ABSTRACT
We have employed a new approach to quantify the amount fraction of nitrous oxide in a synthetic air matrix gas used to prepare high-accuracy reference materials of the same component. Until now, this was the largest contributor to the measurement uncertainty of nitrous oxide in air reference materials at atmospheric amount fractions (â¼330 nmol mol-1), as identified in a recent international comparison. A novel preconcentration method has resulted in a measurement of 363 pmol mol-1 of nitrous oxide in a synthetic air matrix gas with an expanded uncertainty of 27 pmol mol-1. This represents a significant breakthrough as using these developments with an optimized dilution hierarchy (to minimize the gravimetric uncertainty) promises to result in SI traceable reference materials with expanded uncertainties as low as 0.032% relative (k = 2). This supports the World Meteorological Organization-Global Atmosphere Watch network compatibility goal for underpinning atmospheric observations.
ABSTRACT
A novel pipette-tip extractor of a graphene/poly (vinyl alcohol) cryogel (graphene/PVA) composite sorbent was prepared to preconcentrate carbamate pesticides in environmental water samples before analysis with a gas chromatograph-flame ionization detector (GC-FID). This novel pipette-tip extractor with the graphene/PVA sorbent exhibited a high porosity when observed through a scanning electron micrograph (SEM). Under optimal conditions, using only 1.0 mL of sample and 0.75 mL of eluting solvent, the developed method provided a wide linear range of 10-700 ng mL(-1) and 10-500 ng mL(-1) with limit of detection (LOD) of 6.40 ± 0.18 and 9.17 ± 0.34 ng mL(-1) for carbofuran (2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate) and carbaryl (1-naphthyl methylcarbamate), respectively. The pipette-tip extractor provided high extraction efficiency with high accuracy indicated, by good recoveries in the range of 74.5 ± 4.8% to 119.7 ± 1.6% and 76 ± 15% to 114 ± 19% for carbofuran and carbaryl, respectively. In addition, the fabrication procedure showed a good pipette-tip extractor-to-pipette-tip extractor reproducibility with a relative standard deviation of 1.3-9.8% (n = 5). When the developed pipette-tip extractor was applied for the extraction of carbofuran and carbaryl in surface water samples near vegetable plantation areas, 25.9 ± 8.2 ng mL(-1) of carbofuran was found, and carbaryl was also detected in concentrations that ranged from 45.0 ± 4.0 to 191 ± 13 ng mL(-1).
