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.

Application of controlled mesocosms for understanding mercury air-soil-plant exchange.

Whole system elemental mercury (Hg0) flux was measured for approximately 1.5 years using two large gas exchange mesocosms containing approximately 100 two-year old aspen trees (Populus tremuloides) planted in soil with elevated mercury concentrations (12.3 microg/g). We hypothesized that during leafout, whole mesocosm Hg0 flux would increase due to movement of Hg0 in the transpiration stream from the soil to the air. This hypothesis was not supported; plants were found to assimilate Hg0 from the contaminated air, and whole system Hg0 emissions were reduced as plants leafed-out due to shading of the soil. Surface disturbance, watering, and increases in soil moisture, light, and temperature were all found to increase whole system Hg0 flux, with light being a more significant factor. Although surface soils were maintained at 15-20% moisture, daily watering caused pulses of Hg0 to be released from the soil throughout the experiment. Data developed in this experiment suggested that those processes acting on the soil surface are the primary influence on Hg emissions and that the presence of vegetation, which shields soil surfaces from incident light, reduces Hg emissions from enriched soils.

Importance of the forest canopy to fluxes of methyl mercury and total mercury to boreal ecosystems.

The forest canopy was an important contributor to fluxes of methyl mercury (MeHg) and total mercury (THg) to the forest floor of boreal uplands and wetlands and potentially to downstream lakes, at the Experimental Lakes Area (ELA), northwestern Ontario. The estimated fluxes of MeHg and THg in throughfall plus litterfall below the forest canopy were 2 and 3 times greater than annual fluxes by direct wet deposition of MeHg (0.9 mg of MeHg ha(-1)) and THg (71 mg of THg ha(-1)). Almost all of the increased flux of MeHg and THg under the forest canopy occurred as litterfall (0.14-1.3 mg of MeHg ha(-1) yr(-1) and 110-220 mg of THg ha(-1) yr(-1)). Throughfall added no MeHg and approximately 9 mg of THg ha(-1) yr(-1) to wet deposition at ELA, unlike in other regions of the world where atmospheric deposition was more heavily contaminated. These data suggest that dry deposition of Hg on foliage as an aerosol or reactive gaseous Hg (RGM) species is low at ELA, a finding supported by preliminary measurements of RGM there. Annual total deposition from throughfall and litterfall under a fire-regenerated 19-yr-old jack pine/birch forest was 1.7 mg of MeHg ha(-1) and 200 mg of THg ha(-1). We found that average annual accumulation of MeHg and THg in the surficial litter/fungal layer of soils since the last forest fire varied between 0.6 and 1.6 mg of MeHg ha(-1) and between 130 and 590 mg of THg ha(-1) among sites differing in drainage and soil moisture. When soil Hg accumulation sites were matched with similar sites where litterfall and throughfall were collected, measured fluxes of THg to the forest floor (sources) were similar to our estimates of longterm soil accumulation rates (sinks), suggesting that the Hg in litterfall and throughfall is a new and not a recycled input of Hg to forested ecosystems. However, further research is required to determine the proportion of Hg in litterfall that is being biogeochemically recycled within forest and wetland ecosystems and, thus, does not represent new inputs to the forest ecosystem.

Atmospheric mercury speciation: laboratory and field evaluation of a mist chamber method for measuring reactive gaseous mercury.

Knowledge of atmospheric mercury speciation is critical to modeling its fate. Thus there is a crucial need for reliable methods to measure the fraction of gaseous atmospheric Hg which is in the oxidized Hg(II) form (termed reactive gaseous mercury, RGM). We have developed a novel method for measurement of RGM using a refluxing mist chamber, and we recently reported the results of sampling campaigns for RGM in Tennessee and Indiana. In general, measured RGM levels were about 3% of total gaseous mercury (TGM), and our results support prevailing hypotheses about the nature and behavior of RGM in ambient air. Because its use for RGM is growing, we now report in more detail the development and testing of the mist chamber method. Several styles of mist chambers have been investigated. The most versatile design employs a single nebulizer nozzle and can operate at flows of 15-20 L/min. The water-soluble Hg is collected in ca. 20 mL of absorbing solution, which is then analyzed for Hg(II) by SnCl2 reduction and CVAFS. One-hour samples (ca. 1 m3 of air) generally contain 50-200 pg of RGM. The method detection limit for 1-h samples is approximately 6-10 pg/m3. Thus short sample times can reveal temporal variations in RGM that would not otherwise be observable. The efficiency of collecting RGM in mist chambers is highly dependent on Cl- concentration in the absorbing solution, in keeping with equilibrium calculations. Artifact formation of Hg(II) by oxidation of Hg0 under ozone ambient conditions appears to be sufficiently slow so as to be negligible for the short (ca. 1 h) runs that are typically employed. We observed no significant error from cosampled particles or aerosols in rural nonimpacted air samples. We have developed a simple approach to analyzing mist chamber samples in the field using an automated Hg sampler.

Sunlight and iron(III)-induced photochemical production of dissolved gaseous mercury in freshwater.

Mechanistic understanding of sunlight-induced natural processes for production of dissolved gaseous mercury (DGM) in freshwaters has remained limited, and few direct field tests of the mechanistic hypotheses are available. We exposed ferric iron salt-spiked fresh surface lake water (Whitefish Bay, Lake Superior, MI) in Teflon bottles and pond water (Oak Ridge, TN) in quartz bottles to sunlight in the field to infer if sunlight and Fe(III)-induced photochemical production of DGM could mechanistically contribute partly to natural photochemical production of DGM in freshwaters. We found that exposure of freshwater spiked with fresh Fe(III) (approximately 5 or 10 microM) to sunlight led to repeatable, significantly larger increases in DGM production (e.g., 380% in 1 h, 420% in 2 h, and 470% in 4 h for Whitefish Bay water) than exposure without the spike (e.g., 200% in 6 h). DGM increased with increasing exposure time and then often appeared to approach a steady state in the tests. Higher Fe(III) spike levels resulted in the same, or even less, DGM production. Storage of the water with or without Fe(III) spike in the dark after sunlight exposure led to significant, apparently first-order, decreases in DGM. These phenomena were hypothetically attributed to sunlight-induced photochemical production of highly reducing organic free radicals through photolysis of Fe(III)-organic acid coordination compounds and subsequent reduction of Hg(II) to Hg(0) by the organic free radicals; the reduction was also accompanied by dark oxidation of Hg(0) by photochemically originated oxidants (e.g., .OH). This study suggests that sunlight and Fe(III)-induced photochemical reduction of Hg(II) could be one of the mechanisms responsible for natural photochemical production of DGM in freshwaters and that Fe species may be influential in mediating Hg chemodynamics and its subsequent toxicity in aquatic ecosystems.

Is there synchronicity in nitrogen input and output fluxes at the Noland Divide Watershed, a small N-saturated forested catchment in the Great Smoky Mountains National Park?

High-elevation red spruce [Picea rubens Sarg.]-Fraser fir [Abies fraseri (Pursh.) Poir] forests in the Southern Appalachians currently receive large nitrogen (N) inputs via atmospheric deposition (30 kg N ha(-1) year(-1)) but have limited N retention capacity due to a combination of stand age, heavy fir mortality caused by exotic insect infestations, and numerous gaps caused by windfalls and ice storms. This study examined the magnitude and timing of the N fluxes into, through, and out of a small, first-order catchment in the Great Smoky Mountains National Park. It also examined the role of climatic conditions in causing interannual variations in the N output signal. About half of the atmospheric N input was exported annually in the streamwater, primarily as nitrate (NO3-N). While most incoming ammonium (NH4-N) was retained in the canopy and the forest floor, the NO3-N fluxes were very dynamic in space as well as in time. There was a clear decoupling between NO3-N input and output fluxes. Atmospheric N input was greatest in the growing season while largest NO3-N losses typically occurred in the dormant season. Also, as water passed through the various catchment compartments, the NO3-N flux declined below the canopy, increased in the upper soil due to internal N mineralization and nitrification, and declined again deeper in the mineral soil due to plant uptake and microbial processing. Temperature control on N production and hydrologic control on NO3-N leaching during the growing season likely caused the observed inter-annual variation in fall peak NO3-N concentrations and N discharge rates in the stream.

Assessing the contribution of natural sources to the global mercury cycle: the importance of intercomparing dynamic flux measurements.

In order to constrain the contribution of natural sources of mercury to the global atmospheric cycle we need to: 1. assess the methods used to measure mercury flux, 2. characterize those factors most important in controlling emissions, 3. develop a database of emissions from representative locations, and 4. develop a means of scaling up measured emissions to estimate fluxes on a regional basis. This paper describes how an international multi-collaborator project, the Nevada SToRMS Project, held September 1997 in Reno, Nevada, USA, contributed to our ability to constrain natural source mercury emissions. This study entailed a field intercomparison of those methods typically applied to measure mercury flux from substrate combined with evening workshops and round-table discussions. The project was unique in that it focused on assessing our ability to measure the flux of an environmental contaminant. This is more difficult than measurement of the concentration of a contaminant because of the number and nature of the variables which influence the field flux measurements, including experimental design, spatial heterogeneity, and temporally changing environmental conditions. As a result of the Nevada SToRMS Project, rapid and significant advances in our understanding of how to constrain emission fluxes from large areas of mercury enrichment were realized. Because this intercomparison was a multi-investigator project, the results and implications of the project have been broadly circulated. The sincere scientific collaboration that evolved amongst those working on the study has led to significant advancements in our understanding of the fate and transport of mercury in the environment.

Airborne Emissions of Mercury from Municipal Landfill Operations: A Short-Term Measurement Study in Florida.

Large quantities of mercury (Hg) have been placed in municipal landfills from a wide array of sources, including fluorescent lights, batteries, electrical switches, thermometers, and general waste. Despite its known volatility, persistence, and toxicity in the environment, the fate of this Hg has not been widely studied. Using automated flux chambers and atmospheric sampling, we quantified the primary pathways of Hg vapor releases to the atmosphere at two municipal landfill operations in south Florida for eight days in April 1997. These pathways included landfill gas (LFG) releases from passive and active vent systems, passive emissions from landfill surface covers of different ages (including CH4 "hot spots"), and emissions from daily activities at a working face (WF). Hg vapor was released to the atmosphere at readily detectable rates from all sources measured. Emission rates ranged from ~1 to 20 ng m-2 hr-1 over aged surface covers (generally comparable to background soils), from ~6 to 2400 ng/hr from LFG vents and flares, and from ~5 to 60 mg/hr at the WF. In general the fluxes increased from older to newer landfills, from fresh to aged cover, and from passive to active venting systems. Limited data suggest that methyl- and other organo-mercury compounds may also be emitted from these sites, suggesting an important area for future research. We estimate that atmospheric Hg releases from municipal landfill operations in the state of Florida are on the order of 10 kg/yr, or <1% of the estimated total anthropogenic Hg releases to air in this region.

Atmospheric deposition and canopy interactions of major ions in a forest.

Airborne particles and vapors contributed significantly to the nutrient requirements and the pollutant load of a mixed hardwood forest in the eastern United States. Dry deposition was an important mechanism of atmospheric input to the foliar canopy, occurring primarily by vapor uptake for sulfur, nitrogen, and free acidity and by particle deposition for calcium and potassium. The canopy retained 50 to 70 percent of the deposited free acidity and nitrogen, but released calcium and potassium. Atmospheric deposition supplied 40 and 100 percent of the nitrogen and sulfur requirements, respectively, for the annual woody increment. This contribution was underestimated significantly by standard bulk deposition collectors.

Atmospheric deposition of metals to forest vegetation.

Atmospheric deposition during the growing season contributes one-third or more of the estimated total flux of lead, zinc, and cadium from the forest canopy to soils beneath an oak stand in the Tennessee Valley but less than 10 percent of the flux of manganese. The ratio of the wet to dry deposition flux to the vegetation during this period ranges from 0.1 for manganese to 0.8 for lead to approximately 3 to 4 for cadmium and zinc. Interactions between metal particles deposited on dry leaf surfaces and subsequent acid precipitation can result in metal concentrations on leaves that are considerably higher than those in rain alone.

Cycling of organic and inorganic sulphur in a chestnut oak forest.

Sulfur (S) cycling in a chestnut oak forest on Walker Branch Watershed, Tennessee, was dominated by geochemical processes involving sulfate. Even though available SO 42- was present far in excess of forest nutritional requirements, the ecosystem as a whole accumulated ∼60% of incoming SO4-S. Most (90%) of this accumulation occurred by SO 42- adsorption in sesquioxide-rich subsurface soils, with a relatively minor amount accumulating and cycling as SO 42- within vegetative components. Organic sulfates are thought to constitute a large proportion of total S in surface soils, also, and to provide a pool of readily mineralized available S within the ecosystem.

Mass balance of trace elements in Walker branch watershed: relation to coal-fired steam plants.

A mass balance study of trace element flows at the TVA Allen Steam Plant at Memphis showed that most of the released Hg, some Se, and probably most Cl and Br are discharged to the atmosphere as gases. The elements As, Cd, Cu, Ga, Mo, Pb, Sb, Se, and Zn were concentrated in fly ash compared to slag and were more concentrated in the ash discharged through the stack than in that collected by the precipitator, while Al, Ba, Ca, Ce, Co, Eu, Fe, Hf, K, La, Mg, Mn, Rb, Sm, Sr, Ta, Th, and Ti showed little preferential partitioning between the slag and the collected or discharged fly ash. The elements Cr, Cs, Na, Ni, U, and V exhibited behavior intermediate between the latter two groups. This information about stack emissions of trace elements from the Allen Plant was used to estimate the likely range of air concentrations and input (dry and wet deposition) to the Walker Branch Watershed. The watershed, which is on the ERDA reservation at Oak Ridge, is within 20 km of three coal-fired steam plants, two in the TVA system and one belonging to ERDA. The estimated input values are compared to measurements of Cd, Cr, Cu, Hg, Mn, Ni, Pb, and Zn in wet precipitation falling on the watershed during 1973 and 1974. Dry deposition of these elements could not be measured directly but estimates indicated that this could be of the same order of magnitude as the rainwater input. A six-month mass balance indicated that the watershed efficiently retains Pb (97-98% of the atmospheric input,) Cu (82-84%), while Cr (69%), Mn (57%), Zn (73%), and Hg (69%) are less well retained.