A novel dielectric barrier discharge reactor (DBDR) was utilized to trap/release arsenic coupled to hydride generation atomic fluorescence spectrometry (HG-AFS). On the DBD principle, the precise and accurate control of trap/release procedures was fulfilled at ambient temperature, and an analytical method was established for ultratrace arsenic in real samples. Moreover, the effects of voltage, oxygen, hydrogen, and water vapor on trapping and releasing arsenic by DBDR were investigated. For trapping, arsenic could be completely trapped in DBDR at 40 mL/min of O2 input mixed with 600 mL/min Ar carrier gas and 9.2 kV discharge potential; prior to release, the Ar carrier gas input should be changed from the upstream gas liquid separator (GLS) to the downstream GLS and kept for 180 s to eliminate possible water vapor interference; for arsenic release, O2 was replaced by 200 mL/min H2 and discharge potential was adjusted to 9.5 kV. Under optimized conditions, arsenic could be detected as low as 1.0 ng/L with an 8-fold enrichment factor; the linearity of calibration reached R(2) > 0.995 in the 0.05 μg/L-5 μg/L range. The mean spiked recoveries for tap, river, lake, and seawater samples were 98% to 103%; and the measured values of the CRMs including GSB-Z50004-200431, GBW08605, and GBW(E)080390 were in good agreement with the certified values. These findings proved the feasibility of DBDR as an arsenic preconcentration tool for atomic spectrometric instrumentation and arsenic recycling in industrial waste gas discharge.
The mechanisms of arsenic gas phase enrichment (GPE) by dielectric barrier discharge (DBD) was investigated via X-ray photoelectron spectroscopy (XPS), in situ fiber optic spectrometer (FOS), etc. It proved for the first time that the arsenic species during DBD trapping, release, and transportation to the atomic fluorescence spectrometer (AFS) are probably oxides, free atoms, and atom clusters, respectively. Accordingly, a novel in situ DBD trap as a GPE approach was redesigned using three-concentric quartz tube design and a modified gas line system. After trapping by O at 9.2 kV, sweeping for 180 s, and releasing by H at 9.5 kV, 2.8 pg detection limit (LOD) was achieved without extra preconcentration (sampling volume = 2 mL) as well as 4-fold enhancement in absolute sensitivity and ∼10 s sampling time. The linearity reached R > 0.998 in the 0.1-8 μg/L range. The mean spiked recoveries for tap, river, lake, and seawater samples were 100-106%; and the measurements of the certified reference materials (CRMs) were in good agreement with the certified values. In situ DBD trap is also suitable to atomic absorption spectrometry (AAS) or optical emission spectrometry (OES) for fast and on-site determination of multielements.
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