Development of accurate dimethyl sulphide primary standard gas mixtures at low nanomole per mole levels in high-pressure aluminium cylinders for ambient measurements

Dimethyl sulphide (DMS) plays an important role in atmospheric chemistry and climate change. Ambient DMS is monitored in a global network and reported at sub-nanomole per mole (nmol/mol) levels. Developing traceable, accurate DMS standards at ambient levels is essential for tracking the long-term trends and understanding the role of DMS in the atmosphere. Gravimetrically prepared gas standards in cylinders are widely used for calibrating instruments. Therefore, a stable primary standard gas mixture (PSM) is required for traceable ambient DMS measurement at remote sites. In this study, to evaluate adsorption loss on the internal surface of the gas cylinder, 6 nmol mol^-1 DMS gas mixtures were prepared in three types of aluminium cylinders: a cylinder without a special coating on its internal surface (AL), an Aculife IV + III-treated cylinder (AC), and an Experis-treated cylinder (EX). There was little adsorption loss on the EX cylinder, whereas there was substantial adsorption loss on the other two cylinders. The EX cylinder was used to prepare 0.5, 2, 5, and 7 nmol mol^-1 DMS PSMs with relative expanded uncertainties of less than 0.4%. The DMS PSMs were analytically verified and consistent within a relative expanded uncertainty of less than 1.2%. The long-term stability of the 7 nmol mol^-1 DMS PSM was assessed by tracking the ratio of the DMS to the internal standard, benzene. The results showed that the DMS was stable for about seven months and it was projected to be stable for more than 60 months within a relative expanded uncertainty of 3%.