Application of a rule-based model to estimate mercury exchange for three background biomes in the continental United States.

Ecosystems that have low mercury (Hg) concentrations (i.e., not enriched or impacted by geologic or anthropogenic processes) cover most of the terrestrial surface area of the earth yet their role as a net source or sink for atmospheric Hg is uncertain. Here we use empirical data to develop a rule-based model implemented within a geographic information system framework to estimate the spatial and temporal patterns of Hg flux for semiarid deserts, grasslands, and deciduous forests representing 45% of the continental United States. This exercise provides an indication of whether these ecosystems are a net source or sink for atmospheric Hg as well as a basis for recommendation of data to collect in future field sampling campaigns. Results indicated that soil alone was a small net source of atmospheric Hg and that emitted Hg could be accounted for based on Hg input by wet deposition. When foliar assimilation and wet deposition are added to the area estimate of soil Hg flux these biomes are a sink for atmospheric Hg.

Determination of the potential for release of mercury from combustion product amended soils: part 2--coal fly ash generated stabilized soil and degradation products.

The potential for mercury (Hg) releases to the air and water from three soils, two subbituminous coal fly ashes, and mixtures of these materials as stabilized soil was assessed. In addition, the potential for Hg release from crushed stabilized material mixed into soil simulating degradation over time was investigated. In general, atmospheric Hg deposition was measured for the ash and materials made using the ash with the higher Hg concentration (ash 1, 0.25 microg x g(-1)), whereas the second ash material (ash 2; approximately 0.08 microg x g(-1)) and materials generated using this ash exhibited emission as the dominant flux. Fluxes measured from stabilized material were less than that measured for the pure ash material but of the same direction. Although the stabilized and degraded stabilized materials exhibited Hg fluxes that were significantly different from base soils, values were within the range reported for low Hg-containing background soils. Because of limitations of the experimental design (i.e., reduced light exposures and measurement of flux from dry materials) reported fluxes are most likely underestimates of that which would occur in the natural environment. Materials made to simulate degradation of the stabilized material did not exhibit higher releases than the stabilized material alone. Synthetic Precipitation Leaching Procedure (SPLP; EPA method 1312) results showed that the chemistry of a soil, especially pH, may influence the amount of Hg released to soil solutions, with more acidic soils potentially enhancing Hg release.

Determination of the potential for release of mercury from combustion product amended soils: Part 1--Simulations of beneficial use.

This paper describes a project that assessed the potential for mercury (Hg) release to air and water from soil amended with combustion products to simulate beneficial use. Combustion products (ash) derived from wood, sewage sludge, subbituminous coal, and a subbituminous coal-petroleum coke mixture were added to soil as agricultural supplements, soil stabilizers, and to develop low-permeability surfaces. Hg release was measured from the latter when intact and after it was broken up and mixed into the soil. Air-substrate Hg exchange was measured for all materials six times over 24 hr, providing data that reflected winter, spring, summer, and fall meteorological conditions. Dry deposition of atmospheric Hg and emission of Hg to the atmosphere were both found to be important fluxes. Measured differences in seasonal and diel (24 hr) fluxes demonstrated that to establish an annual estimate of air-substrate flux from these materials data on both of these time steps should be collected. Air-substrate exchange was highly correlated with soil and air temperature, as well as incident light. Hg releases to the atmosphere from coal and wood combustion product-amended soils to simulate an agricultural application were similar to that measured for the unamended soil, whereas releases to the air for the sludge-amended materials were higher. Hg released to soil solutions during the Synthetic Precipitation Leaching Procedure for ash-amended materials was higher than that released from soil alone. On the basis of estimates of annual releases of Hg to the air from the materials used, emissions from coal and wood ash-amended soil to simulate an agricultural application could simply be re-emission of Hg deposited by wet processes from the atmosphere; however, releases from sludge-amended materials and those generated to simulate soil stabilization and disturbed low-permeability pads include Hg indigenous to the material.

Air-surface exchange of mercury with soils amended with ash materials.

Air-surface exchange of mercury (Hg) was measured from soil low in Hg (0.013 mg/kg) amended with four different ash materials: a wood ash containing -10% coal ash (0.070 mg/kg Hg), a mixture of two subbituminous coal fly ashes (0.075 mg/kg Hg), a subbituminous coal ash containing -10% petroleum coke ash (1.2 mg/kg Hg), and an ash from incinerated municipal sewage sludge (4.3 mg/kg Hg) using a dynamic flux chamber. Ash was added to soil to simulate agricultural supplements, soil stabilization, and pad layers used in livestock areas. For the agricultural amendment, -0.4% ash was well mixed into the soil. To make the stabilized soil that could be used for construction purposes, -20% ash was mixed into soil with water. The pad layer consisted of a wetted 1-cm layer of ash material on the soil surface. Diel trends of Hg flux were observed for all of the substrates with significantly higher Hg emissions during the day and negligible flux or deposition of Hg during the night. Hg fluxes, which were measured in the summer months, were best correlated with solar radiation, temperature, and air O3 concentrations. Mean Hg fluxes measured outdoors for unamended soils ranged from 19 to 140 ng/m2 day, whereas those for soil amended with ash to simulate an agricultural application ranged from 7.2 to 230 ng/m2 day. Fluxes for soil stabilized with ash ranged from 77 to 530 ng/m2 day and for soil with pads constructed of ash ranged from -50 to 90 ng/m2 day. Simple analytical tests (i.e., total Hg content, synthetic precipitation leaching procedure, heating, and indoor gas-exchange experiments) were performed to assess whether algorithms based on these tests could be used to predict Hg fluxes observed outdoors using the flux chamber. Based on this study, no consistent relationships could be developed. More work is needed to assess long-term and seasonal variations in Hg flux from (intact and disturbed) substrates before annual estimates of emissions can be developed.

Assessing the potential for re-emission of mercury deposited in precipitation from arid soils using a stable isotope.

A solution containing 198Hg in the form of HgCl2 was added to a 4 m2 area of desert soils in Nevada, and soil Hg fluxes were measured using three dynamic flux chambers. There was an immediate release of 198Hg after it was applied, and then emissions decreased exponentially. Within the first 6 h after the isotope was added to the soil, approximately 12 ng m(-2) of 198Hg was emitted to the atmosphere, followed by a relatively steady flux of the isotope at 0.2 +/- 0.2 ng m(-2) h(-1) for the remainder of the experiment (62 days). Over this time, approximately 200 ng m(-2) or 2% of the 198Hg isotope was emitted from the soil, and we estimate that approximately 6% of the isotope would be re-emitted in a year's time. During the experiment, dry deposition of elemental Hg from the atmosphere was measured with an average deposition rate of 0.2 +/- 0.1 ng m(-2) h(-1). Emission of ambient Hg from the soil was observed after soil wetting with the isotope solution and after a storm event. However, the added moisture from the storm event did not affect 198Hg flux. Results suggest that in this desert environment, where there is limited precipitation, Hg deposited by wet processes is not readily re-emitted and that dry deposition of elemental Hg may be an important process.