S. E. Lindberg

A Synthesis of Progress and Uncertainties in Attributing the Sources of Mercury in Deposition

Abstract A panel of international experts was convened in Madison, Wisconsin, in 2005, as part of the 8th International Conference on Mercury as a Global Pollutant. Our charge was to address the state of science pertinent to source attribution, specifically our key question was: “For a given location, can we ascertain with confidence the relative contributions of local, regional, and global sources, and of natural versus anthropogenic emissions to mercury deposition?” The panel synthesized new research pertinent to this question published over the past decade, with emphasis on four major research topics: long-term anthropogenic change, current emission and deposition trends, chemical transformations and cycling, and modeling and uncertainty. Within each topic, the panel drew a series of conclusions, which are presented in this paper. These conclusions led us to concur that the answer to our question is a “qualified yes,” with the qualification being dependent upon the level of uncertainty one is willing to accept. We agreed that the uncertainty is strongly dependent upon scale and that our question as stated is answerable with greater confidence both very near and very far from major point sources, assuming that the “global pool” is a recognizable “source.” Many regions of interest from an ecosystem-exposure standpoint lie in between, where source attribution carries the greatest degree of uncertainty.

Whole-ecosystem study shows rapid fish-mercury response to changes in mercury deposition

Methylmercury contamination of fisheries from centuries of industrial atmospheric emissions negatively impacts humans and wildlife worldwide. The response of fish methylmercury concentrations to changes in mercury deposition has been difficult to establish because sediments/soils contain large pools of historical contamination, and many factors in addition to deposition affect fish mercury. To test directly the response of fish contamination to changing mercury deposition, we conducted a whole-ecosystem experiment, increasing the mercury load to a lake and its watershed by the addition of enriched stable mercury isotopes. The isotopes allowed us to distinguish between experimentally applied mercury and mercury already present in the ecosystem and to examine bioaccumulation of mercury deposited to different parts of the watershed. Fish methylmercury concentrations responded rapidly to changes in mercury deposition over the first 3 years of study. Essentially all of the increase in fish methylmercury concentrations came from mercury deposited directly to the lake surface. In contrast, <1% of the mercury isotope deposited to the watershed was exported to the lake. Steady state was not reached within 3 years. Lake mercury isotope concentrations were still rising in lake biota, and watershed mercury isotope exports to the lake were increasing slowly. Therefore, we predict that mercury emissions reductions will yield rapid (years) reductions in fish methylmercury concentrations and will yield concomitant reductions in risk. However, a full response will be delayed by the gradual export of mercury stored in watersheds. The rate of response will vary among lakes depending on the relative surface areas of water and watershed.

Air/surface exchange of mercury vapor over forests : The need for a reassessment of continental biogenic emissions

Atmospheric sources are significant in the cycling of Hg in the biosphere, but there are few reliable data on air/surface exchange of Hg in terrestrial systems. We developed a tower-based micrometeorological gradient method for measuring gas-phase Hg° fluxes over soils and vegetation. We describe here results of the modified Bowen ratio approach from three separate flux sampling campaigns: over a mature deciduous forest at the Walker Branch Watershed in Tennessee, over a young pine plantation in Tennessee, and over the boreal forest floor at the Lake Gardsjon watershed in Sweden. Our data show that Hg° exchange over these surfaces is bidirectional, but is primarily characterized by emissions from plants and soil. Dry deposition (foliar uptake) is less frequent, of generally lower magnitude, and may be enhanced by surface wetness. We measured emissions over tree canopies in Tennessee in the range of ∼ 10–300 ng m−2 h−1, and over the boreal forest floor in Sweden of ∼ 1–4 ng m−2 h−1. Fluxes were influenced by temperature, solar radiation, and atmospheric turbulence. The ability of trees to emit Hg° from soil pools has now been established. Others have proposed a significant biotic re-emission of Hg° from the oceans, and our data provide the first direct evidence of a similar process in terrestrial systems. These data have been combined with results from chamber studies to estimate the overall flux of gas-phase Hg° between the atmosphere and terrestrial systems. Transpiration of Hg° represents a previously unmeasured mobilization of Hg from the continents to the troposphere. Including this new source term could increase current estimates of so-called natural emissions by over 100%.

Atmosphere‐surface exchange of mercury in a forest: Results of modeling and gradient approaches

We have modified recently published dry deposition models to estimate deposition velocities (Vd) for Hg in both fine aerosol and vapor form to forest canopy surfaces. Aerosol and total vapor phase Hg concentrations in air previously measured at Walker Branch Watershed in Tennessee have been used with model results to estimate dry deposition to a deciduous forest. The concentration data confirm that airborne Hg is dominated by vapor forms at this site and exhibits concentrations moderately above continental background levels. The modeled Vd values reflect published data which suggest that dry deposition of Hg vapor is strongly controlled by surface transport processes, notably stomatal and mesophyll resistances, the latter dominating. Weekly mean Vd values ranged from 0.006 (winter) to 0.12 (summer) cm s−1. We have also measured concentration gradients of Hg vapor in air above this forest to estimate air-surface exchange during short-term experiments. While the model results indicate that the canopy is a sink for Hg vapor, the concentration profiles suggest that the forest soils are a source during some periods, the combined effect of which is net Hg fluxes in the upward direction. Application of a detailed canopy turbulence model yielded soil emission rates of the order of 50 ng Hg m−2 h−1, ∼10% of which is deposited in the canopy. Our modeled dry deposition estimates plus limited measurements of wet deposition in this area suggest that dry and wet deposition may be comparable in magnitude.

Nevada STORMS project: Measurement of mercury emissions from naturally enriched surfaces

Diffuse anthropogenic and naturally mercury-enriched areas represent long- lived sources of elemental mercury to the atmosphere. The Nevada Study and Tests of the Release of Mercury From Soils (STORMS) project focused on the measurement of mercury emissions from anaturally enriched area. During the project, concurrent measurements of mercury fluxes from naturally mercury-enriched substrate were made September 1-4, 1997, using four micrometeorological methods and seven field flux chambers. Ambient air mercury concentrations ranged from 2 to nearly 200 ng m- 3 indicating that the field site is a source of atmospheric mercury. The mean day time mercury fluxes, durin p conditions of no precipitation, measured with field chambers were 50 to 360 ng m -2 h - , and with the micrometeorological methods we re 230 to 600 ng m- 2 h -1. This wide range in mercury emission rates reflects differences in method experimental designs and local source strengths. Mercury fluxes measured by many field chambers were significantly different (p < 0.05) but linearly correlated. This indicates that field chambers responded similarly to environmental conditions, but differences in experimental design and site heterogeneity had a significant influence on the magnitude of mercury fluxes. Data developed during the field study demonstrated that field flux chambers are ideal for assessment of the physicochemical processes driving mercury flux and development of an understanding of the magnitude of the influence of individual factors on flux. In general, mean mercury fluxes measured with micrometeorological methods during day time periods were nearly 3 times higher than me an fluxes measured with field flux chambers. Micrometeorological methods allow for derivation of a representative mercury flux occurring from an unconstrained system and provide an assessment of the actual magnitude and variability of fluxes occurring from an area.

Foliar Exchange of Mercury Vapor: Evidence for a Compensation Point

Historical studies for crop and weed species documented elemental Hg vapor (Hg°) deposition to foliage, but they used Hg° concentrations that were orders of magnitude higher than levels now known to occur under background conditions, possibly creating artificially high gradients between the atmosphere and landscape surfaces. Measurements of Hg° exchange with white oak (Quercus alba L.), red maple (Acer rubrum L.), Norway spruce (Picea abies L.), and yellow-poplar (Liriodendron tulipifera L.) foliage were conducted in an open gas exchange system that allows for simultaneous measurements of CO2, H2O and Hg° exchange under controlled environmental conditions. When Hg° concentrations were held at 0.5 to 1.5 ng m-3, red maple (Acer rubrum L), Norway spruce(Picea abies L.), yellow-poplar {Liriodendron tulipifera L.), and white oak {Quercus alba L.) foliage exhibited mean Hg° emissions of 5.5, 1.7, 2.7, and 5.3 ng m–2 h-1respectively. At Hg° concentrations between 9 and 20 ng m-3 little net exchange of Hg° was observed. However at concentrations between 50 and 70 ng m-3 the Hg° was deposited to foliage at rates between 22 and 38 ng m-2 h–1 These data suggest that dry foliar surfaces in terrestrial forest landscapes may be a dynamic exchange surface that can function as a source or sink dependent on the magnitude of current Hg° concentrations. These data provide evidence of species-specific compensation concentrations (or compensation points) for Hg° deposition to seedling foliage in the 10–25 ng m-3 range.

Intercomparison of methods for sampling and analysis of atmospheric mercury species

An intercomparison for sampling and analysis of atmospheric mercury species was held in Tuscany, June 1998. Methods for sampling and analysis of total gaseous mercury (TGM), reactive gaseous mercury (RGM) and total particulate mercury (TPM) were used in parallel sampling over a period of 4 days. The results show that the different methods employed for TGM compared well whereas RGM and TPM showed a somewhat higher variability. Measurement results of RGM and TPM improved over the time period indicating that activities at the sampling site during set-up and initial sampling affected the results. Especially the TPM measurement results were affected. Additional parallel sampling was performed for two of the TPM methods under more controlled conditions which yielded more comparable results.

Mercury Distribution Across 14 U.S. Forests. Part I: Spatial Patterns of Concentrations in Biomass, Litter, and Soils

Results from a systematic investigation of mercury (Hg) concentrations across 14 forest sites in the United States show highest concentrations in litter layers, strongly enriched in Hg compared to aboveground tissues and indicative of substantial postdepositional sorption of Hg. Soil Hg concentrations were lower than in litter, with highest concentrations in surface soils. Aboveground tissues showed no detectable spatial patterns, likely due to 17 different tree species present across sites. Litter and soil Hg concentrations positively correlated with carbon (C), latitude, precipitation, and clay (in soil), which together explained up to 94% of concentration variability. We observed strong latitudinal increases in Hg in soils and litter, in contrast to inverse latitudinal gradients of atmospheric deposition measures. Soil and litter Hg concentrations were closely linked to C contents, consistent with well-known associations between organic matter and Hg, and we propose that C also shapes distribution of Hg in forests at continental scales. The consistent link between C and Hg distribution may reflect a long-term legacy whereby old, C-rich soil and litter layers sequester atmospheric Hg depositions over long time periods. Based on a multiregression model, we present a distribution map of Hg concentrations in surface soils of the United States.

Dynamic flux chamber measurement of gaseous mercury emission fluxes over soils: Part 2—effect of flushing flow rate and verification of a two-resistance exchange interface simulation model

Both field and laboratory tests demonstrated that soil Hg emission fluxes measured by dynamic flux chamber (DFC) operations strongly depend on the flushing air flow rates used. The general trend is an increase in the fluxes with increasing flushing flow rates followed by an asymptotic approach to flux maximum at sufficiently high (optimum) flushing flow rates. This study indicates that the DFC measurements performed at low flushing flow rates can underestimate Hg emission fluxes over soils, especially Hg-enriched soils. High flushing flow rates therefore are recommended for accurate estimation of soil Hg emission fluxes by DFC operations. The dependence of DFC-measured soil Hg emission fluxes on flushing flow rate is a physical phenomenon inherent in DFC operations, regardless of DFC design and soil physical characteristics. Laboratory tests using DFCs over different soils confirmed the predictions of a two-resistance exchange interface model and demonstrated the capability of this model in quantitatively simulating Hg emissions from soils measured by DFC operations.

NO2 deposition to elements representative of a forest landscape

Abstract Measurements of NO 2 deposition to elements representative of a forest landscape (e.g. foliage, bole, soil) were conducted in an open gas exchange system. Deposition rates (nmol m −2 s −1 ) were calculated as the product of flow rate and the inlet/outlet concentration differential normalized for surface area and corrected for losses to chamber walls. Under daylight conditions and a mean NO 2 concentration of 33 nl l −1 , NO 2 deposition to foliage of forest tree species varied by more than an order of magnitude, ranging from 0.35 ( Pinus taeda L.) to 5.75 nmol m −2 s −1 ( Platanus occidentalis L.), and deposition of NO 2 to most broadleaf species was greater than that to conifers. Sequential light-dark measurements of NO 2 deposition indicated that the principal foliar site of deposition was the leaf interior in support of other observations of stomatal control over NO 2 deposition. Vegetation surfaces typically snowed greater conductance to NO 2 than did distilled water alone, and forest floor samples had a disproportionately high conductance to NO 2 when compared to bark or foliage surfaces. Laboratory data for several forest species were extrapolated to stand-level rates of NO 2 deposition using leaf area index as a scaling factor. Based on appropriate NO 2 concentrations, NO 2 deposition was calculated to provide annual N inputs between 0.08 and 1.9 kg ha −1 a −1 of NO 2 derived N(NO 2 — N) for natural forests and up to 12kg NO 2 -N ha −1 a −1 for forest canopies in urban environments.