Direct analysis of trace level bisphenol A, octylphenols and nonylphenol in bottled water and leached from bottles by ultra-high-performance liquid chromatography/tandem mass spectrometry.

A high-throughput method was developed for the direct analysis of trace level bisphenol A (BPA), 4-n-octylphenol (4-n-OP), 4-tert-octylphenol (4-t-OP) and 4-n-nonylphenol (4-n-NP) in water samples by ultra-high-performance liquid chromatography/tandem mass spectrometry (uHPLC/MS/MS) using an isotope-labeled internal standard. Aliquots of water samples were spiked with the internal standard and analyzed without sample cleanup or enrichment. All target analytes were chromatographically separated within 3 min and detected using the highly selective multiple reaction monitoring (MRM) detection mode. The method detection limits were statistically calculated and ranged from 0.040 ppb (BPA) to 0.057 ppb (4-n-NP). Excellent correlation of determination was achieved for each analyte with r greater than 0.995. Precision was achieved within 8% relative standard deviation (RSD) for all analytes, and recoveries from spiked samples ranged from 97% to 106.2% except for 4-n-OP which may be corrected by using an isotope-labeled analog as internal standard. This method was used for analyzing eight randomly selected bottled water samples and found no detectable target analytes. This method was also used to analyze target analytes leached from bottles (6 low cost bottles and 6 brand-name baby-feeding bottles). Low levels of BPA were found in three bottles after they had been heated in a microwave oven, and a trace amount of 4-n-NP was also found in three bottles. 4-t-OP, which has not been reported as a leachable chemical, was found in two brand name baby-feeding bottles from the same manufacturer, and was confirmed with bottles from different batches.

Optimizing mass spectrometric detection for ion chromatographic analysis. I. Common anions and selected organic acids.

We describe a systematic method of optimizing mass spectrometric (MS) detection for ion chromatographic (IC) analysis of common anions and three selected organic acids using response surface methodology (RSM). RSM was utilized in this study because it minimized the number of experiments required to achieve the optimum MS response and included the interactions between individual parameters for multivariable optimization. Five MS parameters, including probe temperature, nebulizer gas, assistant makeup flow, needle voltage and cone voltage, were screened and systematically optimized by two steps. Central composite design (CCD) was used to design the experiment points and a quadratic model was applied to fit the experimental data. Analysis of variance (ANOVA) was carried out to evaluate the validity of the statistical model and to determine the most significant parameters for MS response. The optimum MS conditions for each analyte were summarized and the method optimum condition was achieved by applying desirability function. Our observation showed good agreements between statistically predicted optimum response and the responses collected at the predicted optimum condition. Operable range of each parameter (with normalized MS response greater than 0.8 for each analyte) was provided for general anionic IC/MS applications.

Simultaneous quantitation of 2-acetyl-4-tetrahydroxybutylimidazole, 2- and 4-methylimidazoles, and 5-hydroxymethylfurfural in beverages by ultrahigh-performance liquid chromatography-tandem mass spectrometry.

An ultrahigh-performance liquid chromatography (UHPLC) tandem mass spectrometric (MS/MS) method was developed for the simultaneous quantification of 2-acetyl-4-tetrahydroxybutylimidazole (THI), 2- and 4-methylimidazoles (2-MI and 4-MI), and 5-hydroxymethylfurfural (HMF) in beverage samples. A C30 reversed-phase column was used in this method, providing sufficient retention and total resolution for all targeted analytes, with an MS/MS instrument operated in selected reaction monitoring (SRM) mode for sensitive and selective detection using isotope-labeled 4-methyl-d(3)-imidazole (4-MI-d(3)) as the internal standard (IS). This method demonstrates lower limit of quantification (LLOQ) at 1 ng/mL and coefficient of determination (r(2)) >0.999 for each analyte with a calibration range established from 1 to 500 ng/mL. This method also demonstrates excellent quantification accuracy (84.6-105% at 5 ng/mL, n = 7), precision (RSD < 7% at 5 ng/mL, n = 7), and recovery (88.8-99.5% at 10, 100, and 200 ng/mL, n = 3). Seventeen carbonated beverage samples were tested (n = 2) in this study including 13 dark-colored beverage samples with different flavors and varieties and 4 light-colored beverage samples. Three target analytes were quantified in these samples with concentrations in the range from 284 to 644 ng/mL for 4-MI and from 706 to 4940 ng/mL for HMF. THI was detected in only one sample at 6.35 ng/mL.

Preliminary demonstration of an IonCCD as an alternative pixelated anode for direct MCP readout in a compact MS-based detector.

We report on the preliminary testing of a new position-sensitive detector (PSD) by combining a microchannel plate (MCP) and a charge-sensitive pixilated anode with a direct readout based on charge-coupled detector (CCD) technology, which will be referred to as IonCCD (Hadjar et al. J Am Soc Mass Spectrom 22(4):612-623, 2011; Johnson et al. J Am Soc Mass Spectrom 22(8):1388-1394, 2011; Hadjar et al. J Am Soc Mass Spectrom 22(10):1872-1884, 2011). This work exploits the recently discovered electron detection capability of the IonCCD (Hadjar et al. J Am Soc Mass Spectrom 22(4):612-623, 2011), allowing it to be used directly behind an MC. This MCP-IonCCD configuration potentially obviates the need for electro-optical ion detector systems (EOIDs), which typically feature a relatively difficult-to-implement 5-kV power source as well as a phosphorus screen behind the MCP for conversion of electrons to photons prior to signal generation in a photosensitive CCD. Thus, the new system (MCP-IonCCD) has the potential to be smaller, simpler, more robust, and more cost efficient than EOID-based technologies in many applications. The use of the IonCCD as direct MCP readout anode, as opposed to its direct use as an ion detector, will benefit from the instant three-to-four-order-of-magnitude gain of the MCP with virtually no additional noise. The signal/noise gain can be used for either sensitivity or speed enhancement of the detector. The speed enhancement may motivate the development of faster IonCCD readout speeds (currently at 2.7 ms) to achieve the 2 kHz frame rate for which the IonCCD chip was designed, a must for transient signal applications. The presented detector exhibits clear potential not only as a trace analysis detector in scan-free mass spectrometry and electron spectroscopy but also as a compact detector for photon and particle imaging applications.