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PAPER

www.rsc.org/jaas | Journal of Analytical Atomic Spectrometry

Reversed phase ion-pairing HPLC-ICP-MS for analysis of organophosphorus chemical warfare agent degradation productsw
Douglas D. Richardson, Baki B. M. Sadi and Joseph A. Caruso*
Received 16th March 2005, Accepted 6th January 2006 First published as an Advance Article on the web 23rd January 2006 DOI: 10.1039/b503857j The separation and analysis of three organophosphorus chemical warfare degradation products is described. Ethyl methylphosphonic acid (EMPA, the major hydrolysis product of VX), isopropyl methylphosphonic acid (IMPA, the major hydrolysis product of Sarin (GB)), and methylphosphonic acid (MPA, the final hydrolysis product of both) were the analytes and were separated by reversed phase ion-pairing high-performance liquid chromatography (RP-IP-HPLC) with the use of myristyl trimethylammonium bromide as ion-pairing reagent and an ammonium acetate–acetic acid buffer system (pH 4.85). An Agilent 7500ce inductively coupled plasma mass spectrometer (ICP-MS) equipped with collision/reaction cell technology was coupled to the chromatographic system for detection of 31P and 47PO1. Historically, ICP-MS detection of phosphorus has been limited due to its high first ionization potential (10.5 eV) and the presence of severe nitrogen polyatomic interferences (such as 14N16O1H1 and 15N16O1) overlapping its only isotope at m/z = 31. Implementation of an octopole reaction cell with helium as the cell gas allowed for removal of the nitrogen polyatomic interferences and reduction of background signal. Detection limits for EMPA, IMPA, and MPA were found to be 263, 183 and 139 pg mLÀ1, respectively, with separation in less than 15 min. The developed method was successfully applied to the analysis of spiked environmental water and soil samples.

Introduction
Recent increases in terrorist activity and the threat of chemical weapon attacks have lead to the demand for a rapid and reliable method for the analysis of chemical warfare agents (CWA) and their degradation products. As a result of the Chemical Weapons Conventions (CWC), which banned the production, acquisition, retention, and direct or indirect transfer of chemical weapons, destruction of all chemical weapons held in reserve was mandated.1,2 These chemicals, which include nerve and vesicant agents, pose a deadly threat not only to the human population but also to vital aqueous and agricultural resources (Table 1.).1,3–6 Based on these facts the development of a sensitive and selective analytical technique for the analysis of CWA and their degradation products is of high importance to ensure homeland security. Phosphorus containing nerve agents, along with their degradation products, present difficulties for ultra-trace analysis due to their high polarity, low volatility, and lack of a good chromophore. Direct analysis of CWA degradation products provides an indirect technique for CWA detection. Previous studies have successfully utilized methods such as gas chromatography-mass spectrometry (GC-MS), ion mobility-mass spectrometry (IMMS), and liquid chromatography-mass spectrometry (LC-MS) for the analysis of organophosphorus containing degradation products with detection limits in the
Department of Chemistry, University of Cincinnati, McMicken College of Arts and Sciences, Cincinnati, Ohio 45221-0172, USA E-mail: joseph.caruso@uc.edu; Web: http//www.uc.edu/plasmachem/ w Presented at the 2005 Winter Conference on Plasma Spectrochemistry, January 30–February 3, 2005, Budapest, Hungary.

ng mLÀ1 range.4,5,7 However, considering the lethal doses reported in Table 1, lower detection limits in the pg mLÀ1 range are desirable for such nerve agents and their degradation products. To achieve this lower level detection requires a more selective analytical detection technique such as inductively coupled plasma mass spectrometry (ICP-MS). Elemental speciation analysis by ICP-MS allows for high sensitivity, low level detection, and elemental selectivity, making it the instrument of choice for ultra-trace elemental speciation studies.8–14 Phosphorus (m/z = 31) analysis by ICP-MS, until recently, was limited due to its high first ionization potential (10.5 eV) and polyatomic interferences, including 14N16O1H1 and 15N16O1 (m/z = 31).15 Sector-field MS detection with ICP sources does provide a potential resolution enhancement but at the expense of losing part of the beam. For elements with high ionization potentials the throughput is clearly diminished. Recent developments in collision/reaction cell technology16,17 have allowed for the analysis of elements prone to isobaric and polyatomic interferences through removal by collisional dissociation (collision energy c bond energy), chemical reaction, and/or energy discrimination.9 Recently Sadi et al.9 applied ICP-MS detection to phosphorus containing herbicides through the use of state of the art collision/reaction cell technology. Separation of two phosphorus based general purpose herbicides, as well as aminomethylphosphonic acid (AMPA) by reversed phase ionpairing high-performance liquid chromatography (RP-IPHPLC)18 achieved detection limits of less than 32 pg mLÀ1.9 In this study reversed phase ion-pairing chromatography was coupled with ICP-MS detection for the analysis of three organophosphorus degradation products of Sarin (GB) and
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396 | J. Anal. At. Spectrom., 2006, 21, 396–403

The Royal Society of Chemistry 2006

20 mm Nalgene nylon–cellulose acetate (CA) syringe filters (Nalge Nune International Corporation. Preparation of the soil samples consisted J. b Cerilliant MSDS. All water was prepared by passing through a NanoPure (18 MO) treatment system (Barnstead. 396–403 | 397 The Royal Society of Chemistry 2006 . NJ) solution with 5 mmol LÀ1 ion pairing agent and 2% methanol (TEDIA. Experimental Reagents The three chemical warfare degradation products (ethyl methylphosphonic acid (EMPA). Rochester.85 was used as the chromatographic buffer. myristyl trimethylammonium bromide (Aldrich. TX) as 1 mg mLÀ1 certified reference materials (CRMs).09–2 mg-min mÀ3 (Agent MSDS).14 Chemical warfare degradation products Degradation product pKa 2. Further dilutions of these stock solutions in HPLC buffer. their precursors. isopropyl methylphosphonic acid (IMPA). A detailed description of the ion-pairing chromatography employed as well as the selection of optimum ion-pairing reagent is provided. was used as the collision/reaction gas throughout all experiments. as well as preparation of standard mixtures over the range 20–400 ng mLÀ1.5 Stock solutions of 10 mg mLÀ1 for each degradation product were prepared through dilution in HPLC buffer. with a purity of 99. 1. Parisppany. corresponding to a phosphorus concentration of 5 ng mLÀ1. St. Spectrom. Boston. Both water samples were filtered through 0.) Environmental water samples used in this experiment were collected in polypropylene bottles from laboratory tap water and the Little Miami River in Cincinnati. are presented. 21. NJ). Environmental soil samples were collected from top soil outside of the laboratory and potting soil kindly provided by the greenhouse at the University of Cincinnati. were performed as needed. the developed technique was applied to spiked samples of Little Miami (Ohio) River water. WI). ethyl methylphosphonic acid (EMPA). MO). Instrument tuning was accomplished through the use of a 30 ng mLÀ1 adenosine 5 0 -triphosphate (Sigma.. MO). NY) to remove unwanted particulate matter from entering the system. and soil samples. or 3 toxic chemicals. Milwaukee. 2006. Finally. CRMs are used as standard analytical solutions for analysis of Schedule 1. OH) at pH 4. Anal. Louis. tap water. Helium collision/reaction cell optimization experiments for the removal of polyatomic interferences through collisional processes and by application of an appropriate energy barrier are also described. Analytical figures of merit for each species studied.1. Louis.16 Degradation product oral human LDLO/mg kgÀ1 24 2. and hexadecyl trimethylammonium bromide (Sigma. 2.999%. NJ). WI).41 pKa2 = 7. Fairfield. Ion pairing agents used in these experiments consisted of: tetrabutylammonium hydroxide (Aldrich. OH. Gas flow rate was optimized during instrument tuning prior to each experiment and controlled by the mass flow controller provided with the instrument (Fig. Milwaukee.54 a Vapor form LD50 values range from B0. MA). St. Fairlawn. and methylphosphonic acid (MPA)) used were obtained from Cerilliant (Austin. Helium gas (Matheson Gas Products. At. and/or degradation products as mandated by the CWC for verification.24 143–428b See above pKa1 = 2. VX. isopropyl methylphosphonic acid (IMPA). Adjustment of the pH was accomplished through addition of glacial acetic acid (Fisher Scientific.Table 1 Chemical warfare agents and degradation products Chemical warfare agent Agent liquid LD50/mg kgÀ1a 0. The buffer was prepared fresh from stock solution before starting the experiments. and methylphosphonic acid (MPA). This journal is  c The reagents utilized throughout this experiment were of analytical grade prepared fresh daily through dilution of stock standards with DDI water. A 50 mmol LÀ1 ammonium acetate (Fisher Scientific. Fairlawn.

100 A. Japan) ICP-MS equipped with shielded torch and collision/reaction cell technology was used for the element specific detection of 31P and 47 PO1 throughout this experiment. 0 units.24 (Table 1). hexadecyltrimethylammonium bromide (HAB).. The source parameters were as follows: sheath gas flow. 398 | J. pKa2 7. 5 mm.20 L minÀ1 Glass expansion Microconcentric E2 1C (Scott double channel) 6 mm Nickel 0. This journal is  c The Royal Society of Chemistry 2006 . pKa 4. myristyltrimethylammonium bromide (TTAB). All environmental samples were processed as blanks and 100 ng mLÀ1 spiked mixtures (prior to filtration) of ethyl methylphosphonic acid. ion-pairing chromatography was investigated as the chromatographic separation technique.Table 2 HPLC-ICP-MS instrumental parameters ICP-MS parameters Forward power Plasma gas flow rate Auxiliary gas flow rate Carrier gas flow rate Nebulizer Spray chamber Sampling depth Sampling and skimmer cones Dwell time Isotopes monitored (m/z) Octopole reaction system HPLC parameters Instrument Flow rate Injection volume Buffer 1500 W (with shielded torch) 15. 5 mm. and diode array detector was used for the separation of the three chemical warfare degradation products. 35 units. thermostated column compartment.85 was used in the separation experiments.5 Â 3.0 mL of DDI water and stirring for 15 min. 396–403 Results and discussion Owing to the charged nature of the compounds of interest.41. Lyophilized peak fractions were dissolved in DDI water (14 mg mLÀ1) and analyzed following the procedure described above. California) high-performance liquid chromatograph (HPLC) equipped with a binary pump. An Agilent 7500ce (Agilent Technologies. 21. Based upon the acid dissociation constants a buffer system (acetic acid–ammonium acetate.8) at pH 4. of placing 1. The resulting solution was filtered through 0. Alltech Associates Inc. Parameters were optimized by insertion of an EMPA (10 mg mLÀ1) standard solution at 3 mL minÀ1 using a syringe pump.20 mm Nalgene nylon–cellulose acetate syringe filters (Nalge Nune International Corporation.1 s 31 P and 47PO1 He (Flow optimized prior to experiment) Agilent 1100 HPLC 0. Instrumentation HPLC conditions. and methylphosphonic acid. The collision/ reaction cell consisted of an octopole ion guide operated in rf only mode which also served for the removal of polyatomic interferences. IL) was used for all separation experiments. A detailed description of ICP-MS operating conditions is provided in Table 2. Palo Alto. Electronic coupling of the ICP-MS with the HPLC was accomplished through the use of a remote cable which allowed for simultaneous starting prior to each chromatographic run.00 kV. It was believed that the hydrophobicity and difference in effective charges of the different species would allow for separation by the proposed chromatography. The acid dissociation constants for the chemical warfare degradation products are: methylphosphonic acid (MPA) pKa1 2. San Jose. Alltech Associates Inc. Tetrabutylammonium hydroxide (TBAH) was first investigated as the ion-pairing reagent for the separation of the three species of interest. CA) linear ion trap mass spectrometer equipped with an Ion Max source and Xcalibur (version 1. Full scan MS and MS/MS spectra were acquired by insertion of the sample solutions at 3 mL minÀ1. Anal. 3. vacuum degasser. ethyl methylphosphonic acid pKa1 2. IL) with a guard column (Alltima C8.4 SR1) data software. Electrospray mass spectrometry (ESI-MS). Deerfield. and isopropyl methylphosphonic acid pKa1 2.0 L minÀ1 1.0 g of solid material in 5. Deerfield.0 mm. autosampler.2 Â 150 mm) 5 mm pH Column Fig. A C8 column (Alltima ˚ C8. NY). 7. 2% Methanol 5 mM Myristyl trimethylammonium bromide 4. Rochester. An Agilent 1100 (Agilent Technologies. The ESI-MS spectra were acquired in negative ion mode using a Finnigan LTQ (Thermo Electron Corporation. and capillary temperature. Spectrom.6 L minÀ1 1.5 mL minÀ1 100 mL 50 mM ammonium acetate. The collision energy for MS/MS experiments was 41%. auxiliary and sweep gas flow. isopropyl methylphosphonic acid. 1 Separation comparison of three ion-pairing reagents: tetrabutylammonium hydroxide (TBAH).54.16.2 Â 150 mm. A detailed description of the HPLC separation conditions is provided in Table 2. 300 1C. At. Inductively coupled plasma mass spectrometer (ICP-MS). 4. 2006. Baseline resolution was not achieved between the ion-pairs formed with this compound.85 Alltima C8 (3. Tokyo. spray voltage.

Other researchers depended upon the formation of PO1 (m/z = 47). and IMPA were found to be 139. and isopropyl methylphosphonic acid with the selected column in less than fifteen minutes (Fig. Optimization of the helium gas flow rate was accomplished through the use of a mass flow control valve and constant introduction of 30 ng mLÀ1 adenosine 5 0 -triphosphate (corresponding to 5 ng mLÀ1 phosphorus) in buffer. Spectrom. ICP-MS detection Element specific detection by ICP-MS is a popular analytical technique based on the high sensitivity and selectivity offered by this instrument. This work consisted of the use of a helium collision cell for the removal of 14N16O1H1 and 15N16O1 interferences through a collision/energy discrimination process. 2. 3 Separation of blank and 100 ng mLÀ1 spiked Little Miami River (Ohio) water. 263. Phosphorus response versus helium flow rate was plotted and the flow rate corresponding to optimal signal with minimal background (buffer signal m/z = 31) was selected (Table 2. baseline resolution was also not achieved. phosphorus analysis by ICP-MS has grown in popularity due to the ability to remove nitrogen-based polyatomic interferences to 31P and the ability to ionize phosphorus sufficiently in spite of its high first ionization potential. respectively. Anal. All regression coefficients (r2) values were acceptable with the lowest value being 0. The detection limits for these three species are an improvement of at least one order of magnitude compared with those reported J. consisting of an intermediate length alkyl chain.20 or the use of high-resolution mass spectrometers to differentiate between the polyatomic interferences and the phosphorus signal at m/z = 31.). Helium was chosen as the collision gas for all experiments due to its light/nonThis journal is  c Fig. Myristyl trimethylammonium bromide (TTAB). Any fragmentation of the polyatomic interferences would need to overcome the nitrogen–oxygen bond energy by using helium. 3). 21. EMPA.993. 2 Separation of 100 ng mLÀ1 mixture of MPA. selective ion transmission through adjustment of the pole bias plays a vital role in analyte response. Detection limits (3s) based on three times the standard deviation of seven replicates of the blank peak areas (IUPAC) for the analysis of MPA. Hexadecyltrimethylammonium bromide (HAB) was then investigated as an ion-pairing reagent due to its longer alkyl chain: however.21 After overcoming the polyatomic interferences with collisional dissociation. 396–403 | 399 The Royal Society of Chemistry 2006 .. 2006. was then investigated as an ion-pairing reagent. ethyl methylphosphonic acid.0 mL minÀ1 helium for all experiments based upon the optimization results. Recently. Myristyl trimethylammonium bromide along with an ammonium acetate–acetic acid buffer (pH 4.12. reactive nature to allow for reduction of the background signal at m/z 31.19. and 183 pg mLÀ1. At. Analytical figures of merit Calibration curves were prepared through the use of standard mixtures ranging from 20 to 400 ng mLÀ1. EMPA and IMPA.5–4.21–23 Monitoring of PO1 in these experiments was performed to ensure no loss of 31P signal by oxide formation.85) and 2% methanol for the mobile phase allowed separation of methylphosphonic acid. A comparison of the separation achieved with each ion-pairing reagent is provided in Fig. The gas flow used ranged from 3.Fig.9. In this experiment instrument selectivity was vital because of the need for element specific detection of phosphorus (m/z = 31) and the complex nature of the environmental matrices analyzed.

although these detection limits were calculated based upon a concentration that would give a signal three times that of the noise. 21. filtered through a strong cation exchange column to remove the ion pairing agent. 3.263e Based on concentration producing a signal three times that of the noise. 6 and 7 show both blank and spiked top soil and potting soil samples. b Estimated in SIM mode at concentrations down to 50 ng mLÀ1 for signal-to-noise ratio of 3 : 1. tap water. Based upon the mass spectrometric data EMPA was determined not to be the unknown species present in water and soil samples.. and lyophilized. c Estimated from signal-tonoise characteristics (S/N = 3) of the response for 150 ng mLÀ1 mixture. Anal. Samples were treated with the sample preparation procedure described in the Experimental section.0 RSD (%) peak area 2.75 5. 396–403 The Royal Society of Chemistry 2006 . This journal is  c 400 | J.38 0. and potting soil samples. An unknown peak around 600 seconds is observed in both samples and overlaps with the EMPA spike. The analytical figures of merit are summarized in Table 4. Characterization efforts Initial characterization efforts of the unknown peak overlapping EMPA in the standard separation consisted of electrospray ionization mass spectrometry (ESI-MS) and time elapsed hydrolysis experiments. Mass spectrometric analysis of standard EMPA showed a strong molecular ion peak at m/z 123 (data not shown). the trend of the spiked top soil sample shows an increase in the EMPA peak compared with the standard sample chromatogram (Fig. The blank chromatograms do not show the presence of any unknown peaks. top soil. 2006. Analysis of the concentrated river water fractions did not show the presence of EMPA (no m/z 123 peak). 4 Separation of blank and 100 ng mLÀ1 spiked laboratory tap water. d Based on IUPAC.2 73. 4 and 5 show blank and spiked Little Miami River and laboratory tap water samples. These values ranged from 69–86%.). Spectrom. At.139–0. The interfering peak from blank Little Miami River water injections (retention time 600 s) was collected multiple times (>15). reported unknown organophosphorus comTable 4 Analytical figures of merit based on 20 ng mLÀ1 mixture Chemical warfare Detection Column degradation limit/pg recovery product mLÀ1 MPA EMPA IMPA 139 263 183 86. Sadi et al. pounds in raw river water samples: however they were not identified.39 5. The precision for repeated injections of a 20 ng mLÀ1 standard mixture was less than 1% for retention times and less than 6% for peak areas.65 Fig.Table 3 Chemical warfare degradation product detection limits Chemical warfare degradation Analytical products method Ion mobility mass spectrometrya Detection limits/ ng mLÀ1 560–17005 LC-ESI-TOFb Electrophoresis microchip with contactless conductivity detectorc 80–10003 48–8624 RP-IP-HPLC-ICP-MSd 0. Complex samples Investigation of complex sample matrix effects on the method led to the collection of Little Miami (Ohio) River water. a in other analytical techniques (Table 3). however. Column recovery was calculated to evaluate the efficiency of the sample preparation and separation techniques. Figs.96 RSD (%) retention time 0. e This work.2 69.9 Figs. resulting in an increased peak area.55 0.

NJ) were analyzed by the developed separation method (pH 4. At. Identical net charges of these species at the buffer pH of 4. The resulting sample was spiked with 10 mg mLÀ1 MPA and an increase in peak area was observed at 450 s (Fig. and sodium phosphate (Fisher Scientific.16 and 2. Ammonium phosphate (SCP Science. the coupling of ion-pairing reversed phase HPLC with ICP-MS equipped with a collision/reaction cell allowed for trace analysis of three organophosphorus chemical warfare degradation products: MPA. pKa3 12. pKa2 7.5 hours after spiking (Fig. 21. 5 Separation of blank and 100 ng mLÀ1 spiked top soil.12. 8). Anal. Application of the developed method to environmental water and soil samples demonstrated the RP-IP-HPLC-ICP-MS technique to have high potential for complex sample speciation analysis. It is interesting to note that the net charges of EMPA and This journal is  c monobasic phosphate are nearly identical. The shift in retention times for the water spiked samples is attributed to differences in their ionic strength and pH. Fig. based upon their pKa1 values of 2. Conclusion In this work. A large peak for EMPA was observed at 660 s with a minor peak for MPA seen at 450 s. Improvements in the chromatographic resolution through investigation of alternative liquid and gas J. Time elapsed experiments consisted of spiking DDI water with 10 mg mLÀ1 EMPA at ambient temperature in a clear sample vial. All three phosphate salts showed retention times of 600 s overlapping with the EMPA standard. The sample was then analyzed by the developed method 2. 396–403 | 401 The Royal Society of Chemistry 2006 . 7B). Fairlawn. NJ). 6 Separation of blank and 100 ng mLÀ1 spiked potting soil. and IMPA. EMPA. Investigation of other phosphorus containing species commonly found in environmental sample matrices led to the analysis of monobasic phosphate (pKa1 2. Spectrom.. 2006.85 can account for their overlapping migration through the ion-pairing separation. Fig. respectively.12. Data collected from the time elapsed experiment confirms previous predictions that the unknown and interfering species in river water and soil samples was not EMPA due to the lack of hydrolysis to MPA in these complex samples.Fig. This method provides a highly sensitive and selective technique with baseline separation of the three species within 15 min and detection limits of less than 263 pg mLÀ1.85. Ion-pairing chromatography offered the best separation based on interactions of the analyte between the stationary and mobile phases as well as slight charge differences between the species of interest. resulting in hydrolysis to MPA.2. potassium phosphate (Fisher Scientific. Quebec Canada).3) as the interfering species. Fairlawn. 7A).

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