Atmosphere-terrestrial exchange of gaseous elemental mercury: parameterization improvement through direct comparison with measured ecosystem fluxes.

To simulate global mercury (Hg) dynamics in chemical transport models (CTMs), surface-atmosphere exchange of gaseous elemental mercury, Hg0, is often parameterized based on resistance-based dry deposition schemes coupled with a re-emission function, mainly from soils. Despite extensive use of this approach, direct evaluations of this implementation against field observations of net Hg0 exchange are lacking. In this study, we evaluate an existing net exchange parameterization (referred to here as the base model) by comparing modeled fluxes of Hg0 to fluxes measured in the field using micrometeorological techniques. Comparisons were performed in two terrestrial ecosystems: a grassland site in Switzerland and an Arctic tundra site in Alaska, U.S., each including summer and winter seasons. The base model included the dry deposition and soil re-emission parameterizations from Zhang et al. (2003) and the global CTM GEOS-Chem, respectively. Comparisons of modeled and measured Hg0 fluxes showed large discrepancies, particularly in the summer months when the base model overestimated daytime net deposition by approximately 9 and 2 ng m-2 h-1 at the grassland and tundra sites, respectively. In addition, the base model was unable to capture a measured nighttime net Hg0 deposition and wintertime deposition. We conducted a series of sensitivity analyses and recommend that Hg simulations using CTMs: (i) reduce stomatal uptake of Hg0 over grassland and tundra in models by a factor 5-7; (ii) increase nighttime net Hg0 deposition, e.g., by increasing ground and cuticular uptake by reducing the respective resistance terms by factors of 3-4 and 2-4, respectively; and (iii) implement a new soil re-emission parameterization to produce larger daytime emissions and lower nighttime emissions. We also compared leaf Hg0 uptake over the growing season estimated by the dry deposition model against foliar Hg measurements, which revealed good agreement with the measured leaf Hg concentrations after adjusting the base model as suggested above. We conclude that the use of resistance-based models combined with the new soil re-emission flux parameterization is able to reproduce observed diel and seasonal patterns of Hg0 exchange in these ecosystems. This approach can be used to improve model parameterizations for other ecosystems if flux measurements become available.

Spatial assessment and source identification of trace metal pollution in stream sediments of Oued El Maadene basin, northern Tunisia.

An extensive spatial survey was conducted on trace metal content in stream sediments from Oued El Maadene basin, northern Tunisia. Our objectives were to evaluate the level of trace metal pollution and associated ecological risk and identify the major sources of metal pollution. A total of 116 stream sediment samples were collected and analysed for total As, Cd, Cr, Cu, Ni, Pb, V, Zn, and Zr concentrations. The results showed that concentrations of Cr, Ni, V, and Zr were close to natural levels. In contrast, As, Cd, Cu, Pb, and Zn had elevated concentrations and enrichment factors compared to other contaminated regions in northern Tunisia. Ecological risk to aquatic ecosystems was highlighted in most areas. Principal component analysis showed that Cr, Ni, V, and Zr mainly derived from local soil and bedrock weathering, whilst As, Cd, Pb, and Zn originated from mining wastes. Trace metals could be dispersed downstream of tailings, possibly due to surface runoff during the short rainy season. Surprisingly, Cu, and to a lesser extent As, originated from agricultural activities, related to application of Cu-based fungicides in former vineyards and orchards. This study showed that, despite the complete cessation of mining activities several decades ago, metal pollution still impacts the local environment. This large pollution, however, did not mask other additional sources, such as local agricultural applications of fungicides.

Investigation of spatial and temporal metal atmospheric deposition in France through lichen and moss bioaccumulation over one century.

Lichens and mosses were used as biomonitors to assess the atmospheric deposition of metals in forested ecosystems in various regions of France. The concentrations of 17 metals/metalloids (Al, As, Cd, Co, Cr, Cs, Cu, Fe, Mn, Ni, Pb, Sb, Sn, Sr, Ti, V, and Zn) indicated overall low atmospheric contamination in these forested environments, but a regionalism emerged from local contributions (anthropogenic activities, as well as local lithology). Taking into account the geochemical background and comparing to Italian data, the elements from both natural and anthropogenic activities, such as Cd, Pb, or Zn, did not show any obvious anomalies. However, elements mainly originating from lithogenic dust (e.g., Al, Fe, Ti) were more prevalent in sparse forests and in the Southern regions of France, whereas samples from dense forests showed an accumulation of elements from biological recycling (Mn and Zn). The combination of enrichment factors and Pb isotope ratios between current and herbarium samples indicated the historical evolution of metal atmospheric contamination: the high contribution of coal combustion beginning 150 years ago decreased at the end of the 20th century, and the influence of car traffic during the latter observed period decreased in the last few decades. In the South of France, obvious local influences were well preserved during the last century.

Origin and distribution of rare earth elements in various lichen and moss species over the last century in France.

Rare earth elements (REE) are known to be powerful environmental tracers in natural biogeochemical compartments. In this study, the atmospheric deposition of REE was investigated using various lichens and mosses as well as herbarium samples from 1870 to 1998 from six major forested areas in France. The comparison between the REE distribution patterns in organisms and bedrocks showed a regional uniformity influence from dust particles originating from the bedrock and/or soil weathering that were entrapped by lichens and mosses. These lithological signatures were consistent over the last century. The REE patterns of different organism species allowed minor influence of the species to be highlighted compared to the regional lithology. This was even true where the morphological features played a role in the bioaccumulation levels, which were related to the variable efficiency in trapping atmospheric dust particles. A comparison between REE profiles in the organisms and bark indicated a lack of influence of the substrate on lichen REE content. Lichens and mosses appear to be robust passive monitors of REE atmospheric deposition over decades because the mineral data was preserved in herbarium samples despite organic degradation being shown by carbon isotopes and SEM observations. To overcome the bias of REE concentration that resulted from organic degradation, the use of a normalized method is recommended to interpret the historical samples.

Comparing early twentieth century and present-day atmospheric pollution in SW France: A story of lichens.

Lichens have long been known to be good indicators of air quality and atmospheric deposition. Xanthoria parietina was selected to investigate past (sourced from a herbarium) and present-day trace metal pollution in four sites from South-West France (close to Albi). Enrichment factors, relationships between elements and hierarchical classification indicated that the atmosphere was mainly impacted by coal combustion (as shown by As, Pb or Cd contamination) during the early twentieth century, whereas more recently, another mixture of pollutants (e.g. Sb, Sn, Pb and Cu) from local factories and car traffic has emerged. The Rare Earth Elements (REE) and other lithogenic elements indicated a higher dust content in the atmosphere in the early twentieth century and a specific lithological local signature. In addition to long-range atmospheric transport, local urban emissions had a strong impact on trace element contamination registered in lichens, particularly for contemporary data.