Online Sequential Fractionation Analysis of Arsenic Adsorbed onto Ferrihydrite by ICP-MS.

Fractionation information on arsenic (As) in complex samples, particularly solid samples, is of immense interest. Herein, selective extraction of various As species adsorbed onto ferrihydrite as the model substrate was online-adapted to inductively coupled plasma-mass spectrometry (ICP-MS) for sensitive detection. The As-adsorbed ferrihydrite sample was loaded into a homemade online sequential elution device using two commercially available micropipette tips, and then, each fraction of As including nonspecifically adsorbed, specifically adsorbed, iron oxide bonded, and residual species was successively extracted for ICP-MS detection, with H2O, NH4NO3, NH4H2PO4, ammonium oxalate, and HF as the eluents, respectively. While no water-soluble As was detected, the fraction of As bonded to iron oxide was detected as the dominant species (>80%), and the specifically adsorbed As and residual As also accounted for a substantial amount (10%). The method had a detection limit of 0.008 µg/kg for As(III) and 0.013 µg/kg for As(V), with merits such as extremely low sample consumption, high throughput, and minimized experimental manipulation, presenting an alternative strategy for sensitive fractionation analysis of As adsorbed onto solid substrates (e.g., iron oxides, etc.).

Coupling of micro-solid-phase extraction and internal extractive electrospray ionization mass spectrometry for ultra-sensitive detection of 1-hydroxypyrene and papaverine in human urine samples.

Quantification of ultra-trace analytes in complex biological samples using micro-solid-phase extraction followed by direct detection with internal extractive electrospray ionization mass spectrometry (µSPE-iEESI-MS) was demonstrated. 1-Hydroxypyrene (1-OHP) and papaverine at attomole levels in human raw urine samples were analyzed under negative and positive ion detection mode, respectively. The µSPE was simply prepared by packing a disposable syringe filter with octadecyl carbon chain (C18)-bonded micro silica particles, which were then treated as the "bulk sample" after the analytes were efficiently enriched by the C18 particles. Under the optimized experimental conditions, the analytes were readily eluted by isopropanol/water (80/20, V/V) at a high voltage of ± 4.0 kV, producing analyte ions under ambient conditions. The limit of detection (LOD) was 0.02 pg/L (9.2 amol) for 1-hydroxypyrene and 0.02 pg/L (5.9 amol) for papaverine. The acceptable linearity (R2 > 0.99), signal stability (RSD ≤ 10.7%), spike recoveries (91-95%), and comparable results for real urine samples were also achieved, opening up possibilities for quantitative analysis of trace compounds (at attomole levels) in complex bio-samples. Graphical abstract.

Sensitive and isotopic interference-free analysis of Sb using hydride generation-microwave plasma torch-mass spectrometry under ambient condition.

A sensitive and isotopic interference-free analysis method for Sb was developed based on hydride generation-microwave plasma torch-mass spectrometry (HG-MPT-MS). Compared to the conventional ICP-MS, MPT coupled to an ion trap mass spectrometer enabled much "softer" ionization of Sb under ambient condition, which provided multi-detection modes and various ion forms, such as Sb+, SbO+, SbO2-, SbO++H2O and so on. These ion formations can be easily regulated by tuning capillary voltage and tube lens voltage, which facilitated elimination of isotopic interference during analysis, for instance the interference of 123Te on 123Sb could be effectively excluded by optimizing parameters of capillary voltage and tube lens voltage. The potential application of HG-MPT-MS for Sb isotope ratio analysis was also demonstrated, which could be determined in different forms, e.g., 123Sb/121Sb or 123Sb16O/121Sb16O. The value of 123Sb/121Sb was determined to be 0.75110 ± 0.00038 (2σ, n > 50). In addition, the detection limit, linearity and spike recovery were also studied. Overall, HG-MPT-MS performed equally well on detection limit (0.05 µg/L) with ICP-MS or HG-AFS. The linearity (R2 = 0.998) was checked in the concentration range of 10-500 µg/L. Spike recovery were evaluated with two soil samples, and the obtained spike recovery ranged 90-100 %. In general, HG-MPT-MS was expected to be a versatile tool for study the biochemical or geochemical behaviors of Sb and other hydride forming elements under ambient condition in a much simpler and more efficient way.

Enhanced ultrasonic spray ionization for direct mass spectrometry analysis of aqueous solution and complex samples using a single-orifice piezoelectric atomizer.

An efficient and superior soft ionization approach for direct mass spectrometry analysis of a variety of samples such as aqueous solution, raw biological sample and proteins, was developed based on commercially available piezoelectric atomizers. A single conical orifice (5 µm in diameter) was created on the atomizer, which resulted in generation of uniform fine droplets and long-duration of MS signal. The two electrodes of piezoelectric atomizer were connected to the two sides of ceramic ring which was insulated from the metallic substrate. The unique design allowed an additional high voltage input towards the spray reagents, which facilitated direct analysis of more complex samples without sample pre-treatment, such as biological samples (tomato tissue). The ionization was driven by an extremely low electrical power (3.5 V rechargeable battery) yet providing an efficient and superior soft ionization. The method displayed a better thermal and pH stability than nano electrospray ionization (nanoESI) and electrospray ionization (ESI) on direct analysis of Vitamin B and protein aqueous solutions. Quantitative analysis of Vitamin B and Rhodamine B aqueous solutions was also investigated, showing a good linearity (R2 > 0.99). In addition, our results suggested that compared with ESI and nanoESI, the method not only could be used for direct analysis of intact protein, but also provide more information concerning the association between intact protein and the subunits.

Direct Analysis of Aqueous Solutions and Untreated Biological Samples Using Nanoelectrospray Ionization Mass Spectrometry with Pipette Tip in Series with High-Ohmic Resistor as Ion Source.

Commercially available disposable plastic pipette tip with the inner diameter of ca. 120 µm in series with a high-ohmic resistor (10 GΩ) was adapted as a low-cost alternative ion source for high-throughput nanoelectrospray mass spectrometry (nESI-MS) analysis of a variety of samples, especially aqueous solutions, without sample pretreatment. The use of high-ohmic resistor enabled the formation of stable electrospray of aqueous solutions at ambient conditions. In addition, corona discharge was avoided even with a high voltage applied. Quantitative analysis of vitamin B in water was successfully conducted by tip-ESI. The results exhibited a good linearity (R ˃ 0.9983), a low detection limit (0.25 ng/mL), and a wide dynamic response range (0.25-1000 ng/mL). Our study revealed that tip-ESI not only performed equally well to capillary nESI in terms of flow rate (˂ 100 nL/min), signal sensitivity, and sample consumption, but also offered a number of additional advantages, including better signal duration, tolerance to high analyte concentration (> 100 µg/mL) and high ionizing voltage (up to 6 kV), and obviation of tip clogging and corona discharge. High compatibility of tip-ESI with various kinds of samples (aqueous, viscous, solid, or bulk biological samples) makes it a promising tool for direct MS analysis.

Correction to: Direct Analysis of Aqueous Solutions and Untreated Biological Samples Using Nanoelectrospray Ionization Mass Spectrometry with Pipette Tip in Series with High-Ohmic Resistor as Ion Source.

Md. Matiur Rahman's name was incorrect in the original publication of this article.

Real-time monitoring of the reaction between aniline and acetonylacetone using extractive electorspray ionization tandem mass spectrometry.

In this work an on-line monitoring method was developed to study the mechanism of acetic acid catalyzed reaction between aniline and acetonylacetone using extractive electorspray ionization-tandem mass spectrometry (EESI-MS). The signals of reactants, intermediates and various byproducts were continuously detected as a function of reaction time. The chemical assignment of each signal was done via multi-stage collision induced dissociation (CID) analysis, and the reaction mechanism between aniline and acetonylacetone was deduced based on the generated molecular ions and fragment ions. The results indicate that on-line EESI-MS is an effective technique for the real time analysis of chemical reactions. EESI avoids off-line sample pretreatment and provides "soft" ionization, which allows direct analysis of various analytes at molecular level.

High ohmic resistor hyphenated gel loading tip nano-electrospray ionization source for mini mass spectrometer.

The deployment of mini mass spectrometers on the field strongly demands efficient ionization sources that are easy-to-operate. Nano-electrospray (nESI) ion source has been widely used in the field of chemistry, biology, medicine, pharmaceutical industry, clinical assessment and forensic science. In this study, a high ohmic resistor hyphenated gel loading tip nESI source was coupled with our home developed mini mass spectrometer. This ionization source has the advantages of simple-in-design, disposable and low-in-cost, therefore it could be frequently used for analysis of aqueous samples without leading to cross contamination. Performances of the gel loading tip nESI emitter were similar to pulled glass capillary, and highly compatible for the analysis of biomolecule in aqueous solution. Different peptide and small molecules have been confirmed with a continuous atmospheric pressure-interfaced (CAPI) mini mass spectrometer. The corona discharge, which was usually observed at nESI emitter tip under high aqueous solvent conditions, resulting in low ion intensity, has been successfully quenched using a 10 GΩ resistor in both a pulled glass capillary and a gel loading tip as nESI emitter in this study. Compared with conventional ESI, the metal wire assisted gel loading tip facilitated loading and direct analysis of biological samples without sample pretreatment.

As(V) and Sb(V) co-adsorption onto ferrihydrite: synergistic effect of Sb(V) on As(V) under competitive conditions.

Competitive adsorption of As(V) and Sb(V) at environmentally relevant concentrations onto ferrihydrite was investigated. Batch experiments and XPS analyses confirmed that in a binary system, the presence of Sb(V) exhibited a slight synergistic effect on As(V) adsorption. XPS analyses showed that As(V) and Sb(V) adsorption led to obvious diminishment of Fe-O-Fe and Fe-O-H bonds respectively. At pH of 9, a more significant decrease of Fe-O-Fe was observed in the binary system than that in a single system, indicating that As(V) displayed an even stronger interaction with lattice oxygen atoms under competitive conditions. Basically, ionic strength demonstrated a negligible or positive influence on As(V) and Sb(V) adsorption in binary system. Study of adsorption sequence also indicated that the presence of Sb(V) showed a promotion effect on As(V) adsorption at neutral pHs. Considering that co-contamination of As and Sb in waters has been of great concern throughout the world, our findings contributed to a better understanding of their distribution, mobility, and fate in environment.