Comparison of active measurements, lichen biomonitoring, and passive sampling for atmospheric mercury monitoring.

The number of atmospheric mercury (Hg) monitoring stations is growing globally. However, there are still many regions and locations where Hg monitoring is limited or non-existent. Expansion of the atmospheric Hg monitoring network could be facilitated by the use of cost-effective monitoring methods. As such, biomonitoring and passive monitoring offer a unique alternative to well-established monitoring by active measurements, since they do not require a power supply and require minimal workload to operate. The use of biomonitoring (lichens and mosses) and passive air samplers (PASs) (various designs with synthetic materials) has been reported in the literature, and comparisons with active measurement methods have also been made. However, these studies compared either biomonitoring or PASs (not both) to only one type of active measurement. In our work, we used transplanted (7 sampling sites) and in situ lichens (8 sampling sites) for biomonitoring, two PASs from different producers (3 sampling sites), and two different active measurement types (continuous and discontinuous active measurements, 1 and 8 sampling sites, respectively) to evaluate their effectiveness as monitoring methods. In the 9-month sampling campaign, 3 sampling locations with different characteristics (unpolluted, vicinity of a cement plant, and vicinity of a former Hg mine) were used. The results obtained with lichens and PASs clearly distinguished between sampling locations with different Hg concentrations; using both PASs and lichens together increased the confidence of our observations. The present work shows that biomonitoring and passive sampling can be effectively used to identify areas with elevated atmospheric Hg concentrations. The same can be said for discontinuous active measurements; however, the discrepancy between atmospheric Hg concentrations derived from PASs and discontinuous active measurements should be further investigated in the future.

Optimization of a pre-concentration method for the analysis of mercury isotopes in low-concentration foliar samples.

Hg isotope analysis in samples from background regions is constrained by the presence of low Hg concentration and therefore requires a pre-concentration method. Existing Hg pre-concentration methods are constrained by long sample processing time and limited sample loading capacity. Using foliar samples as a test case, an optimized Hg pre-concentration method is presented that involves the microwave-assisted digestion of samples for Hg isotope analysis with the addition of a pre-digestion step. Microwave-digested foliar samples and CRMs were transferred to an impinger, reduced with SnCl2, and collected in a 2.25 mL concentrated inverse aqua regia (3:1 HNO3:HCl, v/v). This resulted in an optimal acid concentration in the solution ideal for analysis on MC-ICP-MS. The time for purging with Hg-free N2 was optimized to 30 min and the efficiency of the pre-concentration method was tested using a combination of approaches. Tests performed on pure reagents and matrix of foliar samples spiked with 197Hg radiotracer showed recoveries averaging 99 ± 1.7% and 100 ± 3.0%, respectively. Mercury at concentrations as low as 1.83 ng g-1 was pre-concentrated by digesting aliquots of foliage samples in individual digestion vessels. Recoveries following their pre-concentration averaged 99 ± 6.0%, whereas recoveries of 95 ± 4.7% and 95 ± 2.5% were achieved for NIST SRM 1575a (pine needle) and reagents spiked with NIST SRM 3133, respectively. Analysis using multicollector-ICP-MS showed low fractionation of δ202Hg during sample pre-concentration with no significant mass-independent fractionation. The proposed method is a relatively simple and robust way to prepare Hg samples for Hg isotopic analysis and is suitable even for complex biological matrices.

Fractionation of mercury stable isotopes in lichens.

Bio-monitoring of mercury (Hg) in air using transplanted and in-situ lichens was conducted at three locations in Slovenia: (I) the town of Idrija in the area of the former Hg mine, where Hg contamination is well known; (II) Anhovo, a settlement with a cement production plant, which is a source of Hg contamination, and (III) Pokljuka, a part of a national park. Lichens from Pokljuka were transplanted to different sites and sampled four times-once per season, from January 2020 to February 2021. Lichens were set on tree branches, fences, and under cover, allowing them to be exposed to different environmental conditions (e.g., light and rain). The in-situ lichens were sampled at the beginning and the end of the sampling period. The highest concentrations were in the Idrija area, which was consistent with previous research. Significant mass-dependent fractionation has been observed in transplanted lichens during summer period. The δ202Hg changed from -3.0‰ in winter to -1.0‰ in summer and dropped again to the same value in winter the following year. This trend was observed in all samples, except those from the most polluted Idrija sampling site, which was in the vicinity of the former Hg ore-smelting plant. This was likely due to large amounts of Hg originating from polluted soil close to the former smelting plant with a distinct isotopic fingerprint in this local area. The Δ199Hg in transplanted lichens ranged from -0.5‰ to -0.1‰ and showed no seasonal trends. These findings imply that seasonality, particularly in summer months, may affect the isotopic fractionation of Hg and should be considered in the sampling design and data interpretation. This trend was thus described in lichens for the first time. The mechanism behind such change is not yet fully understood.