SUMMARY: Isoprene is the dominant non-methane organic compound emitted to the atmosphere 1 – 3 . It drives ozone and aerosol production, modulates atmospheric oxidation, and interacts with the global nitrogen cycle 4 – 8 . Isoprene emissions are highly uncertain 1 , 9 , as is the non-linear chemistry coupling isoprene and the hydroxyl radical, OH—its primary sink 10 – 13 . Here we present the first global isoprene measurements from space, using the Cross-track Infrared Sounder (CrIS). These isoprene measurements, together with observations of its oxidation product formaldehyde, provide new constraints on isoprene emissions and atmospheric oxidation. We find that isoprene:formaldehyde relationships measured from space are broadly consistent with current understanding of isoprene-OH chemistry, with no indication of missing OH recycling at low-NO x . We analyze these datasets over four global isoprene hotspots in relation to model predictions, and present a first demonstration of isoprene emission quantification based directly on satellite measurements of isoprene itself. A major discrepancy emerges over Amazonia, where current underestimates of natural NO x emissions bias modeled OH and hence isoprene. Over southern Africa, we find that a prominent isoprene hotspot is missing from bottom-up predictions. A multi-year analysis sheds light on interannual isoprene variability, and suggests the role of El Niño.

Terrestrial ecosystems are simultaneously the largest source and a major sink of volatile organic compounds (VOCs) to the global atmosphere, and these two-way fluxes are an important source of uncertainty in current models. Here, we apply high-resolution mass spectrometry (proton transfer reaction-quadrupole interface time-of-flight; PTR-QiTOF) to measure ecosystem–atmosphere VOC fluxes across the entire detected mass range (m/z 0–335) over a mixed temperate forest and use the results to test how well a state-of-science chemical transport model (GEOS-Chem CTM) is able to represent the observed reactive carbon exchange. We show that ambient humidity fluctuations can give rise to spurious VOC fluxes with PTR-based techniques and present a method to screen for such effects. After doing so, 377 of the 636 detected ions exhibited detectable gross fluxes during the study, implying a large number of species with active ecosystem–atmosphere exchange. We introduce the reactivity flux as a measure of how Earth–atmosphere fluxes influence ambient OH reactivity and show that the upward total VOC (∑VOC) carbon and reactivity fluxes are carried by a far smaller number of species than the downward fluxes. The model underpredicts the ∑VOC carbon and reactivity fluxes by 40–60% on average. However, the observed net fluxes are dominated (90% on a carbon basis, 95% on a reactivity basis) by known VOCs explicitly included in the CTM. As a result, the largest CTM uncertainties in simulating VOC carbon and reactivity exchange for this environment are associated with known rather than unrepresented species. This conclusion pertains to the set of species detectable by PTR-TOF techniques, which likely represents the majority in terms of carbon mass and OH reactivity, but not necessarily in terms of aerosol formation potential. In the case of oxygenated VOCs, the model severely underpredicts the gross fluxes and the net exchange. Here, unrepresented VOCs play a larger role, accounting for ∼30% of the carbon flux and ∼50% of the reactivity flux. The resulting CTM biases, however, are still smaller than those that arise from uncertainties for known and represented compounds.

Tropical-and subtropical-storm surges combined with sea level rise cause saltwater intrusions into low-lying coastal ecosystems along the southeastern coast of the United States, gradually converting freshwater forested wetland into saltmarsh. The transition zone between freshwater and saltwater ecosystems becomes a degraded forested wetland, where the combination of high levels of soil organic matter and elevated concentrations of halide ions creates a dynamic biogeochemical environment that may be a potential hotspot for halocarbon formation such as chloroform, methyl chloride, and methyl bromide. This study conducted field measurements at a transition zone in coastal South Carolina to quantify halocarbon exchange rates and laboratory soil incubations to determine the contributions of biotic versus abiotic processes. The degraded forested wetland showed significant chloroform emission rates (146 ± 129 nmol m −2 d −1 ). The degraded forested wetland remained a net sink for methyl chloride and a negligible source/sink for methyl bromide, unlike the saltmarsh which was a significant source for both. The laboratory incubations strongly suggest that methyl halide consumption in soils at the field site was biotic and that production of methyl halides and chloroform was largely abiotic and temperature-dependent, although additional experiments are required to rule out possible biotic production involving heat-resistant microbes. The results suggest that sea level rise and more frequent storm surges derived from global climate change, in the long term, may increase emissions of chloroform from coastal degraded forested wetlands and of methyl halides if salt marshes expand, with potential impacts for stratospheric ozone depletion.

Nitrogen oxide (NOx) pollution is emerging as a primary environmental concern across Europe. While some large European metropolitan areas are already in breach of EU safety limits for NO2, this phenomenon does not seem to be only restricted to large industrialized areas anymore. Many smaller scale populated agglomerations including their surrounding rural areas are seeing frequent NO2 concentration violations. The question of a quantitative understanding of different NOx emission sources is therefore of immanent relevance for climate and air chemistry models as well as air pollution management and health. Here we report simultaneous eddy covariance flux measurements of NOx, CO2, CO and non methane volatile organic compound tracers in a city that might be considered representative for Central Europe and the greater Alpine region. Our data show that NOx fluxes are largely at variance with modelled emission projections, suggesting an appreciable underestimation of the traffic related atmospheric NOx input in Europe, comparable to the weekend-weekday effect, which locally changes ozone production rates by 40%.