Micro- and nano-volume samples by electrothermal, near-torch vaporization sample introduction using removable, interchangeable and portable rhenium coiled-filament assemblies and axially-viewed inductively coupled plasma-atomic emission spectrometry

An electrothermal, near-torch vaporization (NTV) sample introduction for micro- or nano-volume samples is described. Samples were pipetted onto coiled-filament assemblies that were purposely developed to be removable and interchangeable and were dried and vaporized into a small-volume vaporization chamber that clips onto any ICP torch with a ball joint. Interchangeable assemblies were also constructed to be small-size (e.g., less than 3 cm long with max diameter of 0.65 cm) and light-weight (1.4 g) so that they can be portable. Interchangeable assemblies with volume-capacities in three ranges (i.e., < 1 μL, 1–10 μL and 10–100 μL) were fabricated and used.The horizontally-operated NTV sample introduction was interfaced to an axially-viewed ICP-AES (inductively coupled plasma-atomic emission spectrometry) system and NTV was optimized using ICP-AES and 8 elements (Pb, Cd, Zn, V, Ba, Mg, Be and Ca). Precision was 1.0–2.3% (peak height) and 1.1–2.4% (peak area). Detection limits (obtained using 5 μL volumes) expressed in absolute-amounts ranged between 4 pg for Pb to 0.3 fg (~ 5 million atoms) for Ca. Detection limits expressed in concentration units (obtained using 100 μL volumes of diluted, single-element standard solutions) were: 50 pg/mL for Pb; 10 pg/mL for Cd; 9 pg/mL for Zn; 1 pg/mL for V; 0.9 pg/mL for Ba; 0.5 pg/mL for Mg; 50 fg/mL for Be; and 3 fg/mL for Ca.Analytical capability and utility was demonstrated using the determination of Pb in pg/mL levels of diluted natural water Certified Reference Material (CRM) and the determination of Zn in 80 nL volumes of the liquid extracted from an individual vesicle. It is shown that portable and interchangeable assemblies with dried sample residues on them can be transported without analyte loss (for the concentrations tested), thus opening up the possibility for “taking part of the lab to the sample” applications, such as testing for Cu concentration-compliance with the lead–copper rule of the Environmental Protection Agency. It is also shown that interchangeable assemblies with volume-capacities in the ranges mentioned above can be used interchangeably in the same calibration curve, thus in some cases and for on-site applications, volume-of-sample can be substituted for sample-dilution.

► Absolute detection limits from 4 pg (Pb) to 0.3 fg (~ 5 million atoms) for Ca.
► Relative detection limits (100 μL) from 50 pg/mL for Pb to 3 fg/mL for Ca.
► Pb was determined in the 100's of pg/mL level using 100 μL of diluted CRM.
► Zn in individual vesicles was determined using 80 nL-volume samples.
► Analytes pipetted on coils on-site and concentration determined in the lab.