David Miljak

75As, 63Cu NMR and NQR characterization of selected arsenic minerals

The direct measurement and identification of solid state arsenic phases using (75)As NMR is made difficult by the simultaneous conditions of large quadrupole moment and low coordination symmetry in many compounds. However, specific arsenic minerals can efficiently be detected and discriminated via nuclear quadrupolar resonance (NQR). We report on the first NMR and NQR measurements in the natural minerals enargite (Cu3AsS4), niccolite (NiAs), arsenopyrite (FeAsS) and loellingite (FeAs2). The NQR frequencies have been determined from both high-field NMR powder patterns and via zero-field frequency sweeps. Density functional theory (DFT) based ab initio calculations support the experimental results. The compounds studied here are common in terms of the known set of As-containing minerals. They are sometimes encountered in the context of base metal or gold mining. The study represents a significant addition to the list of arsenic minerals that can now be detected with NQR techniques.

Rapid detection of arsenic minerals using portable broadband NQR

The remote real-time detection of specific arsenic species would significantly benefit in minerals processing to mitigate the release of arsenic into aquatic environments and aid in selective mining. At present, there are no technologies available to detect arsenic minerals in bulk volumes outside of laboratories. Here we report on the first room-temperature broadband 75As nuclear quadrupole resonance (NQR) detection of common and abundant arsenic ores in the Earth crust using a large sample (0.78 L) volume prototype sensor. Broadband excitation aids in detection of natural minerals with low crystallinity. We briefly discuss how the proposed NQR detector could be employed in mining operations.

121,123Sb and 75As NMR and NQR investigation of the tetrahedrite (Cu12Sb4S13) – Tennantite (Cu12As4S13) system and other metal arsenides

This work is motivated by the recent developments in online minerals analysis in the mining and minerals processing industry via nuclear quadrupole resonance (NQR). Here we describe a nuclear magnetic resonance (NMR) and NQR study of the minerals tennantite (Cu12As4S13) and tetrahedrite (Cu12 Sb4S13). In the first part NQR lines associated with (75)As in tennantite and (121,123)Sb isotopes in tetrahedrite are reported. The spectroscopy has been restricted to an ambient temperature studies in accord with typical industrial conditions. The second part of this contribution reports nuclear quadrupole-perturbed NMR findings on further, only partially characterised, metal arsenides. The findings enhance the detection capabilities of NQR based analysers for online measurement applications and may aid to control arsenic and antimony concentrations in metal processing stages.

75As NQR studies on FeAs2

(75)As NQR spectra and relaxation times of synthetic and natural FeAs2 samples have been studied at variable static magnetic field and temperature. FeAs2 is a well understood diamagnetic semiconductor and occurs as the natural mineral lollingite in selected ore deposits. We observed a spin-spin relaxation time enhancement of up to five in synthetic powders in the presence of a weak external static magnetic field. The effect is of interest with regard to signal-to-noise ratio improvement for materials characterization applications where broad NQR absorption lines are excited with wideband pulse sequences.