World soils are subjected to a number of anthropogenic global change factors. Although many previous studies contributed to understand how single global change factors affect soil properties, there have been few studies aimed at understanding how two naturally co-occurring global change drivers, nitrogen (N) deposition and increased precipitation, affect critical soil properties. In addition, most atmospheric N deposition and precipitation increase studies have been simulated by directly adding N solution or water to the forest floor, and thus largely neglect some key canopy processes in natural conditions. These previous studies, therefore, may not realistically simulate natural atmospheric N deposition and precipitation increase in forest ecosystems. In a field experiment, we used novel canopy applications to investigate the effects of N deposition, increased precipitation, and their combination on soil chemical properties and the microbial community in a temperate deciduous forest. We found that both soil chemistry and microorganisms were sensitive to these global change factors, especially when they were simultaneously applied. These effects were evident within 2 years of treatment initiation. Canopy N deposition immediately accelerated soil acidification, base cation depletion, and toxic metal accumulation. Although increased precipitation only promoted base cation leaching, this exacerbated the effects of N deposition. Increased precipitation decreased soil fungal biomass, possible due to wetting/re-drying stress or to the depletion of Na. When N deposition and increased precipitation occurred together, soil gram-negative bacteria decreased significantly, and the community structure of soil bacteria was altered. The reduction of gram-negative bacterial biomass was closely linked to the accumulation of the toxic metals Al and Fe. These results suggested that short-term responses in soil cations following N deposition and increased precipitation could change microbial biomass and community structure.

We evaluated spatial patterns of mercury (Hg) deposition through analysis of foliage and forest floor samples from 45 sites across Adirondack Park, NY. Species-specific differences in foliar Hg were evident with the lowest concentrations found in first-year conifer needles and highest concentrations found in black cherry (Prunus serotina). For foliage and forest floor samples, latitude and longitude were negatively correlated with Hg concentrations, likely because of proximity to emission sources, while elevation was positively correlated with Hg concentrations. Elemental analysis showed moderately strong, positive correlations between Hg and nitrogen concentrations. The spatial pattern of Hg deposition across the Adirondacks is similar to patterns of other contaminants that originate largely from combustion sources such as nitrogen and sulfur. The results of this study suggest foliage can be used to assess spatial patterns of Hg deposition in small regions or areas of varied topography where current Hg deposition models are too coarse to predict deposition accurately.

Mercury (Hg) emissions from the soils taken from two different sites (deciduous and coniferous forests) in the Adirondacks were measured in outdoor and laboratory experiments. Some of the soil samples were irradiated to eliminate biological activity. The result from the outdoor measurements with different soils suggests the Hg emission from the soils is partly limited by fallen leaves covering the soils which helps maintain relatively high soil moisture and limits the amount of heat and solar radiation reaching the soil surface. In laboratory experiments exposure to UV-A (365 nm) had no significant effect on the Hg emissions while the Hg emissions increased dramatically during exposure to UV-B (302 nm) light suggesting UV-B directly reduced soil-associated Hg. Overall these results indicate that for these soils biotic processes have a relatively constant and smaller influence on the Hg emission from the soil than the more variable abiotic processes. Hg emission measurements from soils indicate that abiotic processes were more important than biotic processes in reducing Hg and controlling emissions.

We evaluated foliar and forest floor chemistry across a gradient of N deposition in the Northeast at 11 red spruce (Picea rubens Sarg.) sites in 1987/1988 and foliar and forest floor chemistry and basal area growth at six paired spruce and deciduous sites in 1999. The six red spruce plots were a subset of the original 1987/1988 spruce sites. In 1999, we observed a significant correlation between mean growing season temperature and red spruce basal area growth. Red spruce and deciduous foliar %N correlated significantly with N deposition. Although N deposition has not changed significantly from 1987/1988 to 1999, net nitrification potential decreased significantly at Whiteface. This decrease in net potential nitrification is not consistent with the N saturation hypothesis and suggests that non-N deposition controls, such as climatic factors and immobilization of down dead wood, might have limited N cycling. Data from the 1999 remeasurement of the red spruce forests suggest that N deposition, to some extent, is continuing to influence red spruce across the northeastern US as illustrated by a significant correlation between N deposition and red spruce foliar %N. Our data also suggest that the decrease in forest floor %N and net nitrification potential across sites from 1987 to 1999 may be due to factors other than N deposition, such as climatic factors and N immobilization in fine woody material (<5 cm diameter).

Recent studies have demonstrated that natural abundance 15N can be a useful tool for assessing nitrogen saturation, because as nitrification and nitrate loss increase, δ15N of foliage and soil also increases. We measured foliar δ15N at 11 high-elevation spruce-fir stands along an N deposition gradient in 1987-1988 and at seven paired northern hardwood and spruce-fir stands in 1999. In 1999, foliar δ15N increased from -5.2 to -0.7[per thousand] with increasing N deposition from Maine to NY. Foliar δ15N decreased between 1987-1988 and 1999, while foliar %N increased and foliar C:N decreased at most sites. Foliar δ15N was strongly correlated with N deposition, and was also positively correlated with net nitrification potential and negatively correlated with soil C:N ratio. Although the increase in foliar %N is consistent with a progression towards N saturation, other results of this study suggest that, in 1999, these stands were further from N saturation than in 1987-1988. Foliar δ15N increased with increasing N deposition from Maine to NY, but decreased between 1987-1988 and 1999

Metal ions interact with biological materials and their decomposition products by ligation (coordination complex-formation with certain moieties containing O, N, S, etc.). The extent of this interaction depends on the identities of both ligand and metal ion and can be described by some equation derived from perturbation theory. Uptake of metal ions - including highly toxic ones - from soils is controlled by a competition between root exudate components and soil organic matter (SOM) for the ions. SOM consists of a variety of potential ligands which evolve during humification towards more efficient binding (retention) of metals such as Cu, Ni, Cr but also of toxicants like U, Cd. The actual way of interaction can be inferred from stoichiometry of the involved compounds and the C/N ratio in the soil, providing predictions as to which metals will be most efficiently shuttled into green plants or fungi, respectively. The latter, selective process is crucial for closing nutrient cycles and sensitively depends on C/N ratio and the extent of “forcing” by onfalling leaf or needle litter. Therefore, analytical data on the soil can be used to predict possible risks of exposition to toxic metals also for human consumption of plant parts. Degradation, amounts and evolution of N-free vs. nitrogenous SOM control transfer of essential and toxic metals from soil into plants, to be estimated from coordination (bio-)chemistry.

Taking advantage of the different histories of Hg deposition in Davos Seehornwald in E-Switzerland and Changbai Mountain in NE-China, the influence of atmospheric deposition on Hg soil dynamics in forest soil profiles was investigated. Today, Hg fluxes in bulk precipitation were similar, and soil profiles were generally sinks for atmospherically deposited Hg at both sites. Noticeably, a net release of 2.07 μg Hg m⁻² yr⁻¹ from the Bs horizon (Podzol) in Seehornwald was highlighted, where Hg concentration (up to 73.9 μg kg⁻¹) and soil storage (100 mg m⁻³) peaked. Sequential extraction revealed that organic matter and crystalline Fe and Al hydr (oxide)-associated Hg decreased in the E horizon but increased in the Bs horizon as compared to the Ah horizon, demonstrating the coupling of Hg dynamics with the podzolisation process and accumulation of legacy Hg deposited last century in the Bs horizon. The mor humus in Seehornwald allowed Hg enrichment in the forest floor (182–269 μg kg⁻¹). In Changbai Mountain, the Hg concentrations in the Cambisol surface layer with mull humus were markedly lower (<148 μg kg⁻¹), but with much higher Hg soil storage (54–120 mg m⁻³) than in the Seehornwald forest floor (18–27 mg m⁻³). Thus, the vertical distribution pattern of Hg was influenced by humus form and soil type. The concentrations of Hg in soil porewater in Seehornwald (3.4–101 ng L⁻¹) and in runoff of Changbai Mountain (1.26–5.62 ng L⁻¹) were all low. Moreover, the pools of readily extractable Hg in the soils at both sites were all <2% of total Hg. Therefore, the potential of Hg release from the forest soil profile to the adjacent aquatic environment is currently low at both sites.

Forest ecosystem has long been suggested as a vital component in the global mercury (Hg) biogeochemical cycling. However, there remains large uncertainties in understanding total Hg (THg) and methylmercury (MeHg) variations and their controlling factors during the whole hydrological processes in forest ecosystems. Here, we quantified Hg mass flow along hydrological processes of wet deposition, throughfall, stemflow, litter leachate, soil leachate, surface runoff, and stream, and litterfall Hg deposition, and air-forest floor elemental Hg (Hg⁰) exchange flux to set up a Hg mass balance in a subtropical forest of China. Results showed that THg concentration in stream was lower than that in wet deposition, while an opposite characteristic for MeHg concentration, and both THg and MeHg fluxes of stream were lower than those of wet deposition. Variations of THg and MeHg in throughfall and litter leachate had strong direct and indirect effects on controlling variations of THg and MeHg in surface runoff, soil leachate and stream, respectively. Especially, the net Hg methylation was suggested in the forest canopy and forest floor layers, and significant particulate bound Hg (PBM) filtration was observed in soil layers. The Hg mass balance showed that the litterfall Hg deposition was the main Hg input for forest floor Hg, and the elemental Hg vapor (Hg⁰) re-emission from forest floor was the dominant Hg output. Overall, we estimated the net THg input flux of 13.8 μg m⁻² yr⁻¹ and net MeHg input flux of 0.6 μg m⁻² yr⁻¹ within the forest ecosystem. Our results highlighted the important roles of forest canopy and forest floor to shape Hg in output flow, and the forest floor is a distinct sink of MeHg.

Systemic neonicotinoid insecticides such as imidacloprid are increasingly applied against insect pest infestations on forest trees. However, leaves falling from treated trees may reach nearby surface waters and potentially represent a neonicotinoid exposure source for aquatic invertebrates. Given imidacloprid's susceptibility towards photolysis and high water solubility, it was hypothesized that the leaves' toxicity might be modulated by UV-irradiation during decay on the forest floor, or by leaching and re-mobilization of the insecticide from leaves within the aquatic ecosystem. To test these hypotheses, the amphipod shredder Gammarus fossarum was fed (over 7 d; n = 30) with imidacloprid-contaminated black alder (Alnus glutinosa) leaves that had either been pre-treated (i.e., leached) in water for up to 7 d or UV-irradiated for 1 d (at intensities relevant during autumn in Central Europe) followed by a leaching duration of 1 d. Gammarids' feeding rate, serving as sublethal response variable, was reduced by up to 80% when consuming non-pretreated imidacloprid-contaminated leaves compared to imidacloprid-free leaves. Moreover, both leaching of imidacloprid from leaves (for 7 d) as well as UV-irradiation reduced the leaves' imidacloprid load (by 46 and 90%) thereby mitigating the effects on gammarids' feeding rate to levels comparable to the respective imidacloprid-free controls. Therefore, natural processes, such as UV-irradiation and re-mobilization of foliar insecticide residues in water, might be considered when evaluating the risks systemic insecticide applications in forests might pose for aquatic organisms in nearby streams.