Interfacial piezoelectric polarization locking in printable Ti3C2Tx MXene-fluoropolymer composites.

Piezoelectric fluoropolymers convert mechanical energy to electricity and are ideal for sustainably providing power to electronic devices. To convert mechanical energy, a net polarization must be induced in the fluoropolymer, which is currently achieved via an energy-intensive electrical poling process. Eliminating this process will enable the low-energy production of efficient energy harvesters. Here, by combining molecular dynamics simulations, piezoresponse force microscopy, and electrodynamic measurements, we reveal a hitherto unseen polarization locking phenomena of poly(vinylidene fluoride-co-trifluoroethylene) (PVDF-TrFE) perpendicular to the basal plane of two-dimensional (2D) Ti3C2Tx MXene nanosheets. This polarization locking, driven by strong electrostatic interactions enabled exceptional energy harvesting performance, with a measured piezoelectric charge coefficient, d33, of -52.0 picocoulombs per newton, significantly higher than electrically poled PVDF-TrFE (approximately -38 picocoulombs per newton). This study provides a new fundamental and low-energy input mechanism of poling fluoropolymers, which enables new levels of performance in electromechanical technologies.

Enhanced methodology for porting ion chromatography retention data.

Porting is a powerful methodology to recalibrate an existing database of ion chromatography (IC) retention times by reflecting the changes of column behavior resulting from either batch-to-batch variability in the production of the column or the manufacture of new versions of a column. This approach has been employed to update extensive databases of retention data of inorganic and organic anions forming part of the "Virtual Column" software marketed by Thermo Fisher Scientific, which is the only available commercial optimization tool for IC separation. The current porting process is accomplished by performing three isocratic separations with two representative analyte ions in order to derive a porting equation which expresses the relationship between old and new data. Although the accuracy of retention prediction is generally enhanced on new columns, errors were observed on some columns. In this work, the porting methodology was modified in order to address this issue, where the porting equation is now derived by using six representative analyte ions (chloride, bromide, iodide, perchlorate, sulfate, and thiosulfate). Additionally, the updated porting methodology has been applied on three Thermo Fisher Scientific columns (AS20, AS19, and AS11HC). The proposed approach showed that the new porting methodology can provide more accurate and robust retention prediction on a wide range of columns, where average errors in retention times for ten test anions under three eluent conditions were less than 1.5%. Moreover, the retention prediction using this new approach provided an acceptable level of accuracy on a used column exhibiting changes in ion-exchange capacity.

Micellar electrokinetic chromatography of organic and peroxide-based explosives.

CE methods have been developed for the analysis of organic and peroxide-based explosives. These methods have been developed for deployment on portable, in-field instrumentation for rapid screening. Both classes of compounds are neutral and were separated using micellar electrokinetic chromatography (MEKC). The effects of sample composition, separation temperature, and background electrolyte composition were investigated. The optimised separation conditions (25 mM sodium tetraborate, 75 mM sodium dodecyl sulfate at 25°C, detection at 200 nm) were applied to the separation of 25 organic explosives in 17 min, with very high efficiency (typically greater than 300,000 plates m(-1)) and high sensitivity (LOD typically less than 0.5 mg L(-1); around 1-1.5 µM). A MEKC method was also developed for peroxide-based explosives (10 mM sodium tetraborate, 100 mM sodium dodecyl sulfate at 25°C, detection at 200 nm). UV detection provided LODs between 5.5 and 45.0 mg L(-1) (or 31.2-304 µM), which is comparable to results achieved using liquid chromatography. Importantly, no sample pre-treatment or post-column reaction was necessary and the peroxide-based explosives were not decomposed to hydrogen peroxide. Both MEKC methods have been applied to pre-blast analysis and for the detection of post-blast residues recovered from controlled, small scale detonations of organic and peroxide-based explosive devices.

Effects of eluent temperature and elution bandwidth on detection response for aerosol-based detectors.

Aerosol detectors provide generally uniform response for most analytes, independent of their optical properties, and have the advantage of being compatible with elevated temperature mobile phases. Therefore, aerosol detectors present an attractive detection alternative for high temperature liquid chromatography (HTLC) separations. The present study has investigated the effects of HTLC conditions using aqueous mobile phases on the detection response of an evaporative light-scattering detector (ELSD) and a corona-charged aerosol detector (C-CAD). The response of the ELSD was increased up to 5-fold by increasing the separation temperature from 30°C to 180°C. The C-CAD showed much smaller increases in response under the same conditions. This increase in response was found not to result from the increased temperature for the mobile phase but rather from compression of the elution bandwidth at elevated temperature. The effect of bandwidth on detector response was confirmed using flow-injection studies in which the same amount of analyte was introduced into the detector at varying bandwidths. Furthermore, it is shown that a temperature gradient can be used to counteract the effects of varying bandwidths associated with isocratic-isothermal separations, with relatively constant bandwidth and detector response being observed with appropriate temperature gradients. This study demonstrates the necessity to consider the elution bandwidth in HTLC-aerosol detector analysis.

On-line simultaneous and rapid separation of anions and cations from a single sample using dual-capillary sequential injection-capillary electrophoresis.

A novel capillary electrophoresis (CE) approach has been developed for the simultaneous rapid separation and identification of common environmental inorganic anions and cations from a single sample injection. The method utilised a sequential injection-capillary electrophoresis instrument (SI-CE) with capacitively-coupled contactless conductivity detection (C(4)D) constructed in-house from commercial-off-the-shelf components. Oppositely charged analytes from a single sample plug were simultaneously injected electrokinetically onto two separate capillaries for independent separation and detection. Injection was automated and may occur from a syringe or be directly coupled to an external source in a continuous manner. Software control enabled high sample throughput (17 runs per hour for the target analyte set) and the inclusion of an isolation valve allowed the separation capillaries to be flushed, increasing throughput by removing slow migrating species as well as improving repeatability. Various environmental and industrial samples (subjected only to filtering) were analysed in the laboratory with a 3 min analysis time which allowed the separation of 23 inorganic and small organic anions and cations. Finally, the system was applied to an extended automated analysis of Hobart Southern Water tap water for a period of 48 h. The overall repeatability of the migration times of a 14 analyte standard sample was less than 0.74% under laboratory conditions. LODs ranged from 5 to 61 µg L(-1). The combination of automation, high confidence of peak identification, and low limits of detection make this a useful system for the simultaneous identification of a range of common inorganic anions and cations for discrete or continuous monitoring applications.

Determination of pharmaceutically related compounds by suppressed ion chromatography: IV. Interfacing ion chromatography with universal detectors.

This work forms the final part of a study investigating gradient elution ion-exchange chromatography of pharmaceutically relevant compounds, aiming at achieving complementary selectivity to reversed-phase HPLC. In this study the coupling of three universal detectors (electro-spray ionisation mass spectrometer (ESI-MS); corona charged aerosol detector (CAD); and evaporative light scattering detector (ELSD)) to suppressed IC using complex elution profiles with potassium hydroxide eluents is demonstrated. The non-volatile ions were removed from the eluent by the suppressor prior to detection, thus allowing a stable detector response, especially with the prototype electrolytic suppressor. The detector response for ten weakly anionic pharmaceuticals followed the expected models and the limits of detection obtained were not compromised by the use of a suppressor, yielding values below 50 ng/mL with MS, low to sub µg/mL levels with CAD and 2-20 µg/mL with ELSD (25 µL injections). When coupled to MS and CAD, the prototype electrolytic suppressor showed percentage relative standard deviations (%RSDs) in peak areas of 0.4-2.5% on average, compared to the chemical suppressor which yielded 1.5-3 fold higher %RSD values for the test analytes. The prototype electrolytic suppressor also generally exhibited wider linear response ranges than the chemical suppressor.

Determination of pharmaceutically related compounds by suppressed ion chromatography: III. Role of electrolytic suppressor design.

For the hyphenation of ion chromatography to nebulising detectors or mass spectrometry, suppression of the non-volatile ionic eluent to water is a required step to avoid elevated detector baselines. Presented here is a study of three new designs of electrolytic suppressors, incorporating high ion-exchange capacity screens and high ion-exchange capacity membranes in different thickness and compositions. These designs aim to minimise hydrophobic interactions of the suppressor with organic analytes and to provide higher compatibility with eluents containing acetonitrile. In comparison with a commercially available electrolytic suppressor and also a commercially available chemical suppressor, the new high-capacity suppressor showed superior performance, exhibiting minimal interactions with a test set of analytes under the examined conditions. This led to the attainment of high recoveries of the analytes after suppression (93-99% recovery) and significantly reduced band broadening during suppression. The new suppressor has been shown to perform well under both isocratic and gradient elution conditions.

Determination of pharmaceutically related compounds by suppressed ion chromatography: II. Interactions of analytes with the suppressor.

For the hyphenation of ion chromatography to nebulising detectors or mass spectrometry, suppression of the non-volatile ionic eluent to water is a required step. However, suppression of weakly acidic or weakly basic organic analytes can potentially lead to losses of analytes during suppression resulting from precipitation, hydrophobic adsorption onto the suppressor, or permeation of the analyte through the suppressor membranes. This study investigates the interactions between the suppressor and weak organic acid analytes, including pharmaceutically related compounds, for eluents containing organic solvent. Correlations were observed between analyte recovery rates after electrolytic suppression and the eluent composition, the suppression conditions, and the physico-chemical properties of the analytes. These results suggest that hydrophobic adsorption interactions occur in the electrolytic suppressor and that these interactions are ameliorated by the addition to the eluent of high levels of organic solvents, especially acetonitrile. Use of eluents containing 80% acetonitrile resulted in very low losses of analyte during suppression. Recovery experiments conducted in various compartments of the electrolytic suppressor showed that some analytes permeated through the suppressor membrane into the regenerant chambers, but this could be prevented by adding organic solvent to the regenerant solution. It was also noted that analyte losses increased with ageing of the electrolytic suppressors. Chemical suppression avoids some of the analyte losses observed with an electrolytic suppressor, but when used under the correct conditions, electrolytic suppressors gave close to equivalent performance to chemical suppressors.

Determination of pharmaceutically related compounds by suppressed ion chromatography: I. Effects of organic solvent on suppressor performance.

This overall study aims to investigate gradient elution ion-exchange chromatography of pharmaceutically relevant compounds using universal nebulisation detectors, such as evaporative light scattering detection (ELSD). Addition of organic solvents to the eluent is necessary to minimise hydrophobic adsorption on the polymeric stationary phase and improve solubility of analytes. It is also necessary to de-salt the eluent prior to detection, and in this work, ion chromatography suppressors were used for this step. Such suppressors have been designed for aqueous eluents, so the purpose of the present study was to investigate the effects of methanol and acetonitrile on suppressor performance. Chemical and electrolytic suppressors were evaluated for baseline drift, noise and efficiency of suppression using aqueous/organic eluents containing up to 40% (v/v) methanol or acetonitrile. Chemical suppression of aqueous/organic eluents showed minimal noise levels, uniform low baseline and low gradient drift. Electrolytic suppression gave good performance, but with higher baseline conductivity levels and baseline drift than chemical suppression. The elevated baseline was found not to be caused by incomplete suppression of the eluent, but was attributed to chemical reactions involving the organic solvents and facilitated by high electric currents and heat generation. It was demonstrated that suppressed ion-exchange separation using a complex KOH elution profile could be coupled with ELSD, with the suppressor effectively de-salting the eluent, producing a stable baseline. Finally, complementary separation selectivity was demonstrated using a set of pharmaceutically related organic acids separated by reversed-phase and ion-exchange methods.

Determination of bromate in sea water using multi-dimensional matrix-elimination ion chromatography.

A multi-dimensional matrix-elimination ion chromatography approach has been applied to the determination of bromate in seawater samples. Two-dimensional and three-dimensional configurations were evaluated for their efficacy to eliminate the interference caused by the high concentration of ubiquitous ions present in seawater, such as chloride and sulfate. A two-dimensional approach utilising a high capacity second dimension separation comprising two Dionex AS24 columns connected in series was applied successfully and permitted the determination of bromate in undiluted seawater samples injected directly onto the ion chromatography system. Using this approach the limit of detection (LOD) for bromate based on a signal to noise ratio of 3 was 1050 µg/L using a 500 µL injection loop. Good linearity was obtained for bromate with correlation coefficients for the calibration curves of 0.9981 and 0.9996 based on peak height and area, respectively. A three-dimensional method utilising two 10-port switching valves to allow sharing of the second suppressor and detector between the second and third dimension separations showed better resolution and detection for bromate and reduced the LOD to 60 µg/L for spiked seawater samples. Good linearity was maintained with correlation coefficients of 0.9991 for both peak height and area. Ozonated seawater samples were also analysed and exhibited a non-linear increase in bromate level on increasing ozonation time. A bromate concentration in excess of 1770 µg/L was observed following ozonation of the seawater sample for 120 min. Recoveries for the three-dimensional system were 92% and 89% based on peak height and area, respectively, taken over 5 ozonated samples with 3 replicates per sample.

Identification of inorganic improvised explosive devices using sequential injection capillary electrophoresis and contactless conductivity detection.

A simple sequential injection capillary electrophoresis (SI-CE) instrument with capacitively coupled contactless conductivity detection (C(4)D) has been developed for the rapid separation of anions relevant to the identification of inorganic improvised explosive devices (IEDs). Four of the most common explosive tracer ions, nitrate, perchlorate, chlorate, and azide, and the most common background ions, chloride, sulfate, thiocyanate, fluoride, phosphate, and carbonate, were chosen for investigation. Using a separation electrolyte comprising 50 mM tris(hydroxymethyl)aminomethane, 50 mM cyclohexyl-2-aminoethanesulfonic acid, pH 8.9 and 0.05% poly(ethyleneimine) (PEI) in a hexadimethrine bromide (HDMB)-coated capillary it was possible to partially separate all 10 ions within 90 s. The combination of two cationic polymer additives (PEI and HDMB) was necessary to achieve adequate selectivity with a sufficiently stable electroosmotic flow (EOF), which was not possible with only one polymer. Careful optimization of variables affecting the speed of separation and injection timing allowed a further reduction of separation time to 55 s while maintaining adequate efficiency and resolution. Software control makes high sample throughput possible (60 samples/h), with very high repeatability of migration times [0.63-2.07% relative standard deviation (RSD) for 240 injections]. The separation speed does not compromise sensitivity, with limits of detection ranging from 23 to 50 µg·L(-1) for all the explosive residues considered, which is 10× lower than those achieved by indirect absorbance detection and 2× lower than those achieved by C(4)D using portable benchtop instrumentation. The combination of automation, high sample throughput, high confidence of peak identification, and low limits of detection makes this methodology ideal for the rapid identification of inorganic IED residues.

Methodology for porting retention prediction data from old to new columns and from conventional-scale to miniaturised ion chromatography systems.

Several procedures are available for simulating and optimising separations in ion chromatography (IC), based on the application of retention models to an extensive database of analyte retention times on a wide range of columns. These procedures are subject to errors arising from batch-to-batch variability in the synthesis of stationary phases, or when using a column having a different diameter to that used when the database was acquired originally. Approaches are described in which the retention database can be recalibrated to accommodate changes in the stationary phase (ion-exchange selectivity coefficient and ion-exchange capacity) or in the column diameter which lead to changes in phase ratio. The entire database can be recalibrated for all analytes on a particular column by performing three isocratic separations with two analyte ions. The retention data so obtained are then used to derive a "porting" equation which is employed to generate the required simulated separation. Accurate prediction of retention times is demonstrated for both anions and cations on 2mm and 0.4mm diameter columns under elution conditions which consist of up to five sequential isocratic or linear gradient elution steps. The proposed approach gives average errors in retention time prediction of less than 3% and the correlation coefficient was 0.9849 between predicted and observed retention times for 344 data points comprising 33 anionic or cationic analytes, 5 column internal diameters and 8 complex elution profiles.

Coupled reversed-phase and ion chromatographic system for the simultaneous identification of inorganic and organic explosives.

There are many methods available to detect and positively identify either organic or inorganic explosives separately, however no one method has been developed which can detect both types of explosive species simultaneously from a single sample. In this work, a unique coupled-chromatographic system is reported for the simultaneous determination of both organic and inorganic explosive species and is used for pre-blast analysis/identification purposes. This novel approach is based on the combination of reversed-phase high performance liquid chromatography and ion chromatography which allows trace levels of organic and inorganic explosives to be determined simultaneously from a single sample. Using this procedure, a 20 min reversed-phase separation of organic explosives is coupled to a 16 min ion-exchange separation of anions present in inorganic explosives, providing a complete pre-blast analysis/identification system for the separation and detection of a complex mixture containing organic and/or inorganic explosive species. The total analysis time, including sufficient column re-equilibration between runs, was <25 min using the coupled system. By this method, the minimum resolution for the organic separation was 1.16 between nitroglycerin and tetryl and the detection limits ranged from 0.31 mg L(-1) for cyclotetramethylene tetranitramine (HMX) and 1.54 mg L(-1) for pentaerythrite tetranitrate (PETN), while the minimum resolution for the inorganic separation was 0.99 between azide and nitrate, and the detection limits ranged from 7.70 µg L(-1) for fluoride and 159.50 µg L(-1) for benzoate.

Preparation and evaluation of solid-phase microextraction fibres based on functionalized latex nanoparticle coatings for trace analysis of inorganic anions.

The use of a functionalized latex nanoparticle coating as a new sorbent phase for solid-phase microextraction (SPME) was examined. By means of electrostatic absorption onto ionized silanol groups, a fused-silica rod was coated with polymeric nanoparticles functionalized with quaternary ammonium groups. Optimum conditions for the preparation of the coated fibre are presented. The fibre was used for the extraction of a mixture of seven anions from water samples which are analysed by coupling the SPME fibre to an ion chromatographic system via a special interface. The results obtained proved the suitability of this novel coating as a new SPME fibre. A linear calibration for the target analytes was achieved over the concentration range from 5 microg L(-1) to 5 mg L(-1) (r(2)>0.988), while limits of detection for these ions were all below 3.7 microg L(-1) (S/N=3). The reproducibility of a single fibre (n=4) under similar conditions was between 7 and 12%, while the fibre to fibre reproducibility (n=5) was between 8.9 and 14%.

Application of retention modelling to the simulation of separation of organic anions in suppressed ion chromatography.

The ion-exchange separation of organic anions of varying molecular mass has been demonstrated using ion chromatography with isocratic, gradient and multi-step eluent profiles on commercially available columns with UV detection. A retention model derived previously for inorganic ions and based solely on electrostatic interactions between the analytes and the stationary phase was applied. This model was found to accurately describe the observed elution of all the anions under isocratic, gradient and multi-step eluent conditions. Hydrophobic interactions, although likely to be present to varying degrees, did not limit the applicability of the ion-exchange retention model. Various instrumental configurations were investigated to overcome problems associated with the use of organic modifiers in the eluent which caused compatibility issues with the electrolytically derived, and subsequently suppressed, eluent. The preferred configuration allowed the organic modifier stream to bypass the eluent generator, followed by subsequent mixing before entering the injection valve and column. Accurate elution prediction was achieved even when using 5-step eluent profiles with errors in retention time generally being less than 1% relative standard deviation (RSD) and all being less than 5% RSD. Peak widths for linear gradient separations were also modelled and showed good agreement with experimentally determined values.

Packing procedures for high efficiency, short ion-exchange columns for rapid separation of inorganic anions.

An optimised packing procedure for the production of high efficiency, short, particle-packed ion-exchange columns is reported. Slurry-packing techniques were applied to a series of interconnected short columns, with the columns situated intermediate between the inlet and outlet ends of the series being used for separations. The fast separation and determination of inorganic anions was achieved using short (4mm ID, 30mm long) columns packed with Dionex AS20 high-capacity anion-exchange stationary phase. Seven inorganic anions (bromate, chloride, chlorate, nitrate, sulfate, chromate and perchlorate) are separated in 2.6min using a hydroxide gradient and a flow-rate of 1.8mL/min (total analysis time including re-equilibration was 3.5min). Under isocratic conditions, the home-packed columns exhibited efficiency values of 43,000N/m for chloride at a flow-rate of 0.3mL/min, compared to 54,000N/m for a commercial 250mm AS20 column at the same flow-rate. However, the short columns gave approximately a threefold higher sample throughput. The short, home-packed columns could be produced reproducibly and gave consistent performance over extended periods of usage.

Prediction of analyte retention for ion chromatography separations performed using elution profiles comprising multiple isocratic and gradient steps.

This study addresses the simulation of ion chromatographic (IC) separations performed under conditions where the elution profile consists of a sequence of isocratic and gradient elution steps (referred to as "complex elution profiles"). First, models for prediction of retention under gradient elution conditions in IC were evaluated using an extensive database of gradient elution retention data. It is shown that one such model is preferred on the basis that it can be used to predict gradient retention times on the basis of isocratic input data. A method is then proposed for using this model for complex elution profiles whereby each step of the elution profile is treated separately and analyte movement through the column is mapped. An empirically based algorithm for predicting peak width under complex elution conditions is also proposed. Evaluation of the suggested approaches was undertaken on a set of 24 analyte anions and 13 analyte cations on 5 different Dionex columns using a range of 5-step complex elution profiles that gave R2 values for correlations between predicted and observed retention times of 0.987 for anions and 0.997 for cations. The simulation of separations of anions and cations using a 3-step complex elution profile is demonstrated, with good correlation between observed and predicted chromatograms. The proposed approach is useful for the rapid development of separations when complex elution profiles are used in IC.

Identification of homemade inorganic explosives by ion chromatographic analysis of post-blast residues.

Anions and cations of interest for the post-blast identification of homemade inorganic explosives were separated and detected by ion chromatographic (IC) methods. The ionic analytes used for identification of explosives in this study comprised 18 anions (acetate, benzoate, bromate, carbonate, chlorate, chloride, chlorite, chromate, cyanate, fluoride, formate, nitrate, nitrite, perchlorate, phosphate, sulfate, thiocyanate and thiosulfate) and 12 cations (ammonium, barium(II), calcium(II), chromium(III), ethylammonium, magnesium(II), manganese(II), methylammonium, potassium(I), sodium(I), strontium(II), and zinc(II)). Two IC separations are presented, using suppressed IC on a Dionex AS20 column with potassium hydroxide as eluent for anions, and non-suppressed IC for cations using a Dionex SCS 1 column with oxalic acid/acetonitrile as eluent. Conductivity detection was used in both cases. Detection limits for anions were in the range 2-27.4ppb, and for cations were in the range 13-115ppb. These methods allowed the explosive residue ions to be identified and separated from background ions likely to be present in the environment. Linearity (over a calibration range of 0.05-50ppm) was evaluated for both methods, with r(2) values ranging from 0.9889 to 1.000. Reproducibility over 10 consecutive injections of a 5ppm standard ranged from 0.01 to 0.22% relative standard deviation (RSD) for retention time and 0.29 to 2.16%RSD for peak area. The anion and cation separations were performed simultaneously by using two Dionex ICS-2000 chromatographs served by a single autoinjector. The efficacy of the developed methods was demonstrated by analysis of residue samples taken from witness plates and soils collected following the controlled detonation of a series of different inorganic homemade explosives. The results obtained were also confirmed by parallel analysis of the same samples by capillary electrophoresis (CE) with excellent agreement being obtained.

Identification of inorganic improvised explosive devices by analysis of postblast residues using portable capillary electrophoresis instrumentation and indirect photometric detection with a light-emitting diode.

A commercial portable capillary electrophoresis (CE) instrument has been used to separate inorganic anions and cations found in postblast residues from improvised explosive devices (IEDs) of the type used frequently in terrorism attacks. The purpose of this analysis was to identify the type of explosive used. The CE instrument was modified for use with an in-house miniaturized light-emitting diode (LED) detector to enable sensitive indirect photometric detection to be employed for the detection of 15 anions (acetate, benzoate, carbonate, chlorate, chloride, chlorite, cyanate, fluoride, nitrate, nitrite, perchlorate, phosphate, sulfate, thiocyanate, thiosulfate) and 12 cations (ammonium, monomethylammonium, ethylammonium, potassium, sodium, barium, strontium, magnesium, manganese, calcium, zinc, lead) as the target analytes. These ions are known to be present in postblast residues from inorganic IEDs constructed from ammonium nitrate/fuel oil mixtures, black powder, and chlorate/perchlorate/sugar mixtures. For the analysis of cations, a blue LED (470 nm) was used in conjunction with the highly absorbing cationic dye, chrysoidine (absorption maximum at 453 nm). A nonaqueous background electrolyte comprising 10 mM chrysoidine in methanol was found to give greatly improved baseline stability in comparison to aqueous electrolytes due to the increased solubility of chrysoidine and its decreased adsorption onto the capillary wall. Glacial acetic acid (0.7% v/v) was added to ensure chrysoidine was protonated and to enhance separation selectivity by means of complexation with transition metal ions. The 12 target cations were separated in less than 9.5 min with detection limits of 0.11-2.30 mg/L (calculated at a signal-to-noise ratio of 3). The anions separation system utilized a UV LED (370 nm) in conjunction with an aqueous chromate electrolyte (absorption maximum at 371 nm) consisting of 10 mM chromium(VI) oxide and 10 mM sodium chromate, buffered with 40 mM tris(hydroxymethyl)aminomethane at pH 8.05. All 15 target anions were baseline separated in less than 9 min with limits of detection ranging from 0.24 to 1.15 mg/L (calculated at a signal-to-noise ratio of 3). Use of the portable instrumentation in the field was demonstrated by analyzing postblast residues in a mobile laboratory immediately after detonation of the explosive devices. Profiling the ionic composition of the inorganic IEDs allowed identification of the chemicals used in their construction.

Simultaneous determination of monofluoroacetate, difluoroacetate and trifluoroacetate in environmental samples by ion chromatography.

A method is reported for the sensitive, simultaneous determination of mono- (MFA), di- (DFA), and trifluoroacetates (TFA) by ion chromatography (IC). These species were separated using a Dionex AS17 anion-exchange column employed with a potassium hydroxide gradient (via a Dionex EG40 eluent generator) and suppressed conductivity detection. The fluoroacetates were successfully separated from a range of inorganic and organic species likely to be present in environmental samples, in a total analysis time of 35 min (including re-equilibration of the column). Detection limits for mono-, di- and trifluoroacetate were 21, 38 and 36 microg/l, respectively, determined using a signal-to-noise ratio of 3, and were obtained using a sample injection volume of 50 microl. Precision was less than 0.83% relative standard deviation (RSD) for replicate injections performed over a period of 30 days. The method was applied to the determination of monofluoroacetate in river water samples and also in carrot baits.