation conditions were optimized through multiple electrophoretic separation analyzes with 5% HCl and 3% NaBH4 (in 0.2% NaOH) determined to be the optimum conditions. After completion of system optimization, detection limits obtained for the arsenic species were less than 40 ng L-1 with electromigration time precision less than 1% within a total analysis time of 9.0 min. Finally, the interface was used for speciation analysis of arsenic in river and tap water samples.

"Trace Humic And Fulvic Acid Determination In Natural Water By Cloud Point Extraction/preconcentration Using Non-ionic And Cationic Surfactants With FI-UV Detection"
Analyst 2003 Volume 128, Issue 5 Pages 453-458
Jorgelina C. A. de Wuilloud, Rodolfo G. Wuilloud, Baki B. M. Sadi and Joseph A. Caruso

Abstract: A pre-concentration and determination method for humic and fulvic acids at trace levels in natural water samples was developed. Cloud point extraction was successfully employed for the pre-concentration of humic acid (HA) and fulvic acid (FA) prior to the determination by using a flow injection (FI) system coupled to a spectrophotometric UV-Vis detector. The quantitative extraction of HA and FA within the pH range 1-12 was obtained by neutralization of the anionic charge on the humic substances with a cationic surfactant, hexadecyltrimethylammonium bromide (CTAB). This generated a hydrophobic species that was subsequently incorporated (solubilized) into the micelles of a non-ionic surfactant polyethylene glycol, tert-octylphenyl ether (Triton X-114). The FI method for HA and FA determination was developed by injection of 100 µL of the extracted surfactant-rich phase using an HPLC pump with spectrophotometric detection at 350 nm. A 50 mL sample solution pre-concentration allowed an enrichment factor of 167. The limit of detection (LOD) obtained under the optimal conditions was 5 ?g l-1. The precision for ten replicate determinations at 0.2 mg L-1 HA was 3.1% relative standard deviation (RSD), calculated from the peak heights. The calibration using the pre-concentration system for HA and FA was linear with a correlation coefficient (r2) of 0.9997 at levels near the detection limits up to at least 1 mg l-1. The method was successfully applied to the determination of HA and FA in natural water samples (river water).

"An Evaluation Of Extraction Techniques For Arsenic Species From Freeze-dried Apple Samples"
Analyst 2001 Volume 126, Issue 2 Pages 136-140
Joseph A. Caruso, Douglas T. Heitkemper and Clayton B'Hymer

Abstract: The extraction of arsenic from freeze-dried apples and subsequent determination of individual arsenic species by HPLC-ICP-MS is described. Solvent extraction with sonication using various aqueous and aqueous/solvent mixtures was initially evaluated by measuring total arsenic extracted by ICP-MS. A two step procedure using overnight treatment with α -amylase enzyme followed by sonication for 6 h with 40 : 60 acetonitrile-water was found to provide good extraction efficiency. The concentration of arsenic extracted was compared with the concentration of total arsenic in the samples determined using ICP-MS after microwave digestion in order to calculate extraction efficiency. Individual arsenic species in the extracts were measured using HPLC-ICP-MS. The three most abundant arsenic species found were arsenite, arsenate and dimethylarsinic acid. Total arsenic concentrations in the freeze-dried apple samples ranged from 8.2 to 80.9 µg kg-1 As, dry mass. By HPLC-ICP-MS, the relative amount of inorganic arsenic in the samples ranged from 73 to 90% of the sum of the arsenic species detected in each sample.
Speciation