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This study investigates the rain-initiated mixing and variability in the mixing ratio of selected trace gases in the atmosphere over the central Amazon rain forest. It builds on comprehensive data from the Amazon Tall Tower Observatory (ATTO), spanning from 2013 to 2020 and comprising the greenhouse gases (GHGs) carbon dioxide (CO2) and methane (CH4); the reactive trace gases carbon monoxide (CO), ozone (O3), nitric oxide (NO), and nitrogen dioxide (NO2); and selected volatile organic compounds (VOCs). Based on more than 1000 analyzed rainfall events, the study resolves the trace gas mixing ratio patterns before, during, and after the rain events, along with vertical mixing ratio gradients across the forest canopy. The assessment of the rainfall events was conducted independently for daytime and nighttime periods, which allows us to elucidate the influence of solar radiation. The mixing ratios of CO2, CO, and CH4 clearly declined during rainfall, which can be attributed to the downdraft-related entrainment of pristine air from higher altitudes into the boundary layer, a reduction of the photosynthetic activity under increased cloud cover, and changes in the surface fluxes. Notably, CO showed a faster reduction than CO2, and the vertical gradient of CO2 and CO is steeper than for CH4. Conversely, the O3 mixing ratio increased across all measurement heights in the course of the rain-related downdrafts. Following the O3 enhancement by up to a factor of 2, NO, NO2, and isoprene mixing ratios decreased. The temporal and vertical variability of the trace gases is intricately linked to the diverse sink and source processes, surface fluxes, and free-troposphere transport. Within the canopy, several interactions unfold among soil, atmosphere, and plants, shaping the overall dynamics. Also, the mixing ratio of biogenic VOCs (BVOCs) clearly varied with rainfall, driven by factors such as light, temperature, physical transport, and soil processes. Our results disentangle the patterns in the trace gas mixing ratio in the course of sudden and vigorous atmospheric mixing during rainfall events. By selectively uncovering processes that are not clearly detectable under undisturbed conditions, our results contribute to a better understanding of the trace gas life cycle and its interplay with meteorology, cloud dynamics, and rainfall in the Amazon.

Soil carbon monoxide (CO) fluxes represent a net balance between biological soil CO uptake and abiotic soil and (senescent) plant CO production. Studies largely from temperate and boreal forests indicate that soils serve as a net sink for CO, but uncertainty remains about the role of tropical rainforest soils to date. Here we report the first direct measurements of soil CO fluxes in a tropical rainforest and compare them with estimates of net ecosystem CO fluxes derived from accumulation of CO at night under stable atmospheric conditions. Furthermore, we used laboratory experiments to demonstrate the importance of temperature on net soil CO fluxes. Net soil surface CO fluxes ranged from −0.19 to 3.36 nmol m−2 s−1, averaging ∼1 nmol CO m−2 s−1. Fluxes varied with season and topographic location, with the highest fluxes measured in the dry season in a seasonally inundated valley. Ecosystem CO fluxes estimated from nocturnal canopy air profiles, which showed CO mixing ratios that consistently decreased with height, ranged between 0.3 and 2.0 nmol CO m−2 s−1. A canopy layer budget method, using the nocturnal increase in CO, estimated similar flux magnitudes (1.1 to 2.3 nmol CO m−2 s−1). In the wet season, a greater valley ecosystem CO production was observed in comparison to measured soil valley CO fluxes, suggesting a contribution of the valley stream to overall CO emissions. Laboratory incubations demonstrated a clear increase in CO production with temperature that was also observed in field fluxes, though high correlations between soil temperature and moisture limit our ability to interpret the field relationship. At a common temperature (25 °C), expected plateau and valley senescent-leaf CO production was small (0.012 and 0.002 nmol CO m−2 s−1) in comparison to expected soil material CO emissions (∼ 0.9 nmol CO m−2 s−1). Based on our field and laboratory observations, we expect that tropical rainforest ecosystems are a net source of CO, with thermal-degradation-induced soil emissions likely being the main contributor to ecosystem CO emissions. Extrapolating our first observation-based tropical rainforest soil emission estimate of ∼ 1 nmol m−2 s−1, global tropical rainforest soil emissions of ∼ 16.0 Tg CO yr−1 are estimated. Nevertheless, total ecosystem CO emissions might be higher, since valley streams and inundated areas might represent local CO emission hot spots. To further improve tropical forest ecosystem CO emission estimates, more in situ tropical forest soil and ecosystem CO flux measurements are essential.

The magnitude of termite methane (CH4) emissions is still an uncertain part of the global CH4 budget and current emission estimates are based on limited field studies. We present in situ CH4 emission measurements of termite mounds and termite mound subsamples performed in the Amazon rainforest. Emissions from five termite mounds of the species Neocapritermes brasiliensis were measured by use of a large flux chamber connected to a portable gas analyser measuring CH4 and CO2. In addition, the emissions of mound subsamples were measured, after which the termites were counted so that a termite CH4 and CO2 emission factor could be determined. Mound emissions were found to range between 17.0 and 34.8 nmol mound−1 s−1 for CH4 and between 1.1 and 13.0 µmol mound−1 s−1 for CO2. A termite emission factor of 0.35 µmol CH4 gtermite-1 h−1 was found, which is almost twice as high as the only other reported value for the Amazon. By combining mound emission measurements with the termite emission factor, colony sizes could be estimated, which were found to range between 55–125 thousand individuals. Estimates were similar to literature values, and we therefore propose that this method can be used as a quick non-intrusive method to estimate termite colony size in the field. The role of termites in the ecosystem's CH4 budget was evaluated by use of two approaches. Termite mound emission values were combined with local mound density numbers, leading to an estimate of 0.15–0.71 nmol CH4 m−2 s−1, on average, emitted by termite mounds. In addition, the termite CH4 emission factor from this study was combined with termite biomass numbers, resulting in an estimate of termite-emitted CH4 of ∼1.0 nmol m−2 s−1. Considering the relatively low net CH4 emissions previously measured at this ecosystem, we expect that termites play an important role in the CH4 budget of this terra firme ecosystem.

Methane (CH4) atmospheric mixing ratio measurements are analyzed for the period between June 2013 and November 2018 at the Amazon Tall Tower Observatory (ATTO). We describe the seasonal and diurnal patterns of nighttime events in which CH4 mixing ratios at the uppermost (79 m a.g.l.) inlet are significantly higher than the lowermost inlet (4 m a.g.l.) by 8 ppb or more. These nighttime events were found to be associated with a wind direction originating from the southeast and wind speeds between 2 and 5 m s−1. We found that these events happen under specific nighttime atmospheric conditions when compared to other nights, exhibiting less variable sensible heat flux, low net radiation and a strong thermal stratification above the canopy. Our analysis indicates that even at wind speeds of 5.8 m s−1 the turbulence intensity, given by the standard deviation of the vertical velocity, is suppressed to values lower than 0.3 m s−1. Given these findings, we suggest that these nighttime CH4 enhancements are advected from their source location by horizontal nonturbulent motions. The most likely source location is the Uatumã River, possibly influenced by dead stands of flooded forest trees that may be enhancing CH4 emissions from those areas. Finally, biomass burning and the Amazon River were discarded as potential CH4 sources.

The rewetting of drained peatlands is currently a common practice for re-establishing near-natural hydrological conditions and for reducing peatland greenhouse gas (GHG) emissions, especially of carbon dioxide (CO2) and nitrous oxide (N2O), which are enhanced under peatland drainage and extraction. In the originally bare and drained peatland Himmelmoor (Quickborn, Germany), the rewetting process started stepwise in 2004 by blocking drainage ditches with peat as well as by creating polders surrounded by peat dams. In this research we examined differences in CO2, methane (CH4) and N2O emissions between a flooded (FL) area, a bare peat dam (PD) area and an abandoned (but still drained) extraction (E) area during a period in 2012 and during a period of two years in 2014–2016. The results showed that all study areas were GHG sources, although large differences were identified between the different sites. Winter CO2 emissions from all sites (FL, PD, E) were within the range previously reported for rewetted peatlands, but summer CO2 emissions from PD (1–20 µmol m-2 s-1) strongly exceeded the reported average range for similar surfaces. Very low and irregular CH4 fluxes were detected at both PD and FL, ranging from -6 to 24 nmol m-2 s-1 at PD and from 13 to 49 nmol m-2 s-1 at FL. In comparison to other peatlands, the observed N2O emissions were high, especially at the PD sites with maximum daily means of 23 nmol m-2 s-1 in the summer of 2012. In general, the flooded excavation sites (FL) showed lower GHG emissions than the not-rewetted excavation area (E). Also, despite the relatively small coverage of the peat dams (PD), these areas showed a larger total GHG emission than the E and FL sites. This negative effect of peat dams during the first years after flooding could be mitigated by stimulating their colonisation by moss or heath vegetation, which reduces the soil N pool and thus can be expected to reduce N2O fluxes from the peat dams.

Carbon monoxide (CO) plays an important role in controlling the oxidizing capacity of the atmosphere by reacting with OH radicals that affect atmospheric methane (CH4) dynamics. We develop a process-based biogeochemistry model to quantify the CO exchange between soils and the atmosphere with a 5 min internal time step at the global scale. The model is parameterized using the CO flux data from the field and laboratory experiments for 11 representative ecosystem types. The model is then extrapolated to global terrestrial ecosystems using monthly climate forcing data. Global soil gross consumption, gross production, and net flux of the atmospheric CO are estimated to be from −197 to −180, 34 to 36, and −163 to −145 Tg CO yr−1 (1 Tg = 1012 g), respectively, when the model is driven with satellite-based atmospheric CO concentration data during 2000–2013. Tropical evergreen forest, savanna and deciduous forest areas are the largest sinks at 123 Tg CO yr−1. The soil CO gross consumption is sensitive to air temperature and atmospheric CO concentration, while the gross production is sensitive to soil organic carbon (SOC) stock and air temperature. By assuming that the spatially distributed atmospheric CO concentrations ( ∼ 128 ppbv) are not changing over time, the global mean CO net deposition velocity is estimated to be 0.16–0.19 mm s−1 during the 20th century. Under the future climate scenarios, the CO deposition velocity will increase at a rate of 0.0002–0.0013 mm s−1 yr−1 during 2014–2100, reaching 0.20–0.30 mm s−1 by the end of the 21st century, primarily due to the increasing temperature. Areas near the Equator, the eastern US, Europe and eastern Asia will be the largest sinks due to optimum soil moisture and high temperature. The annual global soil net flux of atmospheric CO is primarily controlled by air temperature, soil temperature, SOC and atmospheric CO concentrations, while its monthly variation is mainly determined by air temperature, precipitation, soil temperature and soil moisture.

Recent studies have suggested the potential importance of abiotic degradation in arid ecosystems. In this study, the role of photo- and thermal degradation in ecosystem CO2 and CO exchange is assessed. A field experiment was performed in Italy using an FTIR-spectrometer (Fourier Transform Infrared) coupled to a flux gradient system and to flux chambers. In a laboratory experiment, field samples were exposed to different temperatures and radiation intensities. No photodegradation-induced CO2 and CO fluxes of in literature suggested magnitudes were found in the field nor in the laboratory study. In the laboratory, we measured CO2 and CO fluxes that were derived from thermal degradation. In the field experiment, CO uptake and emission have been measured and are proposed to be a result of biological uptake and abiotic thermal degradation-production. We suggest that previous studies, addressing direct photodegradation, have overestimated the role of photodegradation and observed fluxes might be due to thermal degradation, which is an indirect effect of radiation. The potential importance of abiotic decomposition in the form of thermal degradation, especially for arid regions, should be considered in future studies.