Response of nitrous oxide emissions to individual rain events and future changes in precipitation.

Changing precipitation has the potential to alter nitrous oxide (N2 O) emissions from agricultural regions. In this study, we applied the Coupled Model Intercomparison Project Phase 5 end-of-century RCP 8.5 (business as usual) precipitation projections for the U.S. Upper Midwest and examined the effects of mean precipitation changes, characterized by increased early-season rainfall and decreased mid- to late-season rainfall, on N2 O emissions from a conventionally managed corn (Zea mays L.) cropping system grown in an indoor mesocosm facility over four growing seasons. We also assessed the response of N2 O emissions to over 1,000 individual rain events. Nitrous oxide emissions were most strongly correlated with water-filled pore space (WFPS) and soil nitrogen (N) status. After rain events, the change in N2 O emissions, relative to pre-rain emissions, was more likely to be positive when soil NO3 - was >40 mg N kg-1 soil and soil NH4 + was >10 mg N kg-1 soil and was more likely to be negative when soil NO3 - was >40 mg N kg-1 soil and soil NH4 + was <10 mg N kg-1 soil. Similarly, hourly N2 O emissions remained <5 nmol m- 2 s-1 when combined NH4 + + NO3 - was <20 mg N kg-1 soil or NH4 + and NO3 - were <5 and 20 mg N kg-1 soil, respectively. Rain event magnitude did not substantially affect the change in N2 O flux. Finally, growing-season N2 O emissions, soil moisture, and inorganic N content were not affected by the future precipitation pattern. Near-optimal soil WFPS combined with soil N concentrations above the identified thresholds favor higher N2 O emissions.

Application of copper(II)-based chemicals induces CH3Br and CH3Cl emissions from soil and seawater.

Methyl bromide (CH3Br) and methyl chloride (CH3Cl) are major carriers of atmospheric bromine and chlorine, respectively, which can catalyze stratospheric ozone depletion. However, in our current understanding, there are missing sources associated with these two species. Here we investigate the effect of copper(II) on CH3Br and CH3Cl production from soil, seawater and model organic compounds: catechol (benzene-1,2-diol) and guaiacol (2-methoxyphenol). We show that copper sulfate (CuSO4) enhances CH3Br and CH3Cl production from soil and seawater, and it may be further amplified in conjunction with hydrogen peroxide (H2O2) or solar radiation. This represents an abiotic production pathway of CH3Br and CH3Cl perturbed by anthropogenic application of copper(II)-based chemicals. Hence, we suggest that the widespread application of copper(II) pesticides in agriculture and the discharge of anthropogenic copper(II) to the oceans may account for part of the missing sources of CH3Br and CH3Cl, and thereby contribute to stratospheric halogen load.

Bidirectional Ecosystem-Atmosphere Fluxes of Volatile Organic Compounds Across the Mass Spectrum: How Many Matter?

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.