Surface-air exchanges of H2S and SO2 in an urban wetland in eastern China.

Wetlands are widely recognized as hot spots for the emission or deposition of biogenic sulfur gases, including hydrogen sulfur (H2S) and sulfur dioxide (SO2), which significantly affect air quality and climate change. With the expansion of urban wetlands, it is critical to know the roles that urban wetlands played in atmospheric H2S and SO2 budget. In this study, the surface-air exchange fluxes of H2S and SO2 were measured by the Dynamic Flux Chamber (DFC) method in a typical urban wetland in eastern China from Sep 2022 to July 2023. It was found that the urban wetland did not have the expected high H2S emission, might be caused by the relatively high pH value and low sulfate concentration in the soil. Although H2S showed emission in the daytime of spring and summer, an overall H2S flux of -0.04 kg S ha-1 yr-1 was observed throughout the year. Meanwhile, the urban wetland presented a net sink of SO2, with a deposition flux of 0.14 kg S ha-1 yr-1. The negative peaks of SO2 flux corresponded to the suddenly elevated SO2 concentration in the ambient air especially in spring and winter. Through linear fitting of SO2 flux and concentration, the concept of SO2 "compensation point" was proposed. The compensation point is the concentration level at which the observed SO2 flux equals zero. The "compensation point" changed with the season and was related to temperature and humidity. The "compensation point" in summer and autumn were larger, being 2.37 ppb and 1.40 ppb, respectively, while they were 1.07 ppb and 0.86 ppb in spring and winter respectively. Our results suggest that the urban wetland expansion may have little risk of increasing air H2S but could act as a significant sink of SO2 with high SO2 concentration in the urban region.

Fluxes of H2S and SO2 above a subtropical forest under natural and disturbed conditions induced by temporal land-use change.

Hydrogen sulfide (H2S) is one of predominant biogenic sulfur gases, influencing aerosol formation and climate change. There is considerable uncertainty of the global budget of H2S due to limited field data, especially in subtropical forests. In addition, an interaction between soil-emitted H2S and ambient sulfur dioxide (SO2) might exist within forest ecosystems. In this study, the aerodynamic gradient method was applied to consecutively measure H2S and SO2 fluxes above a subtropical forest canopy in Southwest China under natural and disturbed conditions induced by temporal land-use changes. The average H2S concentration and flux under natural conditions were 0.79 ± 0.07 ppbv and 0.04 ± 0.01 g S m-2 yr-1, respectively. The emission was larger than that in most croplands and freshwater wetlands. Vegetation emissions might account for about 26% of the total forest H2S emissions at this site. The deposition of SO2 was likely balanced by H2S oxidization under the forest canopy, with the mean concentration and net flux as 1.23 ± 0.11 ppbv and -0.03 ± 0.10 g S m-2 yr-1, respectively. Under disturbed conditions with soils excavation and scattering on the forest floor, simultaneously high emissions of H2S and SO2 were observed above the canopy, reaching 5.78 ± 0.16 and 1.60 ± 0.87 g S m-2 yr-1, respectively. This suggested that land-use change in subtropical forests might lead to release of legacy S in subsoils to the atmosphere in the form of H2S and SO2. Regarding the widely documented large S accumulation and expanding deforestation across subtropical forests, potentially high emissions of H2S and SO2 from subtropical forests should be carefully considered in regional air quality control and forest management.

Temporal variations of soil NO and NO2 fluxes in two typical subtropical forests receiving contrasting rates of N deposition.

Soils have been widely acknowledged as important natural sources of nitric oxide (NO) and meanwhile sinks of nitric dioxide (NO2). High nitrogen deposition across South China could potentially result in large NO emissions from subtropical forests soils there. In this study, the dynamic chamber method was applied to monitor NO and NO2 fluxes at two subtropical forest sites in South China, namely "Qianyanzhou" (QYZ) and "Tieshanping" (TSP). Chronically higher N deposition occurred at TSP than that at QYZ. Besides soil water filled pore spaces (WFPS) and temperature, ambient NO concentration could also possibly be important in regulating temporal NO emissions, especially in the winter. For both sites, the optimum soil temperature was above 25 °C, while the optimum WFPS for NO release at QYZ was higher (65-70%) than that at TSP (<23%). Moreover, heavy rainfall could trigger NO emission pulses from moist soils at QYZ, while rainfall-induced NO pulses were only observed after a long drying period at TSP. Distinctly different contents of mineral nitrogen and soil moisture conditions between the two sites might induce the divergent preference of WFPS and responses to rainfall. The cumulative soil emission of NO reached 0.41 ± 0.01 and 0.76 ± 0.01 kg N ha-1 yr-1 at QYZ and TSP, contributing to 2.5% and 1.4% of the annual throughfall N input, respectively. At both sites, NO2 were mainly deposited to soils, accounting for 2% and 21% of soil-emitted NO at QYZ and TSP, respectively. The observed annual NO emissions at these two sites were larger than the median values observed for tropical and temperate forests and unfertilized croplands. Higher N deposition could induce larger NO emission potential, while soil temperature and pH might also be important in regulating regional soil NO emissions as N-loss from subtropical forests.

Fluxes of nitrogen oxides above a subtropical forest canopy in China.

Dry deposition of Nitrogen (N) in forests is commonly estimated from inferential method and/or throughfall measurements, with inevitable uncertainty. In this study, we applied an aerodynamic gradient method to directly measure the nitrogen oxides (NOx) flux above the canopy of a subtropical forest in southeastern China for two consecutive years. The flux and transfer velocity generally reached the maximum absolute values in the midday, with the largest diurnal maximum of absolute flux values observed in the winter of 2015 and that of transfer velocity in the autumn of 2015. The annual average transfer velocity was -0.79 and -0.38 cm s-1 in 2015 and 2016, respectively. Although the net downward NOx fluxes predominated for both years, upward flux (net emission) of NOx was observed during spring months, which reflected the possible bi-directional exchange balanced by soil-atmosphere and foliage-atmosphere exchanges. The NOx concentration seemed to be the most important factor controlling the NOx exchange above canopy, and could mainly explain the seasonal variation of N deposition. The linear regression between the NOx flux and concertation was explored, and it was observed that the deposition of NOx was offset by possible underlayer emission of NOx when the ambient NOx concentration below1.7 ppbv and 1.9 ppbv at night and in the day, respectively. The average dry deposition of NOx for the two years was 6.28 ± 0.06 kg N ha-1 a-1, >40% of which might be uptake by the canopy, estimated by comparing the wet/throughfall deposition measurement of nitrate with the observation of NOx flux. This indicated the importance of stomatal uptake of NOx in nitrogen budget in subtropical forests.

Threshold and multiple indicators for nitrogen saturation in subtropical forests.

The influence of nitrogen (N) deposition on forest ecosystems largely depend on the N status. Developing threshold and practical indicators for N saturation in subtropical forests, with extremely high N deposition, would both enhance forest management and the assessments of global N balance and carbon (C) sequestration. Here, we quantified the N mass balance and assessed current N status at a number of subtropical forest sites in South China, using both N content, C/N ratio, and 15N natural abundance (δ15N) as potential indicators of N saturation. Among the studied sites, N deposition ranged from 13.8 to 113 kg N ha-1 yr-1 in throughfall, and was dominated by ammonium (NH4+). The threshold for N leaching in subtropical forest was first found to be 26-36 kg N ha-1 yr-1, which was 160% higher than in temperate forest (based on prescribed minimum). This indicates that critical parameter inputs in global models of the impact of N deposition are in need of revision, based on specific ecosystem characteristics. We found a critical C/N ratio of 20 for the O/A horizon as indicator of N saturation. Foliar N content and δ15N were positively correlated with N deposition and were well suited to indicate regional N status. The δ15N enrichment factor (Ɛfoli/So2, δ15Nfoliage - δ15NSoil2) was between -10‰ and -1‰, and had similar trend to those obtained from other regions with increasing N deposition. These suggest that the enrichment factor could be used to investigate the influence of N deposition in forest ecosystems, regardless of spatial heterogeneity in δ15N of N input, soil N availability and geomorphology.