A new analytical method for the determination of the sulfur species (SO2, H2S, S8(0)) in volcanic gases is proposed by revising, updating, and improving previous methods. The most significant advantages of the proposed procedure can briefly be summarized, as follows: (i) the reaction among sulfur species stops during the gas sampling by using preevacuated thorion-tapped vials with purified 0.15M Cd(OH)2 in 4 M NaOH to favor the precipitation of H2S as CdS; (ii) all the sulfur species (SO2, H2S, S8(0)) are analyzed by ion chromatography, after conversion to SO4, which allows the detection limit to be lowered significantly with respect to the previous studies; (iii) appropriate aliquots from intermediate steps may be used to determine other species commonly present in volcanic gases such as CO2, HCI, HF, HBr, HI, and so forth; (iv) determination of all the other gas species is not jeopardized by the proposed method, i.e., one single vial can be used for analyzing the full chemical composition of a volcanic gas with the exception of NH3. Statistical parameters calculated from gas sampling data at the F5 crater fumarole in Vulcano Island (Aeolian Islands, southern Italy), suggest that the standard error of mean (s/ root n) is higher for S (0.10), followed by SO2, H2S, and CO2 (0.04, 0.038, and 0.028, respectively). SO2 shows the higher variation coefficient (12.1%) followed by H2S, S, and CO2 (5.7, 1.5, and 0.8%, respectively). Furthermore, if the time dependence of sampling is taken into account, the measured values, instead of fluctuating in a random manner, tend to follow systematic patterns, out of statistical control, possibly suggesting a sort of natural fluctuation of the volcanic system. Other crater fumaroles from volcanic systems located in different geodynamical areas (Hawaii, USA, El Chichon, Mexico, Poas, Costa Rica) have been analyzed as well.
